description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
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BACKGROUND OF THE INVENTION
[0001] Light Emitting Diode (LED) technology offers advantages in efficiency and life over traditional incandescent or halogen lights. Typical LED lamp design approaches use a planar array of LEDs with one or more collimating optics to achieve the desired photometric distribution. Many LED lamps used as alternatives to Parabolic Aluminized Reflector (PAR) lamps cannot match the photometric performance for a given frontal area compared to the conventional lamps they would replace, particularly for applications that require very high peak intensities such as a PAR64 aircraft landing light or an entertainment stage light.
SUMMARY OF THE INVENTION
[0002] Instead of a simple forward facing planar array that might typically be used for a PAR lamp replacement, the present invention uses depth of the package to increase the total peak intensity. One or more layers of LEDs shine into an array of elliptical reflectors. Each elliptical reflector has an LED at one focal point and shares the second focal point with a larger parabolic reflector that collimates the light. The resulting system has a hole in the center of the parabolic reflector where additional layers of LEDs, with or without collimation optics, are placed to further increase the intensity of the system. This configuration allows the distribution to be adjusted for the application (wavelength, peak intensity and beam spread) by changing the number or type of LED, the focal lengths of the ellipses, the parabola and the collimation optics.
[0003] In one aspect of the invention, the LEDs are separated to distribute the thermal load over a larger surface area for higher power applications.
[0004] In still another aspect of the invention, dual-mode capability within the same footprint is provided by replacing some of the visible LEDs with Infrared (IR) LEDs and modifying the drive electronics to control those IR LEDs separately.
[0005] In yet another aspect of the invention, the system provides variable color output by appropriate placement of various colored LEDs (e.g., red, green, blue, amber and/or white) and separate drive electronics for each group of colored LEDs to allow for color mixing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Preferred and alternative embodiments of the present invention are described in detail below with reference to the following drawings:
[0007] FIG. 1 illustrates a perspective view of a light assembly formed in accordance with an embodiment of the present invention;
[0008] FIG. 2 illustrates an exploded view of the light assembly shown in FIG. 1 ;
[0009] FIG. 3 is a cross-sectional view of the light assembly shown in FIG. 1 ;
[0010] FIGS. 4-6 are perspective views of components of the light assembly shown in FIG. 1 ; and
[0011] FIG. 7 is a wire diagram illustrating light production and reflection of the light assembly shown in FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
[0012] FIG. 1 illustrates a perspective view of a light assembly 30 formed in accordance with an embodiment of the present invention. The light assembly 30 is capable of producing a greater intensity of light than that produced by conventional light emitting diode (LED) light assemblies of comparable anterior dimension. The light assembly 30 includes a housing 34 which is capped at one end by a lens 58 . Inside the housing 34 are a large parabolic reflector 36 and a plurality of layers 40 , 42 , 44 of LEDs with elliptical reflectors and/or parabolic reflectors. Light produced by the LEDs either passes directly through ends of the large parabolic reflector 36 or the large parabolic reflector 36 collimates light received from the elliptical reflectors.
[0013] FIG. 2 illustrates an exploded view of the light assembly 30 . In this embodiment, the light assembly 30 includes three LED layers 40 , 42 , 44 . The first and second LED layers 40 , 42 are ring-shaped and the third layer LED layer 44 is sized to fit within an opening of the second LED layer 42 . The first LED layer 40 is held in place within the housing 34 via a first housing section 50 and a second housing section 52 . The second and third LED layers 42 , 44 are held in place between the second housing section 52 and a third housing section 54 . The various housing sections 50 , 52 , 54 are fastened together by suitable means (fasteners, adhesive and/or comparable materials) depending on the thermal, sealing or vibration requirements of the application. In one embodiment, the sections 50 , 52 , 54 are attached one to the next as the assembly is built with fasteners that provide significant clamp force to enhance thermal performance.
[0014] The lens 58 holds the parabolic reflector 36 within the first housing section 50 . The lens 58 may attach to the first housing section 50 in a number of ways, for example threads on the first section 50 and the opposing surface of the lens 38 or an epoxy or other comparable fastener.
[0015] FIG. 3 illustrates a cross-sectional view of the light assembly 30 shown in FIGS. 1 and 2 . The parabolic reflector 36 includes first and second open ends. The first open end has a larger diameter than the second open end. The first open end includes an annular flange 60 that surrounds the opening. The flange 60 makes contact with an annular ledge 61 formed at the first open end of the first housing section 50 . The lens 58 , when attached to the first housing section 50 , holds the parabolic reflector 36 in place by placing pressure on the flange 60 . The parabolic reflector 36 rests within a cavity formed within the first housing section 50 . The first housing section 50 also includes first and second open ends wherein the first open end has a slightly larger diameter than the first open end of the parabolic reflector 36 and the second open end has a slightly larger diameter than the second open end of the parabolic reflector 36 .
[0016] A second ledge 62 formed on a bottom surface of the second open end of the housing section 50 supports an LED board 74 that is part of the first LED layer 40 . The LED board 74 may be attached to the housing section 50 by fasteners or other comparable means. If metal fasteners (e.g. screws) are used then the housing section 50 acts as a heat sink to a metal layer within the LED board 74 . The first LED layer 40 includes first and second open ends. The first open end includes an annular flange 64 . The annular flange 64 and a portion of the LED board 74 securely sits between a first surface 66 of the second housing layer 52 and the second ledge 62 . This allows the first LED layer 40 to sit securely within a cavity formed within the second housing section 52 .
[0017] A similar type of slot is formed between a second surface 68 of the second housing section 52 and a first surface 70 of the third housing section 54 . The slot formed between the second and third housing sections 52 and 54 receives an outer circumferential flange 72 of the second LED layer 42 and a portion of an LED board 76 of the third housing section 54 . This allows the second LED layer 42 to sit securely within a portion of a cavity formed within the third housing section 54 . The third housing section 54 also includes a second cavity portion that receives the third LED layer 44 . A base of the third LED layer 44 is fastened to an interior base of the third housing section 54 using fastener(s), adhesives or comparable components.
[0018] FIGS. 4-1 and 4 - 2 illustrate perspective views of the first LED layer 40 . The first LED layer 40 includes the ring-shaped LED board 74 and a plurality of elliptical reflectors 94 mounted to a first side of the LED board 74 . A plurality of LEDs 92 are also mounted to the first side of the LED board 74 . The elliptical reflectors 94 are mounted such that a single elliptical reflector 94 is positioned around a corresponding single LED 92 . The elliptical reflectors 94 are positioned such that light emanating from the LEDs 92 are reflected off of the elliptical reflectors 94 through the opening in the LED board 74 . The light reflecting off the elliptical reflectors 94 reflects off of a predefined section of the parabolic reflector 36 . This will be shown in more detail below with regard to FIG. 7 . The elliptical reflectors 94 are attached to the LED board 74 (i.e., printed wiring board) by any number of techniques if the elliptical reflectors 94 are not sandwiched between the mated housing sections with a flexible adhesive. There is a keying feature included in the reflector to ensure proper registration with the LEDs for suitable focus.
[0019] FIGS. 5-1 and 5 - 2 illustrate perspective views of the second LED layer 42 . The second LED layer 42 includes a ring-shaped LED board 76 and a plurality of elliptical reflectors 104 mounted to a first side of the LED board 76 . A plurality of LEDs 102 are also mounted to the first side of the LED board 76 . The elliptical reflectors 104 are mounted such that a single elliptical reflector 104 is positioned around a corresponding single LED 102 . The elliptical reflectors 104 are positioned such that light emanating from the LEDs 102 is reflected off of the elliptical reflectors 104 through the open end in the LED board 76 . The light reflecting off the elliptical reflector 104 is then collimated by the parabolic reflector 36 . This will be shown in more detail below with regard to FIG. 7 .
[0020] FIGS. 6-1 and 6 - 2 illustrate perspective views of the third LED layer 44 . The third LED layer 44 includes an LED board 110 , a plurality of LEDs 112 mounted to the LED board 110 and a multi-reflector unit 116 having a plurality of parabolic reflectors 114 . Each of the parabolic reflectors 114 in the reflector unit 116 includes first and second open ends. The first open end has a larger diameter than the second open end. When the reflector unit 116 is mounted to the LED board 110 , via fastener(s), epoxy or comparable means, the second open end is mounted adjacent to the LED board 110 . The reflector unit 116 is mounted such that each of the LEDs 112 mounted on the LED board 110 are exposed via the second open end of a corresponding reflector 114 . The third layer LED 44 includes parabolic reflectors instead of elliptical reflectors because the light emitted by the LEDs 112 is reflected directly through both open ends of the parabolic reflector 36 and do not reflect off of the parabolic reflector 36 . This is shown in more detail in FIG. 7 .
[0021] In one embodiment, the reflectors 94 , 104 , 114 are single units formed by a plastic injection molding process. The reflectors 94 , 104 , 114 are then coated with a reflective coating, such as, but not limited to, aluminum or silver. Other reflector devices may be used. For example, one or more of the parabolic reflectors 36 , 114 may be an uncoated, reflective white plastic, such as that produced by Bayer. Also, the boards 74 , 76 , 110 may be printed circuit boards that include traces that electrically connect the LEDs 92 , 102 , 112 to wires or traces located on or embedded in the housing sections 50 , 52 , 54 . In one embodiment, a wiring harness (not shown) connects to mounted headers (not shown) soldered onto the circuit boards at the time the LEDs are installed. A wiring routing channel and pocket (not shown) are included in each of the housing sections 50 , 52 , 54 to accommodate the wiring harness and mounted headers.
[0022] As shown in FIG. 7 , the light produced by the LEDS 112 reflects off the parabolic reflectors 114 of the third LED layer 44 and directly passes through the parabolic reflector 36 . The elliptical reflectors 94 , 104 of the first and second LED layers 40 , 42 share a focal point with the parabolic reflector 36 . Thus, the light produced by the first LED layer 40 reflects off a lower/aft section of the parabolic reflector 36 than does the light produced by the second LED layer 42 .
[0023] In this example, the light assembly 30 produces light from approximately 37 LEDs with a high percentage of light produced by each LED being reflected either off of the parabolic reflector 36 or passing directly through the parabolic reflector 36 via its own parabolic reflector associated with the LED. In this example, the angular spread of light is approximately 11° to 12° with a production of over 700,000 candelas. Intensity and angular spread of light is adjustable by changing any number of variables: focal length of reflectors, number and type of LEDs, etc.
[0024] In another embodiment, different LED configurations may be used within the light assembly. The following are non-limiting examples of different LED configurations.
[0025] White and Infrared lights are included to produce both visual and non-visual light. In one embodiment, the LEDs used are all of a single color (red, amber, green, blue, etc.).
[0026] In one embodiment, the system includes different colored LEDs (red, green, blue, amber and/or white) distributed throughout the LED boards 74 , 76 , 110 with independent drive electronics (not shown) for producing variable color output. The drive electronics independently control the intensity of each color group, resulting in color mixing.
[0027] In one embodiment, the system is capable of providing variable temperature white. Similar to the aforementioned color mixing method, this embodiment is achieved through the appropriate location on the circuit boards ( 74 , 76 , 110 ) of groups of white LEDs selected from two specific “color” bins (a result of the LED manufacturing process) associated with “blackbody color temperatures” found close to, or along, the Planckian locus within a color space such as the CIE 1931 chromaticity diagram. Separate drive electronics control the intensity of each “color” bin of LEDs independently, thus providing the ability to vary the color temperature of the output light along a line between the two white endpoints defined by the selected LED “color” bins.
[0028] The addition of other white bin groups to the preceding method creates a color temperature polygon (triangle, rectangle, etc.), the boundaries of which are defined by the color points of the selected groups of colored LEDs. Varying the intensities of the component groups changes the output color temperature within the boundaries of the polygon.
[0029] Monochromatic LED groups, such as red, replace white in the previous embodiment for creating another color space polygon (triangle, rectangle, etc.), the boundaries of which will be defined by the color points of the selected groups of colored LEDs. Varying the intensities of the component groups changes the output color and color temperature within the boundaries of the polygon.
[0030] While the preferred embodiment of the invention has been illustrated and described, as noted above, many changes can be made without departing from the spirit and scope of the invention. For example, the device could include only two layers of LEDs with associated reflectors and those two layers could have only elliptical reflectors or one layer has elliptical reflectors and one layer includes parabolic reflectors. In another example, the device could include three or more LED and associated reflector “ring” layers. Further, one of the layers may include both elliptical and parabolic reflectors. Also, in one example the parabolic reflector 36 is replaced with a non-parabolic type reflector. Accordingly, the scope of the invention is not limited by the disclosure of the preferred embodiment. Instead, the invention should be determined entirely by reference to the claims that follow. | An apparatus and method for producing an improved light emitting diode (LED) spotlight. One or more layers of LEDs shine light into an array of elliptical reflectors. Each elliptical reflector has an LED at one focal point and shares the second focal point with a larger parabolic reflector that collimates the light. A hole in the center of the parabolic reflector receives additional LEDs, with or without collimation optics. | 5 |
BACKGROUND OF THE INVENTION
This invention relates to means for supplying matched source and sink currents to a load.
In many applications, it is necessary to drive a load by supplying a current to the load and drawing a like current from the load. A prior art circuit for performing this function is shown in FIG. 1A. The circuit includes a current sourcing circuit 12 connected between VDD and one end of a load L1 and a current sinking circuit 14 connected between the other end of load L1 and ground.
The current sourcing circuit 12 includes a current sensing resistor R1 connected in series with the conduction paths of insulated-gate field effect transistors (IGFETs) PA and NCA between VDD and an output terminal 13, to supply a load current into terminal 13 (also denoted as BPLUS). A fixed bias voltage (PBIAS) is applied to the gate of PA whereby PA functions as a constant current source. A control signal (TRI-STATE CONTROL) is applied to the gate of NCA to selectively turn it on or off. The current sinking circuit 14 includes a current sensing resistor R2 connected in series with the conduction paths of IGFETs NB and NCB between an output terminal 15 (also denoted as BMINUS) and ground. A fixed bias voltage (NBIAS) is applied to the gate of NB whereby NB functions as a constant current generator (sink), and the TRI-STATE CONTROL signal is applied to the gate of NCB to selectively turn it on or off.
The bias voltages applied to the gates of PA and NB ensure that the same amplitude current flows into the load at the BPLUS terminal and out of the load at the BMINUS terminal. A tri-state control signal applied to the gates of transistors NCA and NCB turns them both on or off at the same time. The circuit of FIG. 1 can supply (i.e. source) a current into the load which matches the current drawn (i.e. sunk) from the load.
However, the circuit of FIG. 1 does not have a high degree of power supply isolation. Power supply isolation as defined and used herein requires that there be no conduction (other than leakage) via the current sourcing and sinking circuits to VDD and/or ground when the current sourcing and sinking circuits are turned-off (i.e. disabled). Particularly, there should be no conduction via the turned-off current sourcing and sinking circuits when positive or negative signals are present at the output terminals 13 and 15 (due, for example, to inductive kicks from the load).
The lack of power supply isolation is best explained by reference to FIG. 1B which is a drawing of FIG. 1A showing parasitic and junction diodes associated with the switching and current setting transistors. For purpose of illustration, FIG. 1B shows the source-to-substrate and drain-to-substrate diodes associated with each one of the IGFETs. Consider the case where NB and NCB and PA and NCA are turned-off and a negative potential is produced at output terminals 13 and/or 15. When a signal at output terminals 13 and/or 15 goes negative with respect to ground by more than the forward voltage drop of a diode (i.e., 0.5 to 0.7 volt), diode D1NCB, which represents the subtstrate-to-drain junction of NCB, becomes forward biased and provides a conduction path between ground and the output terminals 13 and 15. Similarly, diode D2NCA which represents the substrate-to-source junction of NCA, becomes forward biased and provides a conduction path between ground and output terminals 13 and 15.
Note that if NCA were replaced by an IGFET of P conductivity type, a parasitic diode would be included as part of the IGFET which would still provide a conduction path for positive going signals at the output terminals. Therefore, the problem with a lack of power supply isolation would still exist.
In theory, diodes could be connected in series between the current source and current sink circuits and load terminals 13 and 15, respectively. However, these series diodes would cause a voltage drop which is generally very undesirable because it limits the output voltage range. In addition, the series diodes could lead to the formation of parasitic bipolar transistors which would introduce undesirable conduction paths.
It is desirable to have a current sourcing or sinking circuit with a high degree of power supply isolation. That is, a current sourcing or sinking circuit in which there is no conduction between the output terminals of the circuit and the power supply lines when the current sourcing and sinking circuits are turned off.
SUMMARY OF THE INVENTION
The problem present in the prior art circuit is overcome in circuitry embodying the invention by including, in each one of the current sink and current source circuits, a bipolar switching transistor connected in series with an IGFET biased to conduct a constant current. Furthermore, circuits embodying the invention include means for compensating for the base current of the bipolar transistors in the source and sink circuits to produce output currents which are matched.
BRIEF DESCRIPTION OF THE DRAWING
In the accompanying drawing, like reference characters denote like components; and
FIG. 1A is a schematic diagram of a prior art load driver;
FIG. 1B is a schematic diagram of the prior art circuit of FIG. 1 showing parasitic diodes;
FIG. 2 is a schematic diagram of a current driver circuit employing bipolar and insulated-gate transistors embodying the invention; and
FIGS. 3a, 3b and 4 are cross section diagrams of bipolar transistors which may be used to practice the invention.
DETAILED DESCRIPTION OF THE INVENTION
The circuit of FIG. 2 includes a load L1 connected between terminal 13 (also denoted as BPLUS) and terminal 15 (also denoted as BMINUS). The load L1 may be, for example, a motor exhibiting some resistance and inductance or any one of a number of load devices through which a current must pass for proper operation. A current sourcing circuit 22 supplies a load current (IL) into load L1 at terminal 13 and a current sinking circuit 24, connected to terminal 15, draws the load current, IL, out of terminal 15.
The current sourcing circuit 22 includes IGFETS P5 and P6 having their conduction paths connected in parallel between power terminal 19, to which is applied a voltage of VDD volts, which is positive with respect to ground, and the emitter of a bipolar transistor, QP1. The collector of QP1 is connected to output terminal 13 and its base is connected to the emitter of an NPN bipolar transistor QN1 and to the drain of an IGFET N3, whose source is grounded. The conduction path of an IGFET P4 is connected between terminal 19 and a node 21 to which is connected the drains of IGFETs N1 and N2 whose source electrodes are grounded. The gates of N2 and N3 are connected to the drain of N2 at node 21 whereby the current in the conduction path of N2 is mirrored in the conduction path of N3. The gate of N1 and the base of QN1 are connected in common to tri-state control terminal 27 to which is applied a control signal CA. When CA is high, N1 and QN1 are turned on and the current sourcing circuit 22 is disabled. When control signal CA is low N1 and QN1 are turned off and the current sourcing circuit 22 is enabled.
The same bias voltage (PBIAS) is applied to the gates of P4, P5 and P6. Assume that P4 and P5 are made the same size and that P6 is ratioed to be "N" times the size of P4 or P5. By making P4 and P5 the same size and by making them using the same process, the current through P5 will be the same as the current through P4. Where P6 is "N" times the size of P4 the current (IP6) through P6 will be "N" times the current (IP4) through P4.
The current sinking circuit 24 includes IGFETS N5 and N6 having their conduction paths connected in parallel between ground terminal and the emitter of a bipolar transistor, QN2. The collector of QN2 is connected to output terminal 15 and its base is connected at node 33 to the emitter of a PNP bipolar transistor QP2 and to the drain of an IGFET P3, whose source is connected to terminal 19. The conduction path of an IGFET N4 is connected between ground terminal and a node 31 to which is connected the drains of IGFETs P1 and P2 whose source electrodes are connected to terminal 19. The gates of P2 and P3 are connected to the drain of P2 at node 31 whereby the current in the conduction path of P2 is mirrored in the conduction path of P3. The gate of P1 and the base of QP2 are connected in common to tri-state control terminal 29 to which is applied a control signal CB, which is the complement of CA. When CB is high, P1 and QP2 are turned off and the curent sinking circuit 24 is enabled. When control signal CB is low P1 and QP2 are turned on and the current sinking circuit 24 is disabled.
The same bias voltage (NBIAS) is applied to the gates of N4, N5 and N6. Assume that N4 and N5 are made the same size and that N6 is ratioed to be "N" times the size of N4 or N5. By making N4 and N5 the same size and by making them using the same process, current (IN5) through N5 will be the same as the current (IN4) through N4. Where N6 is "N" times the size of N4 the current (IN6) through N6 will be "N" times the current through N4.
PBIAS and NBIAS are generated by means of network 40 which includes P-type IGFET P41 and N-type IGFET N41 and a current limiting resistor R41. P41 is connected at its source to terminal 19 and its gate and drain are connected in common to PBIAS TERMINAL 43. Resistor R41 is connected between terminal 43 and NBIAS terminal 45. The gate and drain of N41 are connected to terminal 45 and the source of N41 is connected to ground. It is evident that the same amplitude current flows through P41 and N41 and establishes the bias voltage levels at the PBIAS and NBIAS terminals. PBIAS is applied to the gates of P4, P5, and P6 whose sources are connected to terminal 19, as is the source of P41. Hence, the current through P41 is mirrored in P4, P5, and P6. In a similar manner, NBIAS is applied to the gates of N4, N5, and N6 whose sources are grounded as is the source of N41. Hence, the current through N41 is mirrored in N4, N5, and N6.
The operation of the circuit of FIG. 2 will now be discussed. Note first that PBIAS applied to the gate of P4, P5 and P6 causes currents IP4, IP5, and IP6 to flow through P4, P5 and P6, respectively. Although P41 need not be the same size as P4 or P5, assume for ease of description that P4 and P5 are the same size as P41 and that P6 is N times P41. For these assumptions IP4 and IP5 will equal IP41 and IP6 will be N times IP41. In a similar manner, NBIAS applied to the gates of N4, N5, and N6 causes currents IN4, IN5 and IN6 to flow through N4, N5, and N6, respectively. Although N41 need not be the same size as N4 and N5, assume for ease of description that N4 and N5 are the same size as N41 and that N6 is N times the size of N41. For these assumptions IN4 is equal to IN5 and IN6 is "N" times IN41.
For the condition when CA is low and CB is high, QP1 and QN2 are turned on. A load current IL is supplied to terminal 13 (BPLUS) via current sourcing circuit 22 and a like current is drawn from terminal 15 (BMINUS) via current sinking circuit 24. When CA is low, transistors QN1 and N1 are turned off. When N1 is turned off the current IP4 through P4 flows through the conduction path of N2. The current IN2 through the source-drain path of N2 is mirrored in N3 causing a current IN3 to flow in the drain-to-source path of N3. For the assumptions of N1 equal to N2 and N3, IN3 is equal to IN2 which is equal to IP4. When QN1 is off the current IN3 is drawn out of the base of QP1.
Concurrently, the current into the emitter of QP1 is supplied via P5 and P6. Where P5 and P4 are identical in size and structure, and made by the same process, and where the same voltage is applied between their source and gate electrodes, the current IP5 flowing through the source-drain path of P5 is equal to the current, IP4, flowing through the source-drain path of P4. Concurrently, where P6 is "N" times the size of P5, P4 or P41, the current, IP6, through the source-drain path of P6 is equal to N times IP4 since P6 is N times the size of P4 and P4 and to have the same gate-to-source potential. Thus the emitter current of QP1 is IP5 plus IP6. Since the current drawn out of the base of QP1 is IP4 which is equal to IP5, the net current flowing out of the collector of QP1 into the load is IP6 also denoted herein as IL.
Concurrently, when CB is high, P1 and QP2 are turned-off. When P1 is turned off, the current IN4 flowing through the source-drain path of N4 flows through the source-drain path of P2 whereby the current through the source-to-drain path of P2 is equal to IN4. The current, IP2, is mirrored in the source-to-drain path of P3. Where P3 is the same size as P2 and they are biased in an identical manner, the current IP3 very nearly equals IP2. Since QP2 is turned-off, the current IP3, flowing out of the drain of P3, flows into the base of QN2 causing QN2 to conduct a collector current IL out of termninal 15. The emitter current of QN2 flows via N5 and N6 to ground. The current IN5 through N5 is equal to the current IN4 through N4 where N4 and N5 are the same size and are made by the same process and have the same gate-to-source potential. Since IN4 is also equal to IP3, The current IP3 into the base of QN2 is equal to the current IN5 drawn out of the emitter of QN2. Thus with CB high and P1 turned-off, the current IN4 flows through P2, whereby IP2 is equal to IN4. The current through P2 is mirrored into P3. Where P2 and P3 are the same size and made by the same process and have like gate to source potentials, IP3 flowing into the base of QN2 is equal to the current IN5 drawn out of the emitter of QN2. The remaining current drawn out of the emitter of QN2 is equal to the current (IN6) flowing through the source-to-drain path of N6. The current flowing through IN6 is essentially equal to the current IP6 flowing through P6 and the load connected between the collectors of QP1 and QN2.
Thus, any current imbalance due to the base currents of QP1 and QN2 has been eliminated.
Bipolar transistors QP1 and QN2 may be formed as shown in cross section in FIGS. 3A an 3B. QP1 and QN2 of FIGS. 3A and 3B are lateral bipolar transistors which are designed to provide power supply isolation by preventing unwanted conduction paths as outlined below.
For ease of description, FIGS. 3A and 3B show some of the parasitic diodes superimposed on the cross sectional diagram. Referring to FIG. 3A, there is shown a diode D1 formed between the emitter of QP1 and the N-Well which defines the base region of QP1 with the P+ emitter region defining the anode of D1 and the N-Well region defining the cathode of D1. A diode D2 is formed between the PBODY region and the N-Well of QP1, with the P body collector region defining the anode and the N-Well defining the cathode of D2. A diode D6 is formed between the N+ buried layer and the P-substrate in which QP1 is formed, with the N+ buried layer defining the cathode of D6 and the P-sustrate defining the anode of D6. The N-Well to N+ buried layer are at the same potential with the N-Well defining the base region of QP1 and the N+ buried layer (SINKER) defining the base contact of QP1.
Referring to FIG. 3B, there is shown a diode D3 formed between the N body collector region and the P-Well, which defines the base region of QN2, with the N body collector region defining the cathode and the P-Well region the anode of D3. A diode D4 is formed between the N+ emitter and the P-Well, with the N+ emitter defining the cathode and the P-Well the anode of D4. A diode D4A is formed between the P-Well and the N+ buried layer (SINKER) which is also common to the emitter of QN2, with the P-Well defining the anode and the N+ buried layer the cathode of D4A. Finally, a diode D5 is formed between the N+ buried layer and the P-Substrate in which QN2 is formed with the N+ buried layer defining the cathode and the P-Substrate the anode of D5.
The parasitic diodes associated with QP1 and QN2 as shown in FIGS. 3A and 3B and the parasitic diodes associated with some of the IGFETs in the output stage of FIG. 2, have been combined with the transistors to produce a simplified composite output stage shown in FIG. 4. Referring to FIG. 4, diodes D1 and D2 represent the emitter-to-base and collector-to-base diodes, respectively, of QP1. Diodes D3 and D4 represent the collector-to-base and base-to-emitter diodes, respectively, of QN2. When the voltage V13 at the output terminal 13 goes negative with respect to ground, diode D2 is reversed biased and blocks the signal from being coupled to the internal nodes of the circuit. Whe V13 goes positive by more than the forward voltage drop (Vf) of a diode, D2 conducts the positive signal to the base of QP1, which is also common to node 23. However, the other diodes (D1, D2, DN3A and the base-to-emitter of QN1) connected to node 23 have their cathodes connected to node 23 whereby they are reverse biased and non-conducting and block the positive signal from affecting the operation of the circuit.
When the voltage (V15) at output terminal 15 goes negative by more than the forward voltage drop (Vf) of a diode, diode D3 conducts and passes the negative signal to the base of QN2 which is also common to node 33. However, the other diodes (D4, D2P4 and the emitter-to-base of QP2) connected to node 33 have their anodes connected to node 33 whereby they are reverse biased and non-conducting and block the negative signal at node 33 from affecting the circuit.
When V15 goes positive, diode D3 blocks the positive V15 signal from being coupled to the internal nodes of the circuit.
Hence it has been shown that the circuit of FIG. 4, which represents the output stage of FIG. 2 and incorporates the parasitic diodes of the transistors in the output stage, provides a high degree of power supply isolation. | A first IGFET and a first bipolar transistor are connected in series between a first power terminaland a first load terminal. A second IGFET and a second bipolar transistor are connected in series between a second load terminal and a second power terminal. the first and second IGFETs are biased to pass the same load current. The first and second bipolar transistors are selectively turned on at the same time to permit current flow via a load which may be connected between the first and second terminals. When the first and second bipolar transistors are turned-off, they prevent conduction (except for leakage) between the load terminals and the first and second power terminals, if and when the voltage at the load terminal goes positive and/or negative. The circuit also includes means for compensating for the base current of the first and second bipolar transistors. | 7 |
TECHNICAL FIELD
The present invention pertains generally to doors, and more particularly to a door stop which when installed rotates about its longitudinal axis and therefore cannot be removed by a child.
BACKGROUND OF THE INVENTION
Door stops are attached to a baseboard or other structure to limit the travel of a door when the door is opened. The door stops are typically screwed into the baseboard using an attached projecting screw. A problem exists however in that children can unscrew and remove the door stop and possible injury themselves with the projecting sharp screw. The present invention solves this problem.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to a rotating child-safe door stop which cannot be removed by a child. When the door stop is installed, the shaft of the door stop spins about the base, making it impossible to unscrew the door stop from the baseboard without a screw driver. As such, a child cannot unscrew the door stop and be injured by the projecting screw.
In accordance with a preferred embodiment of the invention, a door stop includes a base member and a stop member having a longitudinal axis. The stop member is connected to the base member so that the stop member may freely rotate with respect to the base member about its longitudinal axis.
In accordance with an aspect of the invention, the base member has a disk. The stop member has (1) a cavity shaped and dimensioned to receive the disk of the base member, (2) a lip for selectively capturing the disk, and (3) a compression mechanism for selectively placing the lip in an expanded state or a compressed state. With the lip in the expanded state the disk may be passed though the lip and received by the cavity. The compression mechanism may then be utilized to place the lip in the compressed state wherein the disk is captured by the lip and held within the cavity thereby rotatably connecting the stop member to the base member.
In accordance with another aspect of the invention, when in the expanded state the lip has a first diameter, when in the compressed state the lip has a second diameter less than the first diameter, and the disk has a third diameter, wherein the third diameter is less than the first diameter and greater than the second diameter.
In accordance with another aspect of the invention, the compression mechanism includes (1) a sleeve which forms the cavity and the lip, the sleeve having a slot, (2) first and second bosses disposed on the sleeve on opposite sides of the slot, and (3) an adjustment screw connecting the first and second bosses, wherein by turning the adjustment screw the bosses may be brought closer together or further apart thereby compressing or expanding the lip.
In accordance with another aspect of the invention, the base member includes a mounting screw for attaching the base member to a baseboard.
In accordance with another aspect of the invention, when the stop member is connected to the base member, a gap exists between the stop member and the baseboard.
Other aspects of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a door stop in accordance with the present invention installed on a baseboard;
FIG. 2 is an exploded perspective view of the door stop;
FIG. 3 is a top plan view of a stop member of the door stop;
FIG. 4 is a side elevation view of the stop member;
FIG. 5 is an end elevation view of the stop member;
FIG. 6 is an opposite end elevation view of the stop member;
FIG. 7 is a side elevation view of a base member of the door stop;
FIG. 8 is an end elevation view of the base member;
FIG. 9 is an opposite end elevation view of the base member;
FIG. 10 is a side elevation view of the base member installed on a baseboard;
FIG. 11 is a side elevation view of the stop member installed on the base member;
FIG. 12 is a cross sectional view along the line 12 — 12 of FIG. 11 ;
FIG. 13 is a partial cross sectional view showing how the base member is rotationally received by the stop member;
FIG. 14 is an exploded side elevation view of a second embodiment of the door stop;
FIG. 15 is an exploded side elevation view of a third embodiment of the door stop; and,
FIG. 16 is a side elevation view of the third embodiment installed on a baseboard.
DETAILED DESCRIPTION OF THE INVENTION
Referring initially to FIGS. 1 and 2 , there are illustrated perspective and exploded perspective views respectively of a door stop 20 in accordance with the present invention installed on a baseboard 500 or other structure. Door stop 20 includes a base member 22 and a stop member 24 having a longitudinal axis 26 . Stop member 24 is connected to base member 22 so that stop member 24 may freely rotate with respect to base member 22 in either direction about longitudinal axis 26 .
Now referring to FIGS. 3–6 , there are illustrated top plan, side elevation, end elevation, and opposite end elevation views respectively of stop member 24 . Elongated stop member 24 has a cavity 28 (also refer to FIG. 13 ) which is shaped and dimensioned to receive a disk 30 of base member 22 (refer also to FIGS. 7–8 ), wherein when so received stop member 24 may freely rotate about its longitudinal axis 26 . Stop member 24 also has a substantially circular lip 32 (also refer to FIG. 13 ) for selectively capturing disk 30 . Stop member 24 also has a compression mechanism 34 for selectively placing lip 32 in an expanded state (refer to FIG. 5 ) or a compressed state (refer to FIG. 12 ). With lip 32 in the expanded state disk 30 may be passed though lip 32 and received by cavity 28 , and compression mechanism 34 may then be utilized to place lip 32 in the compressed state wherein disk 30 is captured by lip 30 and held within cavity 28 thereby rotatably connecting stop member 24 to said base member 22 (refer to FIG. 13 ). End 25 of stop member 24 comes in contact with the opening door.
In an embodiment of the invention, compression mechanism 34 includes a sleeve 36 which forms cavity 28 and lip 32 , sleeve 36 having a slot 38 . First 40 and second 42 bosses are disposed on sleeve 36 on opposite sides of slot 38 . A recessed adjustment screw 44 connects first 40 and second 42 bosses, wherein by turning adjustment screw 44 the bosses may be brought closer together or moved further apart. That is, adjustment screw 44 may be used to alter the diameter of lip 32 by changing the width of slot 38 (refer also to FIG. 12 ). When lip 32 is in the expanded state it has a first diameter D 1 (refer to FIG. 4 ). When lip 32 is in the compressed state it has a second diameter D 2 which is less than first diameter D 1 (refer to FIG. 12 ). Disk 30 (refer to FIG. 9 ) has a third diameter D 3 which is (1) less than first diameter D 1 so that disk 30 may enter cavity 28 when lip 32 is in the expanded state, and (2) greater than second diameter D 2 so that when disk 30 resides within cavity 28 and lip 32 is placed in the compressed state disk 30 is retained within cavity 28 by lip 32 (refer to FIG. 13 ).
FIGS. 7–9 are side elevation, end elevation, and opposite end elevation views respectively of base member 22 . Base member includes disk 30 , shank 31 , and a mounting screw 33 for attaching base member 22 to a baseboard 500 (refer to FIG. 10 ).
FIG. 10 is a side elevation view of base member 22 installed on a baseboard 500 . Mounting screw 33 is used to effect the installation. In this embodiment, disk 30 and shank 31 are attached to baseboard 500 by screw 33 so that disk 30 and shank 31 will not rotate about screw 33 .
FIG. 11 is a side elevation view of stop member 24 installed on base member 22 . In this view, disk 30 (refer to FIG. 10 ) has been received by cavity 28 and lip 32 has been placed in the compressed state by compression mechanism 34 so that stop member 24 is rotatably connected to base member 22 . It is noted that a gap G exist between stop member 24 and baseboard 500 so that stop member 24 will not contact baseboard 500 and is therefore free to rotate with respect to base member 22 about longitudinal axis 26 .
FIG. 12 is a cross sectional view along the line 12 — 12 of FIG. 11 showing lip 32 placed in the compressed state by adjustment screw 44 . That is bosses 40 and 42 have been moved together by adjustment screw 44 there reducing the diameter D 2 of lip 32 .
FIG. 13 is a partial cross sectional view showing how base member 22 is rotationally received by the stop member 24 . Disk 30 is inside cavity 28 and lip 32 has been placed in the compressed state thereby holding disk 30 within cavity 28 .
FIG. 14 is an exploded side elevation view of a second embodiment of the door stop generally designated as 120 . In this embodiment a sleeve 70 connects base member 122 to stop member 124 . Sleeve 70 has cavities 151 and 152 which receive disk 130 of base member 122 and disk 150 of stop member 124 respectively in a manner similar to embodiment 20 .
FIG. 15 is and exploded side elevation view of a third embodiment of the door stop generally designated as 220 , and FIG. 16 is a side elevation view of door stop 220 installed on a baseboard 500 . This embodiment includes a base member 222 having a shank portion 221 having a first diameter D 4 . In the shown embodiment, base member 222 is a screw. Stop 220 further includes a stop member 224 . Stop member 224 includes a door stop portion 225 and a rotational portion 226 . Rotational portion 226 has a through hole 223 having a second diameter D 5 which is greater than first diameter D 4 . Rotational portion 226 is attached to baseboard 500 by base member 222 so that rotational portion 226 is rotatable about shank portion 221 of base member 222 . Door stop portion 225 may then be fixedly connected to rotational portion 226 so that stop member 224 may freely rotate with respect to base member 222 about longitudinal axis 227 . In the shown embodiment door stop portion 225 is press fit onto rotational portion 226 , however the clamping mechanism of embodiments 20 and 120 could also be utilized.
In terms of use, a method for installing a door stop, includes:
(a) providing a baseboard 500 ; (b) providing a door stop 20 including:
a base member 22 having a disk 30 ; a stop member 24 having:
a longitudinal axis 26 ; a cavity 28 shaped and dimensioned to receive disk 30 of base member 22 , wherein when so received stop member 24 may freely rotate about longitudinal axis 26 ; a lip 32 for selectively capturing disk 30 ; a compression mechanism 34 for selectively placing lip 32 in an expanded state or a compressed state;
(c) attaching base member 22 to baseboard 500 ; (d) placing lip 32 in the expanded state; (e) passing disk 30 through lip 32 and into cavity 28 ; and, (f) using compression mechanism 34 to place lip 32 in compressed state wherein disk 30 is captured by lip 32 , wherein stop member 24 is rotatably connected to base member 22 .
The method further including:
in step (b), when in the expanded state lip 32 having a first diameter D 1 ; when in the compressed state lip 32 having a second diameter D 2 less than first diameter D 1 ; and, disk 30 having a third diameter D 3 , wherein third diameter D 3 is less than first diameter D 1 and greater than second diameter D 2 .
The method further including:
in step (b), compression mechanism 34 including:
a sleeve 36 forming cavity 28 and lip 32 , sleeve 36 having a slot 38 ; first 40 and second 42 bosses disposed on sleeve 36 on opposite sides of slot 38 ; and, an adjustment screw 44 connecting first 40 and second 42 bosses, wherein by turning adjustment screw 44 the bosses may be brought closer together or further apart.
The method further including:
in step (b), base member 22 including a mounting screw 33 for attaching base member 22 to baseboard 500 in step (c).
The method further including:
after step (f), when stop member 24 is connected to base member 22 , a gap G existing between stop member 24 and baseboard 500 .
A second method for installing a door stop, includes:
(a) providing a baseboard 500 ; (b) providing a door stop 220 including:
a base member 222 having a shank portion 221 ; a stop member 224 having:
a longitudinal axis 227 ; a door stop portion 225 ; a rotational portion 226 having a through hole 223 to accept base member 222 ;
(c) attaching base member 222 to baseboard 500 so that rotational portion 226 is rotatable about shank portion 221 of base member 222 ; and, (d) connecting door stop portion 225 to rotational portion 226 so that stop member 224 freely rotates with respect to base member 222 about longitudinal axis 227 .
The preferred embodiments of the invention described herein are exemplary and numerous modifications, variations, and rearrangements can be readily envisioned to achieve an equivalent result, all of which are intended to be embraced within the scope of the appended claims. | A rotating door stop includes a base member which is mounted to a baseboard or other structure. A stop member is connected to the base member so that the stop member freely rotates about its longitudinal axis with respect to the base member. Because the stop member rotates, it cannot be grasped and unscrewed by a child. | 8 |
This is a division of application Ser. No. 052,428 filed May 21, 1987 abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of and apparatus for gripping corners of strips of cloth which may be applied to, for example, systems for spreading strips of cloth, systems for sorting linens or other textile products, and systems for spreading linens or the like before they are washed.
2. Description of the Related Art
Generally speaking, in laundry works, received goods such as sheets, towels and wrapping cloth (hereinafter referred to as "strips of cloth") are washed in a continuous washing machine or the like and then dewatered before being cast into a drier. Strips of cloth which have been subjected to the drying process are disentangled and spread. Then, the strips of cloth are ironed and folded for forwarding. In this series of processes, between the drying process and the ironing process, strips of cloth taken out of the drier are transported to a predetermined place by means of a belt conveyor, and five to six operators take out strips, one by one, from a mass of cloth which is stacked, and they spread the strips of cloth and feed them to an ironing device or an auxiliary device thereof (e.g., a spreader, a feeder, etc.).
Spreading of strips of cloth finished with the drying process involves an operation conducted in an atmosphere of high temperature and humidity, which means that the operators suffer from heavy labor in the inferior environment. In these circumstances, it has heretofore been demanded to develop an apparatus which enables automation of the operation of spreading strips of cloth. However, such automated apparatus is not present in the art, and there is only one related art which is a method of holding a strip of cloth in a fixed position, disclosed in Japanese Patent Publication No. 59-24685 (1984).
This prior art method comprises: a first step of suspending a strip of cloth by holding one portion thereof; a second step of holding the lowermost corner portion of the strip suspended in the first step and releasing the strip from the hold made in the first step; a third step of holding the lowermost end portion of the strip suspended in the second step; and a fourth step of stretching the strip while holding substantially horizontal the section of the strip between the two points held in the second and third steps. For the case of a rectangular strip of cloth, the following description is set forth in the specification of the prior art.
Namely, when, in the first step, a rectangular strip S of cloth is suspended by holding it at any one point, the straight line which intersects the held point 27 and the center of gravity 28 is vertical as shown in FIG. 42. When, in the second step, the lowermost corner 29 of the strip S in this state is held to suspend the strip S and further the strip S is released from the hold made in the first step, the distance between the upper and lower corners 29 and 30 is constant as shown in FIG. 43. Therefore, in the third step the lower corner 30 of the strip S as viewed in FIG. 43 is held. Then, in the fourth step, the upper and lower corners 29 and 30 which are points held in the second and third steps, respectively, are held so that the section between these points is substantially horizontal as shown in FIG. 44. Thus, the strip S is held in a fixed position and may be transferred to a subsequent process. To hold the strip S in a spread state, either one of the lower corners 31 and 32 shown in FIG. 44 is held in the fifth step.
FIG. 45 is a front view of an apparatus for holding a strip of cloth in a fixed position which may be employed to carry out the above-described method. For the convenience of description, the apparatus is divided into four sections A to D. The apparatus is arranged as follows. In the section A, a strip of cloth is held and one corner of the strip which is held is detected; in the section B, a corner opposing the corner held in the section A is detected; in the sections B and C, the strip which is held at opposing corners thereof is held so that the diagonal line is horizontal, and either one of the corners which define the lower ends and which overlap each other is held; and in the sections C and D, corners of the strips which are adjacent to each other are held and the strip is thus held in a fixed position. In the figures, a squeezing rod 70 is provided in the vicinity of the extremity of the rightward movement of a chuck 68 in such a manner that the rod 70 is vertically movable along a guide slot 71.
A chuck 72 is provided below the extremity of the rightward movement of the chuck 68 in such a manner that the chuck 72 is vertically movable along a guide slot 73 and also movable rightwardly upward from its top dead center. A squeezing rod 74 is provided in the vicinity of the top dead center of the obliquely vertical movement of the chuck 72 in such a manner that the rod 74 is vertically movable along a guide slot 75. A chuck 76 is provided in such a manner as to be movable in the obliquely vertical direction, the bottom dead center of the chuck 76 being set below the top dead center of the obliquely vertical movement of the chuck 72. A chuck 78 is provided in such a manner as to move vertically along a guide slot 79 below the medium point of the line which intersects the respective top dead centers of the obliquely vertical movements of the chucks 72 and 76 and further in such a manner that the chuck 78 moves in the obliquely vertical direction with its top dead center defined as the bottom dead center of its obliquely vertical movement. It should be noted that the chucks 68, 72, 76, 78 and the squeezing rods 70 and 74 are driven by means of air cylinders (not shown) so as to move along the respective guide slots.
With this apparatus, a rectangular strip of cloth is held in a fixed position according to the following procedure. Referring first to FIG. 46, a portion of a strip 80 of cloth which is to be held in a fixed position is detected and held by the chuck 68, and the chuck 68 rises along the guide slot 69 and then moves rightward, thus bringing the strip 80 into the state shown in FIG. 47. Referring to FIG. 47, the strip 80 which is suspended from the chuck 68, since its lowermost corner is not necessarily disposed directly above the chuck 72, is squeezed with the squeezing rod 70, which is circular and has a notch in part thereof, so that the lowermost corner of the strip 80 comes directly above the chuck 72 located directly below the chuck 68. Thereupon, the chuck 72 moves upward and holds one of the corners of the rectangle which defines the lowermost corner of the strip 80 as shown in FIG. 48. Thereafter, the chuck 68 releases the strip 80, and the chuck 72 moves downward and further moves rightwardly upward along the guide slot 73. At this time the squeezing rod 70 returns to the top dead center of the guide slot 71.
Referring to FIG. 49, the strip 80 which is suspended from the chuck 72 and which has reached the top dead center of the guide slot 73 and faces downward is squeezed with the squeezing rod 74. In consequence, the lowermost corner (the corner opposing the corner held by the chuck 72) of the strip 80 comes to the position of the chuck 76 (a fixed position determined in accordance with the size of the strip 80) and therefore is detected and held by the chuck 76. The chuck 76 holding the lowermost corner of the strip 80 rises along the guide slot 77 to the top dead center, so that the two opposing corners of the strip 80 are held horizontal by means of the chucks 72 and 76 as shown in FIG. 50. At this time, the squeezing rod 74 returns to the top dead center of the guide slot 75.
Referring next to FIG. 50, the strip 80 is held by the chucks 72 and 76 so that the two opposing corners are horizontal. Then, the strip 80 can be held in a fixed position in such a manner that its adjacent corner is held by providing a chuck 81 corresponding to the chuck 76 at the position of either one of the two suspended corners of the strip 80, holding said suspended corner with the chuck 81, opening the chuck 72, and holding the strip 80 with the chucks 76 and 81. It should be noted that, since in this apparatus the distance between the right upper end position of the chuck 72 and the left bottom end position of the chuck 76 is set so as to be substantially equal to the length of the diagonal line of strips which are to be handled, when the chuck 72 holds two corners of the strip 80 which are adjacent to each other in the step shown in FIG. 48, the chuck 76 cannot hold the strip 80, and therefore the strip 80 must try to be held again.
The apparatus for gripping a strip of cloth which is employed in the above-described conventional apparatus has the following problems.
Namely, since the chucks 72, 76 and 81 are located in their respective fixed positions, it is only possible to spread rectangular strips of cloth having specific dimensions, and therefore the apparatus is not practical with respect to strips of cloth having diverse dimensions.
Further, since the chuck 72 cannot move from its fixed position before the chuck 81 holds the strip 80 of cloth, it is necessary in order to spread the strip 80 at high speed to provide a plurality of apparatuses of the same arrangement, which means that the spreading ability is disadvantageously low.
SUMMARY OF THE INVENTION
In view of the above-described problems of the prior art, it is a primary object of the present invention to provide a method of gripping corners of a strip of cloth which enables a strip discharged from a drier to be automatically spread, thus relieving operators from the operation in the inferior environment and automating the operation in laundry works, together with an apparatus which may suitably be employed to carry out said method.
To this end, according to one aspect of the present invention, there is provided a method of gripping corners of a strip of cloth comprising: a first step of suspending a rectangular strip of cloth by gripping one corner thereof; a second step of gripping the lowermost corner portion of the strip suspended in the first step; a third step of raising substantially vertically either one of the gripped points of the strip gripped in the first and second steps; a fourth step of applying braking force to the other gripped point in order to apply tension to the strip; and a fifth step of holding substantially horizontally one side of the strip having a corner portion which is adjacent to the gripped points, and gripping the corner portion of the strip which is adjacent to the gripped points of the strip gripped in the first and second steps, respectively.
According to another aspect of the present invention, there is provided an apparatus for gripping corners of a strip of cloth comprising: a first chuck conveyor for suspending a rectangular strip of cloth by gripping one corner thereof; a second chuck conveyor for gripping the lowermost corner of the strip being suspended by the first chuck conveyor, the second chuck conveyor being disposed so as to be capable of holding one side of the strip substantially horizontal; drive means for raising substantially vertically either one of the gripped points gripped by the first and second chuck conveyors, respectively; chuck braking means for applying braking force to the other gripped point; and a third chuck conveyor for gripping a corner portion of the strip which is adjacent to the points gripped by the first and second chuck conveyors.
According to still another aspect of the present invention, there is provided a method of gripping corners of a strip of cloth comprising the steps of: gripping the strip of cloth at any point thereof with a chuck; transporting the chuck by means of a conveyor, and while doing so, squeezing the strip by squeezing means in a slanted state to detect a corner portion of the strip; arranging empty chucks successively fed so as to stand by in such a manner as to be able to grip the strip; and closing one of the empty chucks so as to grip the detected corner portion of the strip in response to a signal indicating the passage of the corner of the strip.
According to a further aspect of the present invention, there is provided an apparatus of gripping corner of a strip of cloth comprising: means for conveying a chuck gripping the strip of cloth at any point thereof; means for squeezing the strip with squeezing means in a slanted state to detect a corner portion of the strip; and means for successively feeding empty chucks for gripping corner of strips and opening one of the empty chucks so as to be able to grip the strip.
According to a still further aspect of the present invention, there is provided a method of gripping corners of a strip of cloth comprising the steps of: suspending a rectangular strip of cloth by gripping one corner thereof with a chuck; transporting the chuck by means of a conveyor, and while doing so, applying vibrations to the strip to thereby disentangle a short side from the strip; squeezing the strip with squeezing means to detect a lowermost corner portion thereof; and gripping the detected corner with one of the empty chucks fed successively.
According to a still further aspect of the present invention, there is provided an apparatus for gripping corners of a strip of cloth comprising: means for transporting a chuck gripping one corner of a rectangular strip of cloth by means of a conveyor; means for vibrating the strip to disentangle a short side of the strip therefrom; means for squeezing the strip with squeezing means to detect the trailing corner; and means for successively feeding empty chucks for gripping corner of strips and thus gripping the detected corner of the strip with one of the empty chucks.
The above and other objects, features and advantages of the present invention will become more apparent from the following description of the preferred embodiments thereof taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 to 26 show in combination a first embodiment of the present invention, in which:
FIGS. 1 and 2 are flow sheets each showing a cloth spreading system which is provided with an apparatus for gripping corners of a strip of cloth in accordance with the first embodiment;
FIG. 3(a) is a plan view of belt conveyors in the pick-up means shown in FIG. 1;
FIG. 3(b) is a side view of the belt conveyors shown in FIG. 3(a);
FIG. 4(a) is a front view of a chuck employed in the systems shown in FIGS. 1 and 2;
FIG. 4(b) is a sectional side view of the chuck shown in FIG. 4(a);
FIG. 5 is a perspective view of a squeezing means;
FIGS. 6 to 15 illustrate in combination a method of spreading a strip of cloth according to the present invention;
FIG. 16 is a detailed perspective view of an apparatus for gripping corners of a strip of cloth in accordance with the first embodiment of the present invention;
FIGS. 17(a) to 17(d) are side views of the gripping apparatus in different operative states;
FIGS. 18(a) and 18(b) show in combination an empty chuck feeder in accordance with the first embodiment of the present invention, FIG. 18(a) showing the chuck feeder as viewed in the direction of the arrow K in FIG. 16, and FIG. 18(b) being a sectional view taken along the line L--L in FIG. 18(a);
FIG. 19 is a side view of a chuck feed and turn means in accordance with the first embodiment of the present invention;
FIG. 20 is a plan view of an unwrinkling mechanism (air blow type) for unwrinkling the periphery of corner portions of a strip of cloth;
FIG. 21 is a plan view of an unwrinkling mechanism (brush type);
FIG. 22 shows the gripping apparatus as viewed in the direction of the arrow N in FIG. 16;
FIG. 23 is a side view showing a state of a strip of cloth in the case where the chuck has no braking means;
FIG. 24(a) is a sectional side view of one example of a chuck braking means (spring loaded type);
FIG. 24(b) is a sectional view taken along the line P--P in FIG. 24(a);
FIG. 24(c) is a sectional view taken along the line Q--Q in FIG. 24(a);
FIG. 25(a) is a plan view of one example of a chuck braking means (balance weight type);
FIG. 25(b) is a side view of the chuck braking means shown in FIG. 25(a); and
FIG. 26 is a sectional view taken along the line R--R in FIG. 25(b).
FIGS. 27 to 29 show in combination a second embodiment of the present invention, in which:
FIG. 27(a) is a plan view of an apparatus for gripping corners of a strip of cloth having a squeezing means in accordance with the second embodiment;
FIG. 27(b) is a side view of the gripping apparatus shown in FIG. 27(a);
FIG. 27(c) is a perspective view of the gripping apparatus shown in FIG. 27(a);
FIG. 28(a) is a side view of a chuck feeder in accordance with the second embodiment;
FIG. 28(b) is a plan view of the chuck feeder shown in FIG. 28(a); and
FIG. 29 is a sectional view taken along the line K'--K' in FIG. 27(b).
FIGS. 30 to 32 show in combination a third embodiment of the present invention, in which:
FIGS. 30 and 31 are flow sheets each showing the way in which a strip of cloth is spread in accordance with the third embodiment;
FIG. 32(a) is a side view of an apparatus for gripping corners of a strip of cloth in accordance with the third embodiment;
FIG. 32(b) is a perspective view of the vibrating roll; and
FIG. 32(c) is a side view showing the way in which a strip of cloth is handled in a gripping apparatus including no vibrating roll.
FIGS. 33 to 40 show in combination a means which can be employed in the embodiments of the present invention in the part denoted by A in FIG. 1 to hold a strip of cloth by suction and then grip it by means of a chuck, in which:
FIG. 33 shows the arrangement of a cloth pick-up means to which a cloth strip gripping means is applied;
FIG. 34 is a sectional view taken along the line I--I in FIG. 33;
FIG. 35 shows an arm lifting mechanism in the cloth pick-up means;
FIG. 36 is a sectional view showing the arrangement of the arm portion fixing side in the cloth strip gripping means;
FIG. 37 is a front view of the gripping mechanism side in the cloth strip gripping means;
FIG. 38 shows the gripping mechanism as viewed in the direction of the arrows II in FIG. 37;
FIGS. 39 and 40 are sectional views taken along the line III--III in FIG. 38, FIG. 39 showing a strip of cloth in a suction-hold state, and FIG. 40 showing the strip in a gripped state;
FIG. 41 is a block diagram showing a washing process in conventional laundry works;
FIGS. 42 to 44 illustrate a conventional method of gripping ends of a strip of cloth;
FIG. 45 is a front view of one example of a conventional apparatus for gripping a strip of cloth in a fixed position; and
FIGS. 46 to 50 are front views of the conventional apparatus shown in FIG. 45, illustrating the operation procedure thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described hereinunder in detail by way of one embodiment and with reference to the accompanying drawings. FIGS. 1 and 2 show in combination one example of a cloth spreading system to which the cloth strip gripping apparatus according to the present invention is applied. FIG. 1 shows an arrangement which is adapted for spreading a rectangular strip of cloth in the direction of its long sides, while FIG. 2 shows an arrangement adapted for spreading a rectangular strip of cloth in the direction of its short sides. It should be noted that FIG. 2 illustrates only portions which are different in arrangement from those shown in FIG. 1 and the portions which are common to each other are not shown in FIG. 2.
Referring to FIG. 1, the reference numeral 100 denotes a belt conveyor for conveying a rectangular strip S of cloth discharged from a drier (not shown) to this system, and the numerals 101 and 102 denote belt conveyors for receiving the strip S from the belt conveyor 100 and circulating it therethrough. These belt conveyors 100, 101 and 102 are disposed as shown in FIGS. 3(a) and 3(b), and the belt conveyors 101 and 102, together with slide plates 130 and 131, define a circulating passage. It should be noted that a belt conveyor 132 is provided for collecting any strip of cloth which fails to be spread. The reference symbol A in FIG. 1 denotes a pick-up means arranged to suck the strip S of cloth moved on the belt conveyors 101 and 102 by an air vacuum means 104 and to mechanically retain the strip S of cloth by means of a chuck 103. The pick-up means A includes a transfer means 105 arranged to raise the chuck 103 gripping the strip S of cloth and to transfer the strip S of cloth to a first chuck conveyor B.
The first chuck conveyor B receives the strip S of cloth from the pick-up means A and transports the strip S to a second chuck conveyor C in such a manner that the strip S of cloth is retained by and suspended from a chuck 106. The chuck 106 gripping the strip S of cloth is moved along a rail 110 by the operation of drive means 107 and 109. In the second chuck conveyor C, the strip S of cloth which is received from the first chuck conveyor B is squeezed by a squeezing means 111, and while doing so, the lowermost corner portion of the strip S is detected by a photoelectric sensor or the like 112. The lowermost corner portion of the strip S is gripped by means of a chuck 114, and the strip S of cloth is then transported to a third chuck conveyor D while being suspended from the chuck 114. The chuck 114 gripping the strip S is moved along a rail 150 by the operation of drive means 115 and 129.
In the third chuck conveyor D, the strip S of cloth which is received from the second chuck conveyor C is squeezed by a squeezing means 117, and while doing so, the lowermost corner portion of the strip S is detected by a photoelectric sensor 118 or the like, and the lowermost corner portion of the strip S is gripped by means of a chuck 120. The chuck 120 gripping the strip S is pulled by the chuck 114 through the strip S and, in this state, the chuck 120 moves along a rail 151 which extends through fourth and fifth chuck conveyors E and F. It should be noted that the chuck 114 in the second chuck conveyor C rises substantially vertically immediately before the fourth chuck conveyor E.
In the fourth chuck conveyor E, a corner portion (which is adjacent to the point which is gripped by the chuck 120) of the strip S of cloth which has been transported through the second and third chuck conveyors C and D is detected by means of a photoelectric sensor or the like 122, and the detected corner portion is gripped by a chuck 124. The chuck 124 gripping the strip S is conveyed to either the fifth chuck conveyor F or a sixth chuck conveyor G by the operation of a drive means 125. The fifth and sixth chuck conveyors F and G are arranged such as to receive the strip S of cloth from the fourth chuck conveyor E and convey it to a subsequent process (the ironing process) by the operation of a drive means 126 in such a manner that corner portions of the strip S which are adjacent to each other are gripped by means of chucks as illustrated. In the arrangement shown in FIG. 1, which is adapted for spreading the strip S in the direction of its long sides, the strip S is gripped by the chucks 120 and 124. In the arrangement shown in FIG. 2, which is adapted for spreading the strip S in the direction of its short sides, the strip S is gripped by the chucks 114 and 124. It should be noted that in the figures the reference numerals 108, 116 denote intermittent feed means which temporarily suspend the feed of the chucks 106, 114 in order to untwist the suspended strips S of cloth and the numerals 113, 119 and 123 denote air suction means for the squeezing means 111, 117 and a corner gripping apparatus 121.
FIGS. 4(a) and 4(b) show in combination one example of the chucks 106, 114, 120 and 124. FIG. 4(a) is a front view of a chuck, and FIG. 4(b) is a sectional side view of the chuck shown in FIG. 4(a). In the figures, each of the chucks 106, 114, 120 and 124 has a structure in which a pin 134 is constantly pushed downward by the resilient force from a spring 135 to thereby cause levers 133 to clamp a strip S of cloth. When the upper end side portions of the levers 133 are pushed by means of external forces in the direction of the arrows shown in FIG. 4(a), the levers 133 are pivoted about the pin 134 as shown by the two-dot chain line to unclamp the strip S. Each of the chucks 106, 114, 120 and 124 moves along a guide rail 139 on rollers 136 which travel within the guide rail 139. The force for driving the chuck is transmitted through a chain 138 as illustrated. It should be noted that, if the guide rail 139 faces downward, each of the chucks 106, 114, 120 and 124 can move by gravity without the aid of the chain 138. In the figures, the reference numeral 137 denotes a cover, 140 a resin rail for guiding the rollers 136 and the chain 138, and 141 a guide rail for the return passage of the chain 138.
FIG. 5 shows the structure of the squeezing means 111, 117 and 121 in which a strip S of cloth is led into a squeezing groove 142 and pulled in the direction of the arrow in the figure by means of a chuck 143 (corresponding to the chucks 106 and 114 in FIG. 1), and while doing so, the strip S is sucked by an air suction means 144 (corresponding to the air suction means 113 and 119 in FIG. 1), thus squeezing the lower half of the strip S.
The method of spreading a strip of cloth according to the present invention will next be explained with reference to FIGS. 6 to 15.
First, a mass of strips of cloth flowing on the belt conveyor 100 is led to the circulating passage which is defined by the belt conveyor 101, the slide plate 131, the belt conveyor 102 and the slide plate 130. In this case, there is a difference in level between the belt conveyor 102 and the slide plate 130, and therefore the strips S of cloth, when transferred from the former to the latter, are naturally disentangled and stacked in the circulating passage. Then, one of the strips S of cloth stacked on the belt conveyor 101 or on any place is picked up by means of the chuck 103 of the pick-up means A at any point X of the strip S as shown in FIG. 7, and the picked up strip S is then transferred to the first chuck conveyor B, where the strip S of cloth which has been picked up by the chuck 103 is gripped at the same point X by means of the chuck 106 in place of the chuck 103 as shown in FIG. 8 and then untwisted by the intermittent feed means 108 before being led into the squeezing groove of the squeezing means 111 as shown in FIG. 9. In the squeezing means 111, the lower half of the strip S of cloth is squeezed while the strip S is being pulled by the action of the traveling chuck 106, and the lowermost corner portion (the corner a) of the strip S is detected by the sensor 112. Then, the corner a of the strip S is gripped by the chuck 114 as shown in FIG. 10. The strip S is released from the hold by the chuck 106 and gripped by the chuck 114 only, and then the strip S is transported to the third chuck conveyor D while the strip S is being untwisted by the operation of the intermittent feed means 116.
In the third chuck conveyor D, as shown in FIG. 11, the lower half of the strip S of cloth is squeezed by the squeezing means 117, and while doing so, the lowermost corner portion (the corner c) is detected by the sensor 118, and the corner x of the strip S is then gripped by the chuck 120. The chuck 120 gripping the corner c of the strip S moves along the rail 151 while being pulled through the strip S by the chuck 114 which is being moved by the operation of the drive means 129. The chuck 114 rises substantially vertically immediately before the fourth chuck conveyor E, so that the short side portion of the strip S between the corners a and d approaches the open chucking portion of the chuck 124 as shown in FIG. 12.
As the chuck 114 rises vertically, the corner d of the strip S of cloth approaches the position where it is suspended directly below the chuck 114 as shown in FIG. 13. The corner d is detected by the sensor 122 and then gripped by the chuck 124 of the fourth chuck conveyor E. Then, the chuck 114 is pulled by the operation of the drive means 129 in a state wherein the strip S of cloth is gripped at the corner a by the chuck 114 of the second chuck conveyor C, at the corner c by the chuck 120 of the third chuck conveyor D and at the corner d by the chuck 124 of the fourth chuck conveyor E and, at the same time, the chucks 120 and 124 are also pulled through the strip S of cloth. In this state, if the strip S is released from the hold by the chuck 114 and only the chucks 120 and 124 are transferred to the fifth chuck conveyor F and conveyed therethrough, then the strip S of cloth can be transported to the subsequent process (the ironing process) in a state wherein the strip S is spread in the direction of its long sides as shown in FIG. 14. If, in the state shown in FIG. 13, the strips S of cloth is released from the hold by the chuck 120 and only the chucks 114 and 124 are transferred to the sixth chuck conveyor G and conveyed therethrough, then the strip S can be transported to the subsequent process (the ironing process) in a state wherein the strip S is spread in the direction of its short sides as shown in FIG. 15.
The cloth strip gripping apparatus according to the present invention will next be described in detail.
Referring to FIGS. 16 to 18, the reference numeral 151 denotes a rail along which moves the chuck 120 gripping the corner c of the strip S of cloth. It should be noted that in this case no driving force is usually applied to the chuck 120. The numeral 149 denotes a rail along which moves the chuck 124 gripping the corner d of the strip S of cloth. In this case also, no driving force is usually applied to the chuck 124. The numeral 150 denotes a rail to which the drive means 129 is attached and which guides the chuck 114 so as to rise substantially vertically. Guide bars 161 are disposed so as to sandwich the strip S of cloth in order to prevent flapping of the strip S. The numeral 162 denotes a rail along which successively return empty chucks 155 which have transported the strips S of cloth to the subsequent process (the ironing process) and released them from their hold. A rail 163 is arranged so that the chuck 120 in the rail 151 and the chuck 124 in the rail 148 join together, and a junction plate 192 is interposed at the junction of the two rails as shown in FIG. 22. A bar 165 is provided between the strip S of cloth and the rail for the purpose of preventing the cloth S coming into contacting with the rail 150 due to the fact that the chucks 114 and 120 face upward.
Brushes 170 are rotatably supported on drive shafts (not shown) below the rails 150 and 151, respectively, to unwrinkle both sides of the strip S of cloth so that the corner d is readily gripped (see FIG. 21). Air nozzles 175 are provided between the rails 150 and 151, respectively, to jet out compressed air for the purpose of achieving the effects described above (see FIGS. 20 and 21). The numeral 180 denotes a chuck feeder which is arranged such that, as shown in FIG. 18, an air cylinder 182 is provided so as to be pivotal about a pin 183 which is attached to a plate 181 rigidly secured to a rail 162, and a cam 184 is attached to the distal end of the rod of the air cylinder 182 so that the cam 184 is pivotal about a pin 185. The operation of the air cylinder 182 causes the cam 184 to pivot so as to feed chucks 155 downward one by one.
The reference numeral 186 denotes a chuck feed and turn means which is installed below the rails 149 and 162 as shown in FIG. 23. Further, accepting rails 189 are rigidly secured to the surface of a plate 188 attached to the rotating shaft of an indexing means 187 which, in turn, is secured to a fixed frame (not shown). The accepting rails 189 are provided in opposing relation to the rails 149 and 162, respectively, and disposed at such positions that chucks fed from the rails 149 and 162 can smoothly enter the corresponding rails 189. On the plate 188 are secured air cylinders 190 for opening the chucks 155 and arms 191 for transmitting the power from the air cylinders 190 to the chucks 155 (see FIG. 19). A return stopper 193 is prepared in case of ungripping of the strip S of cloth when the chuck 124 in the rail 49 rises through the rail 149 while gripping the corner d of the strip S and while being pulled by the chuck 114 through the strip S. Further, the chuck 124 moves upward against the pressing force applied to the stopper 193 from a spring (not shown), the stopper 193 being provided so as to be pivotal about a pin 194 as shown in FIG. 22.
FIG. 24 shows one example of a chuck braking means (spring loaded type). In the figure, the reference numeral 195 denotes a chuck braking means in which a chuck 120 smoothly moves through a rail 151 since the chuck 120 has the rollers 136 as illustrated in FIG. 4. It is important in order to reliably grip the corner d of the strip S of cloth to apply braking force to the chuck 120 so that the portion of the strip S between the corners a and c is prevented from sagging. The chuck braking means is provided for this purpose. Pins 196 are rigidly secured inside the rail 151, and braking members 197 are provided so as to be pivotal about the corresponding pins 196. The braking members 197 are biased by means of springs 198 so that the braking members 197 are pressed against the back of the chuck 120. The braking force can readily be adjusted by varying the depth to which a bolt 199 is screwed.
The method of gripping the corner d of the strip S of cloth will next be explained with reference to FIG. 17.
Referring first to FIG. 17(a), the chuck 114 which is gripping the corner a of the strip S of cloth is moved through the rail 150 by the operation of the drive means 129. The corner c of the strip S is gripped by the chuck 120. Since the chucks 114 and 120 grip the strip S in the state that the gripping points are situated above, the bar 165 is provided for the purpose of preventing the strip S from being stained and damaged. In this way, the strip S is conveyed as illustrated.
Since the chuck braking means 195 is provided for the chuck 120, an appropriate tension is applied to the portion of the strip S between the corners a and c, and this makes it possible to increase the probability of the corner d of the strip S being successfully gripped. If no tension is applied to the strip S, it sags as shown in FIG. 23 and it is difficult to grip the corner d of the strip S. In addition, the strip S is unwrinkled or disentangled by the action of any one the pairs of brushes 170, air nozzles 175 and guide bars 161 or a combination thereof. In the case where the rate of transport of the strip S is relatively low, these unwrinkling mechanisms may be unnecessary.
Referring next to FIG. 17(b), when the strip S of cloth reaches the illustrated position, the sensor 122 turns ON. At this time, an empty chuck 155 has already been fed to the accepting rail 189 in the chuck feed and turn means 186 and turned by rotating the indexing means 187 so as to stand by at a predetermined position (such a position that it is movable to the rail 149) as a chuck 124 for gripping the corner d of the strip S.
Referring now to FIG. 17(c), as the chuck 114 rises through the rail 150, the strip S of cloth comes out of the detectable range of the sensor 122, and the sensor 122 outputs an OFF signal. At this time, the lower side of the strip S between the corners c and d has already become substantially horizontal, and the corner d of the strip S is thus sucked into the air suction means 123. When a time set on a timer (not shown) has elapsed after the OFF signal has been output from the sensor 122, the air cylinder 190 is activated to disengage the arm 191 from the chuck 124, thereby allowing the chuck 124 to close while gripping the corner d of the strip S.
Referring now to FIG. 17(d), as the chuck 114 further rises through the rail 154, the chucks 120 and 124, which are pulled through the strip S, move through the rails 151 and 149 while gripping the corners c and d of the strip P. Thereafter, a subsequent chuck 155 is turned to the position of the chuck 124 by the operation of the chuck feed and turn means 186, and an empty chuck 155 following this chuck 155 is fed into the chuck feed and turn means 186 by the operation of the chuck feeder 180.
Referring next to FIG. 25, which shows one example of a chuck braking means (balance weight type), a chuck braking means 200 is arranged to brake the movement of the chuck 120 by means of a balance weight 211. A slider 208 is provided on one side of the rail 151 so as to be slidable along bars 209. The slider 208 is provided with a hook 206 in such a manner that the hook 206 is pivotal about a pin 210 and biased by means of the balance weight 211 as shown in FIG. 26. The hook 206, when reaching an opener 212 rigidly secured to the rail 151, is opened as shown by the two-dot chain line in FIG. 26. The balance weight 211 is suspended at the distal end of a wire 213 which is connected to the slider 208, the balance weight 211 being allowed to move vertically through a roller 207. The braking force can readily be changed by varying the weight of the balance weight 211.
One means, which can be used in the part denoted by the symbol A in FIG. 1 showing the above-described first embodiment and which is arranged to suck a strip S of cloth on the belt conveyors 101 and 102 and grip it with a chuck, will next be explained with reference to FIGS. 33 to 40.
FIG. 33 shows the arrangement of a cloth strip pick-up means to which a cloth strip gripping apparatus 401 is applied, and FIG. 34 is a sectional view taken along the line I--I in FIG. 33. The cloth strip gripping apparatus 401 is arranged such as to suck up a portion of a strip from a mass of cloth transported by a transport conveyor 402 and to grip the picked up strip. As shown in FIG. 33, the cloth strip gripping apparatus 401 is attached to the distal end of an arm portion 411 which, in turn, is attached to the body 410 of the cloth strip pick-up means 410 so that the arm portion 411 is movable both vertically and horizontally. The arrangement of the body 410 of the cloth strip pick-up means will first be explained. The body 410 of the pick-up means has two supports 413 and 414 which are rigidly secured to the surface of a base 412. Rails 415 and 416 are respectively provided on the opposing inner sides of the supports 413 and 414. A support plate 417 is provided between the rails 415 and 416 through rollers or other similar means in such a manner that the support plate 417 is vertically movable along the rails 415 and 416 serving as guide rails. The above-described arm portion 411 is attached to the support plate 417. The arm portion 411 is pivotal horizontally by the operation of a first air cylinder 418 provided between the same and the support plate 417.
On the other hand, a plate 419 is rigidly secured between the respective top portions of the supports 413 and 414. A bracket 412 which rotatably supports a pulley 420 is rigidly secured to the plate 419 by means, for example, of a bolt. One end of a second air cylinder 422 is connected to the other end of the bracket 421, and the other end (the rod-side end) of the second air cylinder 422 is connected to a bracket 425 which rotatably supports pulleys 423 and 424. A third air cylinder 426 is connected at one end (the rod-side end) thereof to the bracket 425 and at the other end to the distal end of a bracket 428 which is rigidly secured to the base 412 and which rotatably supports a pulley 427. Ropes 430 and 431 are stretched between and wrapped around the pair of pulleys 420 and 423 and the pair of pulleys 424 and 427, respectively, each of the ropes 430 and 431 being connected at one end thereof to a plate 429 rigidly secured to the bracket 425 and at the other end connected to the above-described support plate 417, as shown in FIG. 35.
The arrangement of the cloth strip gripping apparatus 401 will next be described. The joint between the apparatus 401 and the arm portion 411 will first be explained. As shown in FIG. 36, a guide mechanism 441 is rigidly secured to the distal end of the arm portion 411 in such a manner as to be integral with the arm portion 411, the guide mechanism 441 being arranged to guide an air suction nozzle 442 so that the nozzle 442 is slidable vertically. The air suction nozzle 442 is connected to a suction source (not shown) such as a blower and adapted to suck up a mass of cloth 403 by suction of air, the nozzle 442 being stably retained by a holder 443. A resilient member 444 which is defined by a compression spring or the like is interposed between the holder 443 and the guide mechanism 441. When the arm portion 411 is raised while gripping a strips S of cloth by means of chucks 454 and 455 (described later), the resilient member 444 is compressed in accordance with the level of the lifting force applied to the chucks 454 and 455. Further, a proximity sensor 445 is attached to the holder 443 to detect the amount by which the resilient member 444 is compressed, that is, the gap between the sensor 445 and the arm portion 411.
The arrangement of the gripping mechanism will next be explained. FIG. 37 is a front view of the gripping mechanism, and FIG. 38 shows the gripping mechanism as viewed in the direction of the arrows II in FIG. 37. Further, FIGS. 39 and 40 are sectional views taken along the line III--III in FIG. 38. FIG. 39 shows the way in which a single strip S of cloth is suction-held by the gripping mechanism, and FIG. 40 shows the way in which a single strip S of cloth is gripped by the gripping mechanism. In FIGS. 37 to 40, chuck arms 451 and 452 are pivotally supported by a shaft 453 which extends through the air suction nozzle 442, slide type chucks 454 being rigidly secured to one end of the chuck arm 451, and slide type chucks 455 to one end of the chuck arm 452. These chucks 454 and 455 have a projected planar configuration in accordance with the cross-sectional configuration (circular in this case) of the air suction nozzle 442 and assembled so that, when the chuck arms 451 and 452 are pivoted away from each other, the chucks 454 and 455 slide while minimizing the gap between the circular lower end of the air suction nozzle 442 and the circular upper chuck 455 and the gap between each of adjacent circular chucks 455 and 454. The reference numerals 456 and 457 denote air cylinders which act as drive sources for the chucks 454 and 455. One end of each of the air cylinders 456 and 457 is connected to the air suction nozzle 442, and the other ends thereof are connected to the chuck arms 451 and 452, respectively. A porous plate 458 is provided inside the air suction nozzle 442 for the purpose of preventing a strip S from being excessively sucked up. A distance sensor 459 is disposed at the inner side of the porous plate 458. The distance sensor 459 is adapted to detect the position of the mass of cloth and to thereby control the timing at which the gripping apparatus 401 is moved vertically and the timing at which a strip S of cloth is gripped by the chucks 454 and 455.
It is assumed that the cloth strip gripping apparatus 401 is suspended in a position shown by the broken line in FIG. 33. When, in this state, a mass of cloth 403 is transported by the transport conveyor 402 in a state wherein the mass of cloth 403 is disentangled to a certain extent, the second and third air cylinders 422 and 426 are activated to lower the arm portion 411, and when it is judged on the basis of the detection signal output from the distance sensor 459 that the cloth strip gripping apparatus 401 has lowered to an optimal position (the position shown by the solid line in FIG. 33) with respect to the mass of cloth 403, the operation of the second and third air cylinders 422 and 426 is suspended. Then, the air suction nozzle 442 is activated to suck up the mass of cloth 403, and immediately after the start of the operation of the air suction nozzle 442, the chuck driving air cylinders 456 and 457 are activated to slide the chucks 454 and 455. In this way, when the suction operation is conducted, a portion of a strip S of cloth is sucked up inside the chucks 454 and 455 as shown in FIG. 39, and when the chucks 454 and 455 are activated to slide, the portion of the strip S sucked up is gripped by the chucks 454 and 455 as shown in FIG. 40. Thereafter, the second and third air cylinders 422 and 426 are operated in reverse to the above to raise the arm portion 411, and the cloth strip gripping apparatus 401 is also raised together with it. At this time, if the strip S of cloth gripped by the chucks 454 and 455 is entangled with other strips of cloth to load an excessively large strip lifting force on the chucks 454 and 455, the resilient member 444 is compressed and the gap between the proximity sensor 445 and the arm portion 411 is reduced. Thus, an abnormal state of the strip S is detected in accordance with a detection signal output from the proximity sensor 445, and the chuck driving air cylinders 456 and 457 are activated to return the chucks 454 and 455 to the state shown in FIG. 39, thus releasing the strip S from the gripped state.
On the other hand, when the strip S is raised smoothly, the first cylinder 418 is activated in a state wherein the strip S is gripped. In consequence, the arm portion 411 is pivoted horizontal as shown in FIG. 34. In addition, the second and third air cylinders 422 and 426 are activated to allow the arm portion 411 to move vertically, thus enabling the strip S to be transported to a predetermined position.
Thus, according to this apparatus, the surface of the mass of cloth 403 is sucked to suck up a portion of a strip S of cloth, and the portion of the strip S thus sucked is then gripped by the chucks 454 and 455. Accordingly, it is possible to automatically and reliably pick up and grip a single strip S of cloth alone from the mass of cloth 403 without the need for any manual operation. Since, during the suction operation, the chucks 454 and 455 are opened to define a part of the suction port, there is no fear of the suction pressure being lowered. In addition, the porous plate 458 is provided in the intermediate portion of the air suction nozzle 442 to prevent the strip S from being excessively sucked up. Therefore, there is less fear of two strips S of cloth being picked up at a time and also a less risk of a strip S of cloth being entangled with the tip of the nozzle. Further, if a gripped strip S of cloth is entangled with other strips of cloth to load an excessively large lifting force on the chucks 454 and 455, the strip S is released from the gripped state. Therefore, there is no risk of the strip S of cloth being damaged. In this apparatus, the distance sensor 459 is provided inside the air suction nozzle 442 to detect the distance between the same and a mass of cloth 403 which is to be gripped, thereby controlling the closing operation of the chucks 454 and 455 and also the vertical movement of the arm portion 411. Accordingly, it is possible to effect a cloth strip gripping operation at a preferable position for picking up a strip S regardless of the position and configuration of the mass of cloth 403. In addition, since the distance sensor 459 is positioned at the inner side of the porous plate 459, there is no fear of the sensor 459 being damaged.
A second embodiment of the present invention will next be described with reference to FIGS. 27 to 29. Since this embodiment has an arrangement similar to that of the first embodiment except for a strip end gripping apparatus described below and some other portions, description of the mutual portions is omitted. In the figures, the reference numeral 261 denotes a squeezing means which is similar to those denoted by the numerals 111 and 117 in FIGS. 1 and 2 and which replaces the squeezing means 111 and 117 in the first embodiment. The squeezing means 261 is adapted to squeeze a strip S which is transported while being gripped by a chuck 291 shown in FIG. 27(b). The squeezing means 261 is usually formed from a stainless steel sheet and provided with rotatable guide rolls 263, 264 and 265 in the vicinities of the input and outlet portions of the squeezing means 261 in order to lower the coefficient of friction between the strip S of cloth and the squeezing means 261. The numeral 262 denotes a squeezing groove provided in the squeezing means 261. The strip S of cloth is squeezed along the groove 262 in order to enable the end of the strip S to be readily gripped. A sensor 276 is disposed in a portion of the squeezing groove 262 to output a signal indicating the passage of the strip S.
An air suction means 266 is provided in order to suppress flapping of the strip S by means of suction, thus enabling the strip S to be gripped reliably and effectively. The numeral 271 denotes a guide rail along which a chuck 291 travels, the chuck 291 being usually driven through a chain 138 or the like such as that shown in FIG. 4 so as to move through the guide rail 271. Another guide rail 272 is a transport rail that is used when a chuck 293 gripping a corner portion of the strip S is driven by the chuck 291 through the strip S. Still another guide rail 273 is arranged such that empty chucks 292 travel by gravity through the rail 273 slanted downward, the chucks 292 being fed, one by one, into a chuck feed and turn means 285 (described later) by the operation of a chuck feeder 280.
The reference numeral 274 denotes a predetermined number of guide bars which are provided on the starting portion of the guide rail 272 to prevent the chuck 293 from miscatching the strip S. More specifically, the corner portion of the strip S gripped by the chuck 291 is squeezed by the squeezing means 261 and advanced to pass the air suction means 266. At this time, the corner portion of the strip S may spring up as a reaction due to its own weight, and the chuck 293 may fail to catch the strip S. For this reason, the guide bars 274 are provided to enable the chuck 293 to catch the strip S reliably and effectively. The guide bars 274 are not necessarily limitative, and plates, rolls and the like may also be practically used. A plate 275 is rigidly secured to the guide rail 273 for the purpose of attaching an air cylinder 282 in the chuck feeder 280 (see FIG. 28).
The reference numerals 277 and 278 denote photoelectric sensors, proximity sensors or the like which are rigidly secured to the guide rail 271 to check the passage of the chuck 291 gripping the strip S of cloth. The dimension l 1 shown in FIG. 27(b) is determined so that, when chuck 291 reaches the position of the sensor 277, the operation of the sensor 276 is started. The dimension l 2 for the sensor 278 is determined so that, when the chuck 291 gripping the strip S reaches the position of the sensor 278, the trailing corner portion of the strip S has adequately passed the position of the chuck 293.
A sensor 279 is rigidly secured to the guide rail 272 to check the fact that the chuck 293 gripping the trailing corner portion of the strip S has come out of the chuck feed and turn means 285 by being pulled through the strip S. The chuck feeder 280 is arranged to temporarily stock empty chucks 292 returned to the guide rail 273 as shown in FIG. 28 and to reliably feed them into the guide rail 272 one by one. A pin 281 is rigidly secured to the plate 275 to allow the air cylinder 282 to pivot about the pin 281. Another pin 283 is rigidly secured to the plate 275 for allowing a cam 284 to pivot about it. The cam 284 is connected to the rod of the air cylinder 282 and selectively brought to two positions shown by the solid line and the two-dot chain line, respectively, in FIG. 28(b) in response to the operation of the air cylinder 282. Thus, the cam 284 repeats the temporary stock and feed of a chuck 292 for each stroke of the air cylinder 282, thereby feeding chucks 292, one by one, into the chuck feed and turn means 285. The chuck feed and turn means 285 is arranged such that, as shown in FIG. 29, an empty chuck 292 which is fed from the chuck feeder 280 is accepted into an accepting rail 300 in the section ○A , and an air cylinder 286 is activated so as to cause an arm 287 to apply force to the chuck 292 in the direction of the arrows in FIG. 4(a) in order to open the chuck 292. Thereafter, the chuck 292 is rotated 180° in the direction of the arrow in FIG. 29 by the operation of an indexing means 288 so that the chuck 292 is positioned in the section ○ B . The chuck 293 illustrated in the section ○B is the same as the chuck 292. After the passage of the trailing corner of the strip S has been confirmed, the chuck 293 is closed to grip the corner portion of the strip S and then transported through the guide rail 272 by means of the driving force transmitted thereto from the chuck 291 through the strip S. The accepting rails 300 respectively face the guide rail 273 in the section ○A and the guide rail 272 in the section ○B so that the chucks 292 and 293 can be smoothly moved between the rails 273 and 272. It should be noted that the number (2) of divisions in the indexing means 288 is not necessarily limited thereto. A plate 289 is rigidly secured to the indexing means 288 which, in turn, is secured to a bracket (not shown). On the plate 289 are mounted the rails 300 for accepting chucks 292 and 293, the air cylinders 286 and the arms 287 for opening the chucks 292 and 293. The plate 289 may be associated with a damper (not shown) so as to absorb energy at the time when the rotated plate 289 is suspended.
The following is a description of the operation of the second embodiment. Referring to FIGS. 27 to 29, the chuck 291 gripping the strip S of cloth is transported through the guide rail 271 by means of the chain 238 as shown in FIG. 4. The squeezing means 261 is located below the guide rail 271, and the strip S is thus squeezed by the squeezing means 261. When the passage of the trailing corner portion of the strip S is detected by means of the sensor 276, the chuck 293 is closed in response to the detection signal output from the sensor 276. The temporal relationship between the detection signal output from the sensor 276 and the closing operation of the chuck 293 is usually adjusted by means of a timer (not shown) so that gripping of the trailing corner portion of the strip S is reliably effected.
The guide rolls 263, 264 and 265 are effective in lowering the coefficient of friction between the squeezing means 261 and the strip S. If the squeezing means 261 is installed at an appropriate angle, it may be possible to eliminate the need to provide guide rails. When the trailing corner portion of the strip S reaches a position immediately before the chuck 293, suction is effected by the air suction means 266, so that the corner portion of the strip S is instantaneously gripped and it is thereby possible to eliminate the possibility of the strip S flapping and to apply tension to the strip S, which is effective in allowing the chuck 293 to grip the corner portion of the strip S, particularly the corner of the corner portion. It should be noted that, although in the above-described embodiment air suction is employed, it is also possible to achieve effects equivalent to the above by blowing air against the strip S from the upper side of the squeezing means 261 contrary to the above. However, this alternative procedure has the problems that the rate of consumption of air is disadvantageously high and the noise level is also unfavorably high. The guide bars 274 are adapted to support the weight of the strip S in order to prevent any unstable movement of the strip S by gravity at the position of the air suction means 266 disposed at the outlet of the squeezing means 261, and the guide bars 274 are therefore important members for enabling the chuck 293 to reliably grip the corner portion of the strip S.
Chucks 293 for gripping the corner of a strip S of cloth are fed to the guide rail 272, one by one, from the guide rail 273 by the operation of the chuck feeder 280 and the chuck feed and turn means 285. The dimension l 1 is determined so that, when the chuck 291 reaches the position of the sensor 277, the air suction means 266 is activated. The sensor 278 turns ON when the chuck 291 gripping the strip S reaches the position of the sensor 278. If, at this time, the chuck 293 is present at the previous position, the chuck 293 cannot pass the position of the sensor 279. Accordingly, this is regarded as a failure in gripping, and the chuck 291 is caused to drop the strip S which has been gripped thereby onto the belt conveyor 132 (see FIG. 3), or the strip S is transported onto the belt conveyor 132 by other known means. It should be noted that, although in the above-described embodiment the present invention is applied to the cloth spreading system, the present invention may similarly be applied to a system for sorting linens or other textile products.
A third embodiment of the present invention will next be described with reference to FIGS. 30 to 32. This embodiment features that, as shown in FIGS. 30 and 31, the second chuck conveyor C in accordance with the above-described first and second embodiments is provided with a vibrating roller 308 for vibrating the strip S of cloth which is gripped and moved by the chuck 114, together with a table 310.
As shown in FIG. 32(a), the vibrating roller 309 applies vibrations to the strip S which is gripped and transported by the chuck 114 shown in FIG. 1, to untwist and disentangle a short side of the strip S so that the corner d of the strip S extends below the chuck 114 and in the direction of travel of it. The vibrating roller 309 is usually formed in such a manner that a vibrating plate 302 formed from a stainless steel sheet is rigidly secured to a shaft 303 which rotates at a predetermined number of revolutions, as shown in FIG. 32(b). The shaft 303 is rotated by the operation of the drive means 306 through a drive pulley 304 and a chain 305. Accordingly, while the shaft 303 rotates one full turn, the vibrating plate 302 can tap the strip S twice. Since the drive means 306 is connected to a speed controller (not shown), it is possible to select a rate of tapping in accordance with the strip S. The table 310 is disposed at the downstream side of the vibrating roller 309 at the substantially the same height as the vibrating roller 309, to limit the movement of the rear half of the strip S so that the corner d of the strip S disentangled therefrom is prevented from becoming reentangled in the strip S. Conical flanges 301 are respectively attached to both ends of the vibrating roller 309 so that the strip S is prevented from being twisted around the roller 309. It should be noted that the table 310 is usually formed from a stainless steel sheet, and it is also possible to employ a punching plate and round rods which are welded together.
The operation of this embodiment will next be described. Referring to FIG. 32, the chuck 114 gripping the strip S of cloth is transported through the guide rail 150 by means of the chain 138 as shown in FIG. 4. The vibrating roller 309 and the table 310 are located below the guide rail 150, so that the strip S gripped by the chuck 114 is repeatedly tapped by the operation of the vibrating plate 302. Accordingly, even when the strip S is in the form of a mass, it is readily disentangled, and particularly, when the corner d of the short side of the strips S is in contact with the chuck 114, it can be disentangled so as to extend below the chuck 114 and in the direction of its travel.
The operation which takes place in the case where no vibrating roller 309 is provided as shown in FIG. 32(c) will now be explained. In this case, the strip S of cloth gripped by the chuck 114 may have the corner [the corner d shown in FIG. 32(a)]of a short side thereof entangled in the strip S. In such a case, even if the strip S is squeezed by the squeezing means 117 and the trailing corner portion thereof is gripped, the corner d will not emerge from the strip S in the next step wherein the corner d of the strip S is to be gripped, and therefore it is impossible to grip the corner d.
Results of the test show that such problem occurs at a rate of 30 to 40% and this leads to a considerable lowering in the rate at which the desired corner is successfully gripped. If the vibrating roll is employed, the corner d of the strip S is unfailingly disentangled from the strip S to extend below the chuck 114, and while doing so, the corner d enters the squeezing means 117. Therefore, after the strip S has passed through the squeezing means 117, the corner d of the strip S can be opened infallibly. Accordingly, the chuck 120 in the subsequent chuck conveyor can grip the corner d of the strip S unfailingly.
Since the present invention is arranged as detailed above, it is possible to automate spreading or sorting strips of cloth (linens) which have heretofore been carried out by manual operation. Accordingly, it is possible to relieve operators from a work in the sanitarily inferior environment and to automate the operation in laundry works.
Further, since in the present invention a strip of cloth is squeezed in the squeezing means while being conveyed in a slanted state, the operation is not limited by the dimensions of strips, which provides a practical advantage. Further, in the present invention, while a strip of cloth is being transported, it is untwisted by means of a vibrating roller to disentangle a desired end portion of the strip therefrom, and the strip is then squeezed by a squeezing means. Accordingly, it is possible to achieve a practical advantage that the operation is not limited by the dimensions of strips. It has been experimentally confirmed that the probability of a corner portion of a strip of cloth being successfully gripped can be raised from 50-60% to 90% by disentangling the corner portion of the strip using a combination of the disentangling effect of the vibrating roller and the table.
Although the present invention has been described through specific terms, it should be noted here that the described embodiments are not necessarily limitative and various changes and modifications may be imparted thereto without departing from the scope of the invention which is limited solely by the appended claims. | A method of gripping corner of a strip of cloth, which may be applied to, for example, systems for spreading strips of cloth, including a first step of suspending a rectangular strip of cloth by gripping one corner thereof, a second step of gripping the lowermost corner portion of the strip suspended in the frist step, a third step of raising substantially vertically either one of the gripped points of the strip gripped in the first and second steps, a fourth step of applying braking force to the other gripped point in order to apply tension to the strip, and a fifth step of holding substantially horizontally one side of the strip having a corner portion which is adjacent to the gripped points, and gripping the corner portion of the strip which is adjacent to the gripped points of the strip gripped in the first and second steps, respectively. The method enables a strip of cloth discharged from a drier to be automatically spread, thus relieving operators from the operation in the inferior environment and automating the operation in laundry works. Also disclosed is an apparatus which may suitably be employed to carry out the above-described method. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process of producing dried wood chips made of the wood of broad-leaved and/or coniferous woody plants, particularly of wood from bushes and of waste wood or of wood obtained in wood-growing plantations.
2. Description of the Prior Art
Wood chips are used at increasing rates for heating purposes. Their heating value will strongly depend on the dryness of the wood chips. An adequate drying to a moisture content of 16 to 20% by weight will also be required to ensure that a sooting of the chimneys and an intolerable pollution of the environment by the flue gases from excessively moist wood chips will be avoided.
It is known that wood, particularly waste wood, can be predried in the air, but large drying areas are required, before the wood is chopped and the chips must be subsequently dried to the desired moisture content in drying plants heated by extraneous heat. But the chopping of predried wood is more difficult than the chopping of green wood. Predrying involves the performance of a plurality of operations between the supply of the wood and the chopping operation. Besides, storage times are required for drying and the final drying requires an expenditure of work, time and energy. Whereas a strong predrying will decrease the energy required for the final drying, the predried wood chips will be liable to be infested by pests or fungi when they are kept in intermediate storage under improper or unfavorable conditions and an undesirably high proportion of dust and fine particles may be formed in the chipped material and may even have to be removed for a production of wood chips which can be used in heating plants. Difficulties are involved in the dumping of the separated fines. In a search for alternative cultivation methods in agriculture, so-called wood-growing plantations have become significant, in which fast-growing woody plants, such as poplars, alders, willows and various species of Hibiscus, are grown in most cases as multiple-stem bushes. In some cases a trunk may be left in the ground and only the stems which have offshooted from the trunk may be cropped so that a plurality of harvests are possible in a multi-annual cycle without a need for a new planting. If the wood that has been cropped in such wood-growing plantations is to be used for the production of wood chips for fuel-firing furnaces, an economical utilization by which the costs are recovered or which is profitable is apparently impossible unless the wood chips produced can be dried without a need for extraneous energy. A large proportion of waste wood will also be contained in wood that has been broken by the wind or the snow and which must be processed as soon as possible in order to avoid an infestation by pests.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a process for the production of sufficiently dry wood chips with a low expenditure of work, substantially without a need of intermediate storage and without the use of extraneous energy or with only a small amount of extraneous energy.
In a process of the kind described first hereinbefore that object is accomplished in that the wood in a green state is chopped to form chips, which are then mixed with also comminuted, fermentable green plant material, which consists of the bark and the leaves of broad-leaved woody plants, the leaves of leaved plants, or of grass or of mixtures thereof, and the resulting mixture is compacted to form a compacted body, which is caused to ferment with generation of heat of fermentation in a space that is air-tightly enclosed on all sides and at the bottom, said compacted body is dried in said space under the action of said heat of fermentation, and water vapor and gases evolved during said fermenting and drying are removed from said space.
It had been believed before that wood chips can be stored in bins only in dry state because experience had shown that semimoist or merely predried wood chips stored in bins tend to be infested by fungi or mold so that they may rot in extreme cases and even when only slightly infested by fungi can no longer be combusted for heating purposes at all or can be used for such purposes only with great restrictions and certainly cannot be sold to customers as fuel.
The invention is based on the surprising recognition that at least a major part of the heat required to dry the wood chips can be generated by the fermentation of fermentable green plant material. It has been found that substantially only the fermentable green plant material is fermented and that substantially only the moisture is driven out of the wood. Overheating can be avoided in that the wood and the fermentable green plant material are used in the proper ratio and in that an extraneous cooling is performed, if desired.
If the wood chips are to be made only from the wood of broad-leaved woody plants, the fermentable green plant material may consist of the bark, which has been chopped together with the wood, and of accompanying leaves and the mixture of fermentable green plant material and wood chips may be fermented immediately after the chopping operation. In that case it will be desirable to use the fermentable green plant material in a proportion below 15% by weight and to produce from the wood chips and the fermentable green plant material a mixture having an average moisture content of up to or above 70% by weight. The proportion of the fermentable green plant material may be selected in dependence on the moisture content of the wood chips.
Alternatively, mixtures may be produced, e.g., of green wood chips made of wood of broad-leaved woody plants and wood chips made of wood from green or predried coniferous woody plants. If in such case the wood from the broad-leaved woody plants is not accompanied by a sufficient quantity of fermentable green plant material, additional fermentable green plant material consisting of any or more of the stated substances may be added. It will also be possible to use the process in accordance with the invention for a drying of wood from only coniferous woody plants with the aid of a corresponding quantity of fermentable green plant material. The proportion of the fermentable green plant material will always depend on the average moisture content, on the quantity of heat of fermentation which can be generated by the fermentation of the fermentable green plant material, on the space which is available for carrying out the process and on the heat insulation of such space. If heat at a relatively high rate may be dissipated from the compacted mixture it will be necessary to add somewhat more fermentable green plant material than where heat can be dissipated only at a low rate. The process can be carried out in such a manner that when the fermentation which may result in a temperature rise up to about 80° C. has been terminated and the mixture has subsequently been allowed to cool the completely dried wood chips taken from the drying space have a moisture content of 16 to 20% by weight and can be combusted for heating purposes or can be sold.
If the fermentation is carried out in a space that is defined by heat-insulated bottom and side walls, a sufficient fermentation of the fermentable green plant material and an adequate heating of the wood content for a satisfactory drying will be effected even in the surface layer of the compacted body.
In the drying of large quantities and when the compacted body has a height up to and above 5 meters, exhaust shafts having gas-permeable walls and provided at their top end with an outlet may be disposed in the compacted body so that the gases and water vapor which are evolved can be exhausted through such shafts. A plurality of such shafts may be provided with a spacing of, e.g., 2 meters. In that case the resistance to the exhausting of the gases and water vapor which are evolved will be reduced. An adequate compacting of the mixture can be ensured by trampling or rolling, just as in the ensiling of green forage, in that the wood is chopped to form chips differing in size and having major dimensions between 2 and 35 mm. To dry as fast as possible the compacted body may be formed in an airtightly enclosed space and at least a bottom layer of said body may be formed with a higher proportion of fermentable green plant material or a bottom layer of the compacted body may be formed in a quantity which is only a fractional part of the total quantity of the compacted body and by a supply of energy from an external heat source may be heated to a fermentation temperature above 40° C. immediately when said bottom layer has been formed. In that case the subsequently formed layers of the compacted body will quickly be heated to the fermentation temperature by the heat which has been generated in the bottom layer.
Where relatively large plants are used, two or more fermentation spaces arranged one beside or above the other may be used and may be supplied with the mixture of wood chips and fermentable green plant material during periods of time which are offset from each other and surplus heat of fermentation from a compacted body which is in a state of intense fermentation may be extracted and supplied to the other compacted bodies in order to heat the same to the initial fermentation temperature.
A relatively uniform temperature in the compacted body can be ensured by the above-mentioned insulation of the fermentation space or in that part of the heat of fermentation which has been generated during the drying is dissipated by a heat transfer fluid from the core region of the compacted body to the surface layers of said body. In that case the heat transfer fluid may even consist of the mixture of water vapor and gas, which mixture is suitably passed through a dehumidifier. In addition or alternatively, heat exchangers, which are supplied with a liquid heat transfer fluid, may be provided between the core region of the compacted body and the outside peripheral surface of said body. Adjacent to the core region of said body said heat exchangers may be attached, e.g., to an exhaust shaft. In order to avoid a charring of the wood chips in a mixture which contains an excessively high proportion of fermentable green plant material or if the fermentation is effected at a relatively high rate, the temperature of the compacted body may be monitored and a temperature rise above about 85° C. may be prevented by a cooling action. Cooling may be effected by means of external heat exchangers and the surplus heat may be used to heat water or for other heating purposes. If two or more fermentation spaces are arranged one beside the other or one above the other and are supplied with the mixture of wood chips and fermentable green part material during periods of time which are offset from each other, said heat exchangers may be used for a transfer of heat from one or more compacted bodies which are in a state of intense fermentation to other compacted bodies in order to heat the same to the initial fermentation temperature. The drying process in a given compacted body will substantially have been completed if the drying temperature remains relatively constant for a predetermined period of time, which will depend on the size of said compacted body and the rate at which water vapor can be exhausted therefrom. After that period the compacted body may quickly be cooled by means of externally disposed heat exchangers and the heat which is thus recovered may be utilized.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a diagrammatic longitudinal sectional view showing an embodiment of a plant for carrying out the process in accordance with the invention and
FIG. 2 is a diagrammatic top plan view showing another embodiment of such plant.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of plants for carrying out the process in accordance with the invention and examples of such process will now be described more in detail.
The plant shown in FIG. 1 comprises a container, which has side walls 2, a bottom 3 and a top 4, which enclose a cylindrical or prismatic holding space 1. The parts 2, 3 and 4 may consist of concrete, which may be provided with a corrosion-resisting coating, or may constitute parts of a metal or plastic structure. The top 4 may be provided with one or more charging openings, which are not shown and may be closed by covers. One of the side walls 2 may be provided with an extraction door. In the embodiment shown the side walls 2, the bottom 3 and the top 4 are provided on their inside surfaces with a heat-insulating lining 5, 6 and 7, respectively. A metal or plastic structure may alternatively be provided with heat insulation on the outside.
An exhaust shaft 9 made of perforated material, such as metal wire mesh 8, is disposed at the center of the holding space 1 and contains a pipe 10. Flow passage gaps 13, 14 are defined between the bottom insulation 6 and the underside of a compacted body which lies on an intermediate bottom 11 and between a shell 12 of corrosion-resisting material surrounding the outside peripheral surface of the compacted body and the heat insulation 5 on the side walls 2. In the embodiment shown, the parts 11, 12 are supported by spacers 15. Alternatively, exhaust pipes or shafts in a starlike configuration may be provided on the bottom 3 and may extend to the shaft 9 and said pipes may merge into shafts along the side walls 2.
The exhaust pipe 10 contains a fan 16, which is controlled by a control unit 17. That control unit is controlled by one or more temperature sensors 18, which are disposed in the compacted body and/or in the flow passage gaps 13, 14 or in the equivalent shafts. When the compacted body has been formed in the holding space 1 and the fermentation has been initiated, a damper 19 which is initially in a position in which the damper closes a lateral opening in the pipe 10 is moved to the position which is shown in phantom and in which the damper 19 closes the pipe 10 near its outlet end. When the fan 16 is then started the mixture of gas and water vapor which have been evolved during the fermentation is circulated under the top 4, through the gaps 13, 14, through the shaft 9 and through the portion of the pipe 10 under the damper 19. That circulation results in a heat exchange between the core region and the periphery of the compacted body in the holding space 1. The mixture being circulated may be passed through a dehumidifier, which is attached to the pipe 10 at its lower end or is constituted by cooling surfaces which have been inserted in certain regions of the insulation 6, 5, and the moisture which has been collected may be withdrawn to the outside. In addition, heat exchangers supplied with a liquid heat transfer fluid are provided for an improved heat transfer between the core region and the periphery of the body of compacted mixture. Those heat exchangers are represented in the drawing by pipes 24, 25 and their function will be described more in detail with reference to FIG. 2. The mixture of water vapor and gas can be blown out when the damper 19 has been opened under the control of the control unit 17.
In the embodiment shown in FIG. 2 a holding space 21 is enclosed by a cylindrical outer shell 20. The top and bottom walls defining the space 21 are not shown. The shell, bottom and top walls are provided with heat insulation 22. The holding space 21 may be surrounded by a structure which is similar to that provided in a tower silo for processing feed and existing silos of that kind may be provided with heat insulation and suitable internal fixtures to form a holding space for carrying out the process in accordance with the invention. A central shaft 23 is surrounded by tubes or radiators 24 of a heat exchanger and defines flow passage gaps therewith, which permit an escape of gas and water vapor. Corresponding heat exchanger elements 25 are arranged in a jacket space surrounding the compacted body in the holding space 21. Upper and lower connecting pipes 26 may be provided for conducting a heat transfer fluid preferably consisting of a liquid so that a temperature equalization between the core region and the outer periphery of the compacted body in the holding space 21 will be effected. That fluid may be subjected to a forced circulation, if desired. As is indicated by dotted lines the heat exchangers 24 to 26 may be connected by lines 27, 28 to an external cooling or heating circuit 29. An external heating circuit may be used for a quick heating of a bottom layer of the compacted body to a fermentation temperature of about 40° C. and an external cooling circuit 29 may be operated when the temperature of the compacted body tends to rise above a preselected upper limit. In the latter case the extracted heat may be used for water heating or for room heating or for a heating of a compacted body in a fermenting space in another container, which is operated in parallel and in which the compacted body is in an initial state of fermentation. Particularly in the jacket space 25 the heat exchanger may be divided into a plurality of superimposed sections, which may be operated and shut down in a controlled manner so that the heating of the peripheral regions of the compacted body in different height zones can be controlled.
EXAMPLE 1
Birches were felled early in October. The waste wood which was obtained and consisted of the branches and the twigs connected thereto as well as of the leaves on said twigs was immediately comminuted in a chopping machine to form chips having major dimensions between 2 and 35 mm. Said chips were charged from above into a holding space, which could be walked in through an airtightly closing armored door. The holding space had the basic configuration of a square having side lengths of 5.6 meters and had a height of 4.30 meters and was provided with a square charging opening having a side length of 1.60 meters. The chips were distributed on the bottom to form layers and were compacted by being trampled as they were distributed. At the end of the felling and the succeeding chopping early in November the holding space contained a compacted body of about 120 m 3 . The proportion of the fermentable green plant material amounted to about 10% by weight and the average moisture content of the compacted body amounted to about 60% by weight. The above-mentioned armored door was closed. An exhaust shaft consisting of perforated boards was installed at the center of the compacted body. Because the outdoor temperatures were relatively low, water vapor escaped at the charging opening and through the exhaust shaft and was well visible as a veil of haze. The water which was condensed at the top wall of the holding space was collected and drained by means of plastic films. A temperature rise of the compacted body to about 80° C. was observed. The rate of temperature rise was strongest during the first two weeks after all plant material had been charged. Six weeks after the charging of all plant material the armored door was opened. The wood chips which could now be extracted through said door had cooled down and contained 16 to 20% by weight moisture. An inspection of the wood chips revealed that they had no unpleasant odor and were not infested by molds or other fungi. As a result of the fermentation the wood chips had a slightly yellow to brown color. Part of the wood chips was combusted without difficulty and another part was loaded and sold as bulk fuel.
EXAMPLE 2
In smaller holding spaces, which were provided at the bottom and side walls with heat insulation, green alder wood which contained 10% fermentable green plant material was processed to form wood chips and bushwood was processed to form green wood chips which were similar to the woodchips which are produced from the wood obtained from wood-growing plantations. These green wood chips were dried in accordance with the same process and the drying was also completed after six weeks. In experimental work, mixtures consisting of equal parts by weight of green wood chips from broad-leaved woody plants and wood chips made from waste wood from coniferous woody plants were processed. In addition to the leaves connected to the wood from broad-leaved woody plants, fermentable green plant material obtained from broad-leaved plants and grasses was added so that the mixture contained 10% by weight of fermentable green plant material. In that case the heat which was generated by the fermentation of the fermentable green plant material was also sufficient for an adequate drying within six weeks.
After the fermentation and drying, the wood chips are accompanied by fermented plant material from which water has been removed and which may either be combusted together with the wood chips or, if wood chips having a high purity are required, may be removed from them by conventional mechanical separating operations. | Wood from broad-leaved and/or coniferous woody plants, particularly bushwood or waste wood or wood obtained in wood-growing plantations, is processed in that wood in a green state is chopped to form wood chips and is mixed with accompanying or additional fermentable green plant material, which has also been comminuted. The resulting mixture is compacted to form a compacted body of plant material in a space which is airtightly enclosed at least on the sides and at the bottom. The compacted body is fermented in said space to generate heat of fermentation, which is used to dry the compacted body so that water vapor and gases are evolved, which are permitted to escape. The fermentable green plant material may consist of the bark and leaves of broad-leaved woody plants, of the leaves of leaved plants, of grass, or of mixtures of said materials. | 5 |
TECHNICAL FIELD
[0001] The present disclosure is related to a wear-resistant insert used in such machinery like road paving and mining equipment, and more particularly to a method of joining the wear-resistant insert with a base substrate component using a method of friction welding.
BACKGROUND
[0002] Wear-resistant inserts, herein also referred to as inserts, are commonly brazed or press fit into place to improve wear resistance of road paving or mining equipment. These types of ground engaging elements are high wear parts and so assembling them into machinery in a cheap, yet efficient and sturdy manner, is desired. The inserts are intended to withstand substantial and repetitive forces when used with any ground-engaging tool. For example, the rotor drum of an asphalt reclaimer may include many smaller cutter bits that often are brazed into their respective piece holders. The asphalt reclaimers pulverize the asphalt layer and mix it with the underlying base. The reclaimers can add asphalt emulsions or other binding agents during pulverization or during a separate mix pass. Softer metallic materials do not exhibit the required theoretical strength properties for the purpose of such heavy-wear use with a rotary workpiece or rotor drum. To address that limitation, the design of the parts can be made to avoid or limit the need for such assembly components, but that approach generally involves more machining operations and more parts to produce the desired assembly.
[0003] One problem which may arise when working in the field of ground-engaging road paving or mining equipment is that wear-resistant inserts are often brazed or press-fit into a base component. However, over time, the braze tends to wear out or the insert starts to wear away the base material around it and the insert falls out. Brazing is also time-consuming. This may cause inefficiencies and failures of expensive equipment and slows down processes that rely on multiple small moving parts to be working seamlessly together.
[0004] Alternative approaches have been applied to product assembly, such as the friction welding methods like that disclosed in U.S. Pat. No. 8,708,628, where a component for use with a rotary tool is inserted through a surface of a workpiece made of a material showing friction-induced plasticity and rotated in a first direction while an axial force is applied onto the component. Better methods of friction welding may be desired to create stronger “welds.”
[0005] A problem which may also arise in friction-welding two separate parts together is that the resultant piece often does not produce the desired wear resistance that is needed for repetitive use in heavy machinery. Parameters like cost, efficiency and a first life-cycle of a machine come into play. Achieving a longer-lasting wear-resistant insert and method to better join two components is desired to provide enhanced mechanical traction retention of the wear-resistant insert.
[0006] And yet another problem that may arise is that when welding a wear-resistant insert and a wear base component together, a stress concentration often referred to as a stress riser, occurs on an object where the stress is concentrated. This can lead to a mechanical defect with either or both the wear-resistant insert and the base-wear component which in turn can cause a material to fail. For example, a propagating crack can cause a material to fail when a concentrated stress exceeds the material's strength. Further, fatigue cracks often start at stress risers, so removing such defects increases the fatigue strength.
[0007] Many of these and other shortcomings of the prior art are addressed by the various embodiments desirable in the present disclosure.
SUMMARY
[0008] In some embodiments, an insert may be provided. The insert may include: a body, having an engaging portion and a free portion located opposite the engaging portion; a side portion of the body defining a retention cavity, the retention cavity being located closer to the engaging portion than the free portion; a junction between the retention cavity on a side of the portion defining a rounded surface; and a protrusion extending from a surface on the engaging portion.
[0009] In some embodiments, a ground engaging element for a machine is provided. The ground engaging element may include: a substrate; an insert having a body, which has an engaging portion and a free portion located opposite the engaging portion; a side portion of the body defining a retention cavity, the retention cavity being located closer to the engaging portion than the free portion; a junction between the retention cavity on a side of the portion defining a rounded surface; and a protrusion extending from a surface on the engaging portion; and wherein the insert is embedded into the substrate and the substrate material is located in the retention cavity.
[0010] In some embodiments, a method for attaching an insert to a substrate is provided. The method may include: rubbing the insert against the substrate; forming a heat-affected zone in the substrate; forming plasticized substrate material from friction resulting from the rubbing; moving the insert to a first depth in the heat-affected zone in the substrate; moving the insert to a second depth in the heat-affected zone in the substrate, wherein the first depth is deeper than the second depth; flowing the plasticized material against the insert; and releasing the insert.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a partially cut-away diagram of a ground-engaging machine that includes at least one friction welded wear-resistant insert in accordance with aspects of the present disclosure.
[0012] FIG. 2 is a side view of an exemplary design of a wear-resistant insert with aspects of the present disclosure.
[0013] FIG. 3 is a side view of an exemplary design of a wear-resistant insert with aspects of the present disclosure.
[0014] FIG. 4 is a side view of an exemplary design of a wear-resistant insert with aspects of the present disclosure.
[0015] FIG. 5 is a side view of an exemplary design of a wear-resistant insert with aspects of the present disclosure.
[0016] FIGS. 6-8 are side cross-sectional views of the presently disclosed wear-resistant insert entering a base wear component.
[0017] FIG. 9 is a top view of an embodiment showing orbital friction welding that can be utilized according to the present disclosure.
[0018] FIG. 10 is a top view of an embodiment showing linear friction welding that can be utilized according to the present disclosure.
[0019] FIG. 11 is a flow chart illustrating a method of friction welding the insert and base substrate together.
DETAILED DESCRIPTION
[0020] In one aspect of the present disclosure, friction may be used to generate heat in order to make a base substrate material that is referred to herein as a “plasticized” substrate material so that a wear-resistant insert may be inserted inside the base substrate material. Plasticized, however, and can mean a plasticized, a semi-plasticized material, molten, molten-like, or other material that is softened or will flow as a result of being heated. Once the insert is placed in the base material, the base material and insert will cool and thus be permanently joined. In some embodiments where no melting occurs, friction welding is not actually a welding process in the traditional sense, but a forging technique. However, due to the similarities between these techniques and traditional welding, the term “friction weld” has become common. The insert could be rotated, rubbed, and/or simultaneously pressed into the base by a welding tool that is similar to a friction stir welding machine, mill, or lathe. Frictional heat is generated at the contact point or area between the surfaces caused by the rubbing of the insert on the surface of the base material. Specifically, once a desired depth has been achieved, the insert could be slowly lifted to a second more shallow depth in the substrate to allow a better flow of the plasticized material into any cavities in the insert and/or generally encompassing the engaging end of the insert. Rotation could then be stopped to allow the base material to solidify. Quenching may be done during or at the end of the process to promote high hardness or any other desired qualities of the base material and/or insert.
[0021] In one aspect, it may be desirable to enhance the shape or material strength of the wear-resistant insert. For example, a shape of the insert may be selected to reduce any concentrated stress that could exceed the material's cohesive strength. More specifically, the shape of the insert could also be produced in a way that would reduce the likelihood of the generation of stress risers, which may include, but is not limited to, the use of rounded edges (also termed rounded surfaces) and fillets to reduce such potential for stress concentration. The wear-resistant insert may be made of carbide, ceramic, metal or another material with similar properties that are capable of use in friction welding. The wear-resistant insert may also be coated with a coating material that may promote friction to improve heating of the base material. The coating material may provide an alloying agent to the base material to further ensure higher hardness and wear resistance. In other embodiments, the coating may provide corrosion resistance or any other desired function.
[0022] The shape of the insert and/or the coating material applied to the insert may provide enhanced mechanical fraction retention of the wear-resistant insert. The process may be done with manually controlled equipment or automated equipment. It is contemplated that friction welding can be achieved in many ways, which may include, but is not limited to, spinning, orbital, or linear friction stir welding.
[0023] Referring to FIG. 1 , a road asphalt reclaimer 20 is illustrated. FIG. 1 shows the asphalt reclaimer 20 with an exposed region 22 that has the cover or housing that typically would cover a rotor drum 24 removed to better illustrate the rotor drum 24 . In particular, an example of a ground-engaging tool such as a rotor drum 24 may include multiple welded wear resistant inserts 40 on a rotor drum 24 used to pulverize asphalt 26 . For example, an insert 40 may be a cutter bit. The wear-resistant insert 40 and the substrate 62 may interface and may be permanently joined by friction welding. The base substrate 62 may be pre-manufactured to be shaped to receive a specific insert 40 or may not be pre-manufactured to fit with the insert 40 and can be adjusted or adapted to receive any sized insert 40 .
[0024] Referring now to FIGS. 2-5 , in preferred embodiments a typically unaltered insert 40 is shown. The insert 40 in FIGS. 2-8 is shaped differently than the insert 40 of FIG. 1 , as inserts 40 in accordance with the present disclosure may vary in shape. The insert 40 may be designed with enhancements. These enhancements can be achieved through configuring the shape and/or material strength of the wear-resistant insert 40 depending on the potential use and ultimately ensure a longer lifecycle of the insert 40 . For example, an insert 40 might have rounded edges or a special coating to prevent any concentrated stress (not pictured and also referred to as a stress riser) that could cause material failure by exceeding the material's cohesive strength.
[0025] In one aspect shown in FIG. 2 , an insert 40 may be elongated with engaging portions and free portions such as a free end 42 and an engaging end 44 . The engaging end 44 includes an engaging end surface 46 that can interface with the substrate 62 and substrate surface 64 , as further explained below with respect to FIGS. 6-8 . In one aspect, the insert 40 may include at least one protrusion 48 near the engaging end 44 such that the protrusion 48 is centered to be able to localize and generate a sufficient amount of heat necessary for developing a heat-affected area on the substrate 62 . In one aspect, a rounded edge 52 instead of a squared or sharp corner may cause an object to experience less likelihood of a local increase in the intensity of a stress field.
[0026] In one aspect shown in FIG. 3 , an insert 40 may include at least one type of a retention cavity 49 . Specifically, a retention cavity 49 can be also referred to as a pre-drilled or otherwise formed hole 50 on the engaging end 44 of the insert 40 . The retention cavity 49 can also be referred to as a retention groove 54 to form a stepped or castellated portion 58 on the engaging end 44 of the insert 40 . The groove 54 can encircle the insert 40 or run along the periphery of the insert 40 . A retention cavity 49 can be located closer to an engaging end 44 than the free end 42 and where there is a junction between the retention cavity 49 on a side of the portion defining a rounded surface or rounded edge 52 .
[0027] In an aspect seen in FIG. 4 , an insert 40 may be configured to include a retention cavity 49 such as a second groove 60 near the engaging end 44 . The second groove 60 is defined by a stepped or castellated portion 58 , rounded edges 52 and fillets 56 . The insert 40 may also include a plurality of holes 50 located in close proximity to the first groove 54 and second groove 60 . The insert 40 may also include a plurality of protrusions 48 located at selected locations near the engaging end 44 of the insert 40 .
[0028] The physical shape of an insert 40 to be used in a friction welding process can be any shape, whether the shape be cylindrical (as illustrated in FIGS. 2-4 ), shaped like teeth or cutters ( FIG. 1 ), spherical (not pictured), or can be a quadrilateral shaped tile, as shown in FIG. 5 . For example, brazing or friction welding may be performed on a thin tile insert 40 and then brazed onto the front of a rotor blade. Further, a plurality of protrusions 48 , holes 50 or rounded edges 52 may be included on the insert 40 as seen here in FIG. 5 .
[0029] The friction-welding of an insert 40 will be described hereinafter with reference to FIGS. 6, 7 and 8 . The friction-welding method and the related methods of operation may be controlled in response to one or more operational parameters such as material strength, force needed, pressure needed, time constraints, and other parameters.
[0030] FIG. 6 illustrates a welding tool 74 with an end effector 76 gripping an insert 40 on the free end 42 as it first begins to spin the insert 40 in a rotational direction illustrated by Arrow A around a centered axis 80 against the substrate 62 . In alternate embodiments, the spinning may occur in a direction opposite of Arrow A. The tool 74 may be a mill or lathe, or any type of tool 74 that exerts a lot of force and can withstand the resistance of the workpieces being friction welded. The tool 74 might have an end effector 76 that is shaped to interface with and grip the insert 40 . For example, an end effector 76 might be a chuck. The tool 74 may be manually controlled equipment or automated equipment. In an aspect, the substrate 62 can be homogeneous (not pictured) or have different layers like a first substrate layer 66 , a second substrate layer 68 , or even a third substrate layer 70 into which the insert 40 might be embedded. These layers can further help achieve a desired wear-resistant weld given one layer of a substrate 62 layer might have different melting properties and densities than another substrate layer, yet in combination the two or more layers act in harmony to create the desired tough and resilient weld.
[0031] In one embodiment, an engaging end 44 of the insert 40 interfaces with the substrate surface 64 , and the engaging end 44 may include a protrusion 48 purposefully centered along the axis 80 . This protrusion 48 helps to centralize the heat to create a heat-affected zone 72 in the substrate 62 as the tool 74 moves the insert 40 . The heat-affected zone 72 may soon become a plasticized state that is capable of plastically displace and fusing the insert 40 with the substrate 62 .
[0032] FIG. 7 illustrates the continued operational mode of the welding tool 74 pressing the insert 40 to a first depth in the substrate 62 as the heat-affected zone 72 remains in a plasticized state. As the tool 74 continues to spin, the tool 74 presses the insert 40 in the direction illustrated by Arrow B into the substrate 62 . The heat-affected zone 72 will enlarge in the substrate 62 and can enlarge into a first substrate layer 66 , second substrate layer 68 , or third substrate layer 70 . The insert 40 may be embedded into any type of homogenous or multi-layered substrate 62 . A first depth of how far to press the insert 40 into the substrate initially might be pre-determined depending on the desired use of the insert 40 . If there are retention cavities 49 , then the insert 40 is pressed to a first depth into the substrate 62 so as to allow the retention cavities 49 to surpass the plane of the substrate surface 64 .
[0033] FIG. 8 illustrates the continued operational mode of the welding tool 74 bringing the insert 40 to a second depth of a substrate 62 . In the disclosed embodiment, after the insert 40 is moved to a first desired depth within the substrate 62 , the welding tool 74 moves the insert 40 in the direction of Arrow C to a second depth which is more shallow within the substrate 62 than the first depth. This second depth may be achieved while simultaneously or after slowing the rotation of the tool 74 but the slowing is optional. This type of “pull-back” motion of the tool 74 may enhance the flow of plasticized material 73 from the heat-affected zone 72 into any number of retention cavities 49 that exist on or around the insert 40 as illustrated by Arrow D. Thus the “weld” is further strengthened and reinforced by the substrate 62 when the substrate 62 acts to permanently “grip” or “encapsulate” the insert 40 upon future cooling.
[0034] In one aspect, the combined inclusion of one or more of rounded edges 52 and fillets 56 aid in minimalizing localized stress concentrations on a sharp-edged or cracked insert 40 . Once the insert 40 achieves its fixed position, then the tool 74 movement is finally stopped so as to allow the wear resistant insert 40 and the base component substrate 62 to solidify into one resultant workpiece. During the cooling and hardening period, the grooves 54 , 60 stepped or castellated portions 58 , and holes 50 provide places for plasticized material 73 to flow into the insert 40 to provide a better bond between the insert 40 and substrate 62 .
[0035] Three examples of friction welding operational modes that can be used to embed a wear resistant insert 40 into the desired component substrate 62 are illustrated in FIGS. 6-8 and FIGS. 9-10 .
[0036] Referencing back to FIGS. 6-8 , a first operational friction welding mode known as spin-welding is illustrated. Spin-welding involves spinning an insert 40 at a high rate of rotation shown by Arrow A. Further, the welding tool 74 is gripping and spinning the insert 40 around a center axis 80 of the insert 40 against fixed base substrate 62 to create heat via friction between the insert 40 and the substrate 62 .
[0037] Referencing FIG. 9 , a second operational friction welding mode known as orbital friction welding is shown. Orbital friction welding is similar to spin—or rotary—friction welding where the insert 40 and the substrate 62 are rotated relative to each other but with their respective axes 80 offset. In some embodiments, the axis 80 may be offset by up to 3 mm. The path the insert 40 follows runs in a type of small orbital friction path 82 in a direction indicated by Arrow E.
[0038] Referencing FIG. 10 , a third operational friction welding mode known as linear friction can be used to embed a wear resistant insert 40 into the substrate 62 . Linear friction welding is similar to spin welding except that the welding tool 74 oscillates laterally along a linear friction path 84 as indicated by Arrow F instead of, or in addition to, spinning The speeds may be much lower in general, which may result in the pieces to be kept under pressure at all times. Linear friction welding may be use more complex machinery than spin welding, but has the advantage that parts of any shape can be joined. Another advantage is that in some instances quality of joint is better than that obtained using rotating technique.
INDUSTRIAL APPLICABILITY
[0039] The present disclosure is applicable to any type of friction welding that is contemplated being used with a wear-resistant insert 40 . The operational mode of the friction welding process described below with reference to FIG. 11 as well as FIGS. 2-8 may cater to the various operational requirements of the machinery or ground-engaging tools. This can include adjustment for varying forces and pressures required to friction weld.
[0040] FIG. 11 is a flowchart of the method and process for attaching an insert 40 into a substrate 62 . In Step S 10 , a welding tool 74 begins to rub an insert 40 against a substrate 62 , which over a period of time, as shown in Step S 20 , this rubbing forms a heat-affected zone 72 in the substrate 62 . In Step S 30 , as the tool 74 continues to spin, the tool 74 presses the insert 40 in a direction shown by Arrow B into the substrate 62 . The first depth of how far to press the insert 40 into the substrate 62 may be pre-determined depending on the perceived industrial use of the wear-resistant insert 40 . Step S 40 is an optional step where at any point the tool 74 can be slowed rotationally as the continued rubbing movement of the insert 40 against the substrate 62 persists. In Step S 50 , then the tool 74 moves and extends the insert to a second depth within the substrate 62 . The second depth is more shallow than the first depth. This leads directly to Step S 60 , where the plasticized material 73 flows against the insert 40 . In Step S 70 , this type of “pull-back” motion of the tool 74 set forth in Step S 50 is designed to enhance the flow of plasticized material 73 from the heat-affected zone 72 into any number of retention cavities 49 . During the cooling and hardening period, the grooves 54 , 60 stepped or castellated portions 58 , or holes 50 provide places for plasticized material 73 to flow into the insert 40 to provide a better bond between the insert 40 and substrate 62 . In Step S 80 , the friction welding process also may involve quenching the insert 40 . Quenching can use any common quenching technique to promote high hardness of the base material substrate 62 and/or insert 40 . The quenching Step S 80 may include a quench material like water or oil. In Step S 90 , the tool 74 releases the insert 40 from the end effector 76 .
[0041] The method may further involve the step of coating the insert 40 , or more properly referred to as friction surfacing. Friction surfacing is a process where a coating material is applied, such as a friction-enhancing or alloy-promoting material, before the tool 74 begins to spin the insert 40 into the substrate 62 . A rod composed of the coating material is rotated under pressure, generating a plasticized layer in the rod at the interface of the engaging end surface 46 of the insert 40 with the substrate 62 . By moving a substrate 62 across the face of the rotating rod a plasticized layer is deposited between 0.2-2.5 mm thick depending on rod diameter and coating material. When coating or friction surfacing a piece, the structure might change because the temper in the steel is lost. In friction stir welding, loss of temper is minimal, and performing the coating quickly minimizes the tempering effect. However, it may be desired to coat the material to restore some of the hardness present in the material prior to the steel losing its temper. The coating material might be chrome, carbon, silicon or a material with similar properties. As such, the coating could involve multiple compositions.
[0042] While aspects of the present disclosure have been particularly shown and described with reference to the embodiments above, it will be understood by those skilled in the art that various additional embodiments may be contemplated by the modification of the disclosed machines, systems and methods without departing from the spirit and scope of what is disclosed. Such embodiments should be understood to fall within the scope of the present disclosure as determined based upon the claims and any equivalents thereof. | A method for attaching an insert to a substrate includes: rubbing the insert against the substrate; forming a heat-affected zone in the substrate; forming plasticized substrate material from friction resulting from the rubbing; moving the insert to a first depth in the heat-affected zone in the substrate; moving the insert to a second depth in the heat-affected zone in the substrate where the first depth is deeper than the second depth; flowing the plasticized material against the insert; and releasing the insert. | 2 |
The present invention relates to compositions that are specially useful for preserving and protecting sensitive materials that undergo undesired reaction when they are subjected to degradative environments.
Methods for temporarily protecting reactive materials, such as medicaments, while the medicaments are exposed to environments which ordinarily tend to degrade or decompose the medicament have been known for many years. For example, certain drugs that ordinarily react in an undesirable manner in the acidic environment of the stomach have been coated heretofore with various materials that are resistant to the action of acids. In this manner, drugs for human consumption are sometimes protected during their passage through the stomach. The protective coatings are selected so that, after the passage of the coated material through the stomach, the coating decomposes in the more basic environment of the intestine, thereby releasing the drugs (chemically unchanged) at the place in the body where the drug will be most effectively absorbed. Such coatings have been termed "enteric coatings."
In the case of ruminants such as sheep and cattle, medicaments having "enteric coatings" are, unfortunately, usually not protected from the drastic treatments afforded in the rumens of such animals. Medicaments given orally to ruminants first pass directly into the rumen, which has a large population of microorganisms and is either neutral or slightly acidic. From the rumen the materials then pass into the more acidic abomasum, and subsequently into the animal's intestine. In the case of ruminants, many medicaments, including many desirable nutrients or feedstuffs, such as vitamins, amino acids, and the like, are decomposed or metabolized to at least some extent in an undesirable manner in the environment of the rumen. Such decomposition makes oral treatment of ruminants with such susceptible materials either expensive or impossible.
Thus, there is a definite need, particularly in the fields of veterinary medicine and ruminant nutrition, for a method whereby materials that are ordinarily degraded in the ruminant environment can be administered orally to ruminants without such a high degree of degradation taking place.
SUMMARY OF THE INVENTION
It has now been discovered that materials intended to be administered orally to ruminants can be effectively protected from the ruminant environment if the materials are first coated with a polymer composition of an imidazoline modified styrene-acrylonitrile polymer and preferably an hydroxyethylimidazoline modified styrene-acrylonitrile polymer containing from about 15 to about 35 weight percent polymerized acrylonitrile and, correspondingly from about 85 to about 65 weight percent styrene, and having a molecular weight of from about 60,000 to about 200,000, which polymer contains from 14 to 23 mole percent hydroxyethyl imidazoline modification. It has been found that these polymers resist not only the extremely degradative microbial environment in the rumen, but also the solubilizing action of the rumen in vivo fluid (which has a pH from about 5.5 to about 6.5 or more). The imidazoline modified polymer has been found to remain insoluble at about pH 6 or higher for periods of from about 16 to about 20 hours but is soluble in less than 3 hours at about pH 3 or lower and has therefore been found to be highly suitable in the present invention.
These criteria have been arrived at by consideration of the conditions normally existing in the ruminant digestive system. For normal feedstuffs the residence time in the rumen is from about 4 to about 72 hours, usually around 20 hours, and the residence time in the abomasum and lower intestine is rarely more than 3 hours and frequently less than 30 minutes.
DETAILED DESCRIPTION OF THE INVENTION
The protective medicament and nutrient compositions of this invention can be used successfully when a composition consists mainly of the material to be protected, covered with a very thin continuous layer of the imidazoline modified polymer (wherein the weight of the coating can represent as little as about 5 weight percent or less, but is generally from about 5 weight percent to about 80 weight percent of the total weight of the composition). Preferably, but not necessarily, the medicament or nutrient portion of the rumen stable compositions of this invention should be solid at temperatures below about 40° C. Typical, nonlimiting examples of medicaments that can be utilized in the practice of this invention include anthelmintics such as crufomate, antibiotics such as chloramphenicol, bacitracin, bacitracin zinc, erythromycin, oxytetracycline and the like, antibacterials, antivirals, insecticides, growth stimulants, anthelmintics, hormones, vaccines, estrogens, androgens, steroids, tranquilizers and analgesics as well as materials that are often considered as nutrients of feedstuffs such as carbohydrates, fats, proteins, amino acids, vitamins, minerals and the like. For purposes of the present invention such "nutrients" can be considered the equivalent and inclusive of "medicaments" and "feedstuffs."
In order to obtain coated medicaments in the practice of the present invention, the polymer coating material is dissolved in a selected organic solvent. Suitable solvents include, for example, aliphatic hydrocarbons, such as hexane, cyclohexane or the like; aromatic hydrocarbons, such as toluene and the like; halogenated hydrocarbons, such as trichloroethylene, methylene chloride, chloroform and the like; aliphatic esters, such as ethylacetate or ketones such as acetone and methylethyl ketone, alcohols such as methanol, ethanol and alcohol mixtures and the like, and subsequently spray the resulting solution over particles of the medicament to be protected. Generally, the viscosity of the polymer coating material employed is in the range of from about 10 to about 200 cps.
The particles generally result by simply compressing the material to be protected into a so-called unit dosage form such as a tablet or a smaller particle, several which can be used simultaneously as a unit dose, if desired. Such particles can also be prepared by utilizing known extrusion methods. Conventional methods for coating particulated medicaments and nutrients such as, for example, conventional pill coating procedures, pan coating or fluidized bed procedures can also be readily utilized by those skilled in the art in the preparation of the coated products of the present invention.
In the treatment of ruminants, the rumen stable medicament and/or nutrient compositions of the present invention are generally admixed with the ordinary feed that is to be consumed by the ruminants. Therefore, improved feed compositions comprising a blend of common animal food material with a solid, particulated rumen stable imidazoline polymer coated medicament or nutrient material that can be solubilized in the presence of gastric and/or intestinal fluids constitutes one of the preferred embodiments of the present invention.
It should be understood that the imidazoline polymer composition of this invention need not necessarily be used in the pure state for successful results. For example, other materials (in addition to the medicament and/or nutrient) can also be present in significant amounts in the compositions of this invention, so long as the basic protective abilities of the polymer composition are not destroyed. Materials such as dyes, stabilizers, pigments, plasticizers (such as esters of phthalic acid, e.g., dibutyl-, diethyl-, butylbenzyl- and dioctyl triphenylphosphate-; polyethyleneglycol and the like), can be present in the protected medicaments and/or nutrients of this invention, in some instances, in amounts up to about 10 weight percent, if desired.
The nutrient or therapeutic material may be in the form of discrete bodies or particles or spheres having a substantially continuous surface coating of the polymer or it may be a mixture in which particles of the material are dispersed throughout a matrix of the polymer. Other combinations are also possible, such as an agglomeration of individually surface-coated particles bonded together by the polymer. The coating thickness of polymer on such beads or particles usually ranges from about 20 to about 200 microns.
Where appropriate, the nutrient or therapeutic composition may be in the form of a comparatively large body such as a tablet or lozenge. Generally, however, the composition will be in the form of small sized particles of from about 0.1 to about 2.0 mm., preferably of the order of about 1.0 mm., more preferably between 0.1 and 1.0 mm. Particles of this size can readily pass between the rumen and the abomasum and are not readily trapped by froth in the rumen, thus minimizing losses by mastication. For similar reasons the density of the composition should be as near as practicable to unity. The compositions of the present invention may include two or more nutrients or therapeutic agents and may in addition include biologically inert adjuvants or filler materials to adjust the density or other physical properties of the compositions as discussed above. The present invention also extends to include a method for rendering a nutrient or therapeutic material resistant to microbial attack within the rumen of ruminant animals which method comprises the step of treating the material with the polymer hereinbefore described.
Such a treatment may involve the coating of discrete bodies or particles of the nutrient or therapeutic material with the polymer or the incorporation of such bodies or particles into a matrix of the polymer as hereinbefore described. Another alternative is the precoating of such particles followed or accomplished by agglomeration of the coated particles into larger aggregates held together by the polymer.
In order that the compositions of the invention, particularly those containing amino acids or proteinaceous materials, may be adequately protected, it is necessary to insure that treatment of the particles results in at least the surface portion of each particle being continuously coated or encapsulated as completely as possible with the polymer. Pinholes or other discontinuities in the coating may allow attack on the material by rumen microflora. The use of fairly thick coatings or multiple coating techniques is thus advisable but, on the other hand, excessively thick coatings are generally to be avoided both for economic reasons and because of possible inhibition of efficacious release in the abomasum or intestine.
Generally, for smaller particles of from about 0.1 to about 1.0 mm., coating thicknesses are usually maintained at about 0.001 inch to about 0.0015 inch (0.025 to about 0.04 mm.), which usually corresponds to weight of coating equal to from about 5 to about 80 percent by weight of the material to be coated.
In a further aspect, this invention provides a method of treating ruminant animals, which comprises administering to the animal a nutrient or therapeutic composition or supplement which comprises the combination of a nutrient or therapeutic material and the hereinbefore described polymer, said combination being of such form that the material is thereby rendered resistant to attack and breakdown within the rumen of the animal but remains susceptible to breakdown and digestion within the abomasum or small intestine of the animal. In another aspect, this invention provides a method of protecting a nutrient or therapeutic material from degradation by moisture in storage, said method comprising the combination of said nutrient or therapeutic material and said hereinbefore described polymer, said combination being resistant to penetration by moisture under usual storage conditions.
In order that the present invention in its various aspects may be more fully and completely understood, examples will now be given showing the preparation, characterization, properties and uses of typical animal feed supplements in accordance with the invention. These examples, however, are not to be construed as limiting the invention. Except where otherwise indicated all parts and percentages are by weight and temperatures are uncorrected.
EXAMPLE 1
Preparation of Imidazoline Modified Styrene-Acrylonitrile Polymer
A 500 ml. 3-necked flask equipped with a mechanical stirrer, thermowell with thermometer, a nitrogen purge inlet, and a water cooled condensor was charged with 1.0 g. of zinc sulfate heptahydrate (0.0035 mole), 100.0 g. of aminoethyl-ethanolamine (AEEA) (0.96 mole 4.8 fold excess), and 42.6 g. of a styrene-acrylonitrile resin having a molecular weight of 190,000 and containing about 0.20 mole of nitrile groups. A slow nitrogen purge was started and the reaction mixture was heated to 150° C. at which point ammonia evolution was detected as shown by the change in color of an ammonia trap from yellow to blue (bromocresol green indicator). The reaction mixture was heated to 198° to 209° C. for three hours giving a light yellow solution of polymer. A total of 84.6 cc (0.0846 mole) of 1.000 N HCl was consumed by titration of the ammonia and entrained AEEA collected in the trap.
The polymeric product was recovered by precipitating in water while stirring. Filtration gave a white solid filter cake which was washed three times with water and dried under vacuum overnight at room temperature. The product was a finely divided, white, free-flowing powder. NMR analysis of the dry polymer dissolved in CDCl 3 showed it contained 14.5 mole percent hydroxyethyl imidazoline functionality.
Following the above procedure various imidazoline modified polymers were prepared and tested as shown in Table I.
The imidazoline modified copolymers were tested for performance at pH 6 and 3 by studying the rate of migration of methionine through a thin diaphragm (0.006-0.009 inch) of the pH sensitive resin. Methionine is a common animal feed supplement. The thin diaphragm mimics the coating around the prills. A resin which is a barrier to the migration of the methionine through it as a diaphragm in a pH 6 buffer solution should also be a barrier at pH 6 as a coating over methionine prills. Also, a resin which swells enough at pH 3 to allow rapid migration of methionine through it as a diaphragm should also release methionine at pH 3 as a coating over methionine prills. The credibility of results with a diaphragm depends upon its thinness and its integrity during the experiment. The diaphragms were produced by first casting sheets from one gram of resin dissolved in about 9 g of chloroform and poured evenly over an area of 21/4 by 4 inches marked out upon a taut flat sheet of Tedlar (polyvinyl fluoride film) taped to a level surface (e.g., Formica board) in a hood. After about 16-20 hours of drying (overnight), the sheets were carefully removed from the Tedlar without damage and one inch diameter disks are punched out with a sharp punch. The disks were used as diaphragms in the cell used to test the performance of the resin. A plasticizer was usually included with the resin in the chloroform solution in order to reduce brittleness and increase the rate and amount of swelling at pH 3. The disks were allowed to dry for at least two days at room conditions before testing. To test a resin for performance two elbows of #15 Pyrex glass O-ring joints were clamped together with gaskets and a diaphragm to form a cell. The cell parts had been warmed to about 80° C. in an oven in order to keep the diaphragm slightly softened when the flanges of the cell are clamped. An intact disk of resin (free of pinholes or cracks) had been selected by viewing against a source of bright light. The disk had been warmed on a surface of about 70° C. (e.g., the flat metal rack in the 80° C. oven) and flattened by gentle pressing before clamping into the cell. After the cell was formed about 10 g of a pH buffer solution containing 3% of dissolved methionine was added to the left arm of the cell and 10 g of the same pH buffer without the methionine was added to the right arm of the cell. The integrity of the diaphragm was established by placing a stainless steel rod in each arm of the cell and measuring the electrical resistance across the diaphragm. When the resistance was greater than 10 7 ohms (top of the range of the Leeds and Northup AC bridge), it was assumed that the diaphragm was intact. Without the diaphragm, the resistance of the buffer solution between the electrodes was less than 10 3 ohms. The tops of the cell were then capped with a thin plastic film (e.g., SARAN WRAP®) held tightly in place with small rubber bands and the cell placed on a slowly revolving rack (e.g., 2.3 RPM for these studies) in a 38°-40° C. chamber. (The body temperature of a cow is 38° C.) For the pH 6 buffer, about 24 hours of incubation was allowed to match the residence time of food in the rumen of a cow. For the pH 3 buffer, 3 hours of incubation was allowed to match the residence time of food in the abomasum and upper intestine of a cow. After the incubation period, the solutions were separately filtered and the concentration of methionine in each solution was determined by NMR spectrometry (EM 360 60 MH z NMR Spectrometer, Varian Instruments), using the area of the major peak for methionine (pendant CH 3 attached to S in the molecule [CH 3 SCH 2 CH 2 CH(NH 2 )COOH]) related to the area at a concentration of 3%. The accuracy of the determination appears to be ±0.05% methionine. The percent migration was calculated for the time period involved. The maximum migration would be 50% of the 3% methionine; or 1.5% methionine in the right arm.
Table I__________________________________________________________________________Methionine Migration and Swelling Experiments with Thin Cast Resins inpH 6.3 and pH 3.2 Buffer Solutions at 40° C.10% Methionine Migration Swelling Weight GainChloroforms (% of 3%) (%)Viscosity pH 6.3 pH 3.2 pH 6.3 pH 3.2Run (cps) Diaphragm Composition Hrs % Hrs % Hrs % Hrs %__________________________________________________________________________1 45.5 12.8 mole % IM.sup.6 -S/An.sup.1 + 10% DBP.sup.4 21 0 3 0 24 33 3 552 35 14.5 mole % IM.sup.6 -S/AN.sup.1 + 10% DBP 21 7 3 15 21.5 44 3 1563 27.5 16.1 mole % IM.sup.6 -S/AN.sup.1 + 10% DBP 21 13 3 50 21 60 3 3344 18.5 16.7 mole % IM.sup.6 -S/AN.sup.2 + 5% DBP 23 17 3 50 23 41 3 disintegrated5 28 18.2 mole % IM.sup.6 -S/AN.sup.1 + 10% DBP 18.5 15 3 50 18 62 3 disintegrated6 95,000 20 mole % IM.sup.6 -S/AN.sup.1 + 10% C.A-4.sup.5 23 10 3 14 24 52 3 4597 29.5 21.9 mole % IM.sup.6 -S/AN.sup.3 + 5% DBP 24 32 3 50 24 99 3 dissolved8 28 22.4 mole % IM.sup.6 -S/AN.sup.1 (no plas- 23.5 20 3 50 23.5 67 3 disintegrated ticizer)9 28 22.4 mole % IM.sup.6 -S/an.sup.1 + 10% DBP 18 17 1 50 17 84 1 disintegrated 10 26.5 25 mole % IM.sup.6 -S/an.sup.1 + 5% DBP 25 50 1 50 25 141 1 disintegrated__________________________________________________________________________ Footnotes to Table I .sup.1 Polymer containing about 75 weight percent polymerized styrene and 25 weight percent polymerized acrylonitrile and having a molecular weight of about 185,000. .sup.2 Same as .sup.1 except MW about 65,000 .sup.3 Polymer containing about 65 weight percent polymerized styrene and 35 weight percent polymerized acrylonitrile and having a molecular weight of about 150,000. .sup.4 DBP = dibutylphthalate plasticizer. .sup.5 C.A. 4 = Citroflex ® A4 plasticizer. .sup.6 IM = Hydroxyethyl imidazoline modification.
From Table I, Run 1, it is seen that a modification of 12.8 mole % allowed no methionine migration in 3 hours at pH 3.2. Thus, this amount of modification is too low. At 25 mole % modification, Run 10, the diaphragm did not prevent migration at pH 6.3, which indicates that this modification is too high. The preferred amount of modification appears to be about 16 mole %, Run 3.
Various modifications may be made in the present invention without departing from the spirit or scope thereof and it is understood that we limit ourselves only as defined in the appended claims. | An imidazoline modified styrene-acrylonitrile polymer composition which is substantially insoluble in aqueous media at about pH 6 or more but swellable or soluble at pH 3 or less is employed as a coating for nutrient or therapeutic substances for administration to ruminants. The substances thus are rendered resistant to attack and breakdown in the rumen yet remain susceptible to release and digestion within the abomasum or small intestine of the animal. | 2 |
TECHNICAL FIELD
The present invention relates generally to an apparatus and method for isolating vibrating structures and in particular, to a vibration cancellation mount and method that comprises a fluidic driver filling and venting an elastomeric air spring so that the spring oscillates at the frequency and phase that cancels the vibrations emanating from the vibrating structure mounted thereto. By employing a fluidic driver, the vibration cancellation mount does not suffer from high distortion when subjected to frequencies substantially higher than 100 Hz.
BACKGROUND OF THE INVENTION
Olson, U.S. Pat. No. 2,964,272 discloses the basic concept behind vibration cancellation systems. Olson discloses a system comprised of a driving element, a vibration sensing element and an electrical signal amplifier. The sensing element senses the vibration of a structure and converts the vibration to an electrical signal which is then sent to the amplifier. The amplifier amplifies this signal which operates the driver. The driver, which is mounted between the vibrating structure and a static structure, converts the signal from the amplifier into a mechanical force. By adjusting the phase of the signal coming from the amplifier the driver can be operated so as to counteract the vibration emanating from the structure.
Over the years various forms and types of vibration cancellation systems have been suggested and employed in a variety of applications.
Boothe, U.S. Pat. No. 3,189,303 discloses an active mount for supporting heavy machinery comprised of a pneumatic container or air spring for supporting a load, and a system for supplying air to the container in accordance with the force applied thereto by the load. The pneumatic system utilizes an air source for supplying air to a first valve which is positioned to be actuatable by the force of the load and designed to produce a pressure which is proportional to the force of the load. Air from the first regulator is directed through a stabilizing zone to a second valve and from the second valve, the air is delivered to the air spring.
Curwen, U.S. Pat. No. 3,216,679 discloses an active vibration isolator comprised of a vertically displaceable piston disposed within a cylinder and having means for receiving a load. A valve controls the flow of gas into the cylinder so as to move the piston vertically in response to the load.
Scharton et al., U.S. Pat. No. 3,606,233 discloses a combined active and passive isolation mount wherein the active portion includes a piston, coupled to the vibration sources via a piston rod, adapted for movement within a cylinder to which the isolated mass is mechanically coupled. The piston separates two chambers within the cylinder. The system provides isolation by using a servovalve to control the relative pressure between the chambers in such a manner that the velocity of the cylinder counteracts the velocity of the piston.
Schubert et al., U.S. Pat. No. 3,701,499 discloses an active isolation system that includes a servovalve controlled hydraulic actuator to cancel vibrations
Malueg, U.S. Pat. No. 4,033,541 discloses a system that uses linear actuators to stabilize sensitive apparatus from translational and rotational vibrations emanating from the structure on which the apparatus is mounted.
Phillips, U.S. Pat. No. 4,336,917 discloses a shock and vibration isolation system having a plurality of isolators. Each isolator has two gas driven pistons connected to an accumulator/controller that supplies controlled amounts of air. The flow of gas into the accumulator/controller is governed by a valve.
Van Gerpen, U.S. Pat. No. 4,363,377 discloses an active seat suspension control system in which a hydraulic cylinder is coupled to the seat. A source of pressurized fluid to the cylinder allows the vertical position of the seat to be adjusted. The amount of gas flow into the cylinder is governed by an electro-hydraulic valve.
Abrams et al., U.S. Pat. No. 4,546,960 discloses a vibration isolation assembly which includes a servovalve in operative communication between a fluid supply source, a gas supply source and a viscous damper. Control logic means governs the servovalve to adjust both the gas and fluid pressures in the viscous damper in response to sensed vibration so as to attenuate the vibration.
Schubert, U.S. Pat. No. 4,757,980 discloses a vibration isolation system comprising a damper having a servovalve fluidly coupling a load supporting actuator to an accumulator.
Decker et al., U.S. Pat. No. 4,802,648 discloses an engine mount having an air cushion which functions like a pneumatic spring element and which can be inflated and vented via a valve device.
Hoying et al., U.S. Pat. No., 4,828,234 discloses a hydraulic mount assembly with a self-pumping air bladder. The pressurization of the bladder is controlled by a pneumatic control circuit that includes check valves and shuttle valves.
Each of the arrangements described in the above mentioned patents employs some type of mechanical device such as a valve, servovalve or actuator to transform the amplitude and frequency of an electrical cancelling signal into a mechanical cancelling oscillation having the same frequency and amplitude. Because these devices are comprised of mechanically linked, moving parts, they suffer from high distortion when subjected to high frequency signals, and consequently, are unable to vary the pressure of a gas or fluid fast enough to generate a consistent cancelling signal. Thus for example, the systems in Abrams et al., Scharton et al., Schubert et al., and Malueg all have an upper frequency limit of about 100 Hz.
Accordingly, a need exists for a vibration cancellation mount that can operate at frequencies substantially greater than 100 Hz without suffering from the high distortion experienced by the systems found in the prior art.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a vibration cancellation mount that has a minimum of moving parts.
Another object of the present invention is to provide a vibration cancellation mount that is compact and lightweight.
Yet another object of the present invention is to provide a vibration cancellation mount that can operate at frequencies substantially greater than 100 Hz.
The present invention achieves the above-stated objects by incorporating within a vibration cancellation system a fluidic driver that fills and vents an elastomeric air spring so that the spring's oscillations cancel any vibrations emanating from a vibrating structure mounted thereto.
These and other objects, features, and advantages of the present invention are specifically set forth in or will become apparent from the following detailed description of a preferred embodiment of the invention when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic of a vibration cancellation system incorporating the vibration cancellation mount contemplated by the present invention.
FIG. 2 is a fluidic circuit diagram of the vibration cancellation mount of FIG. 1.
FIG. 3 is a schematic representation in the form of a fluidic lamina of a fluidic amplifier used in the vibration cancellation mount of FIG. 2.
FIG. 4 is a exploded view of the fluidic driver of the cancellation mount of FIG. 1.
FIG. 4A is a cross-sectional view taken along line 4A--4A of FIG. 4.
FIG. 4B is a bottom plan view of the sectional view driver of FIG. 4.
FIG. 5 is a partly cutaway, plan view of an alternative embodiment of the cancellation mount of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, FIG. 1 schematically depicts a vibration cancellation system generally denoted by the reference numeral 10, a supporting structure 12 which is to be isolated from any vibrations emanating from a vibrating supported structure 14. The vibration cancellation system 10 is comprised of a cancellation controller 16, an air supply 18, vibration sensors or accelerometers 20 and 21, and a vibration cancellation mount 40 which is operably disposed between the supporting structure 12 and the supported structure 14. The cancellation controller 15 receives electrical vibration signals from the sensor 20 mounted on the vibrating structure 14 and the sensor 21 mounted on the supporting structure 12, preferably, in close proximity to the mount 40. The controller 16 then generates an electrical cancellation signal. For example, if the sensors 20 and 21 detect a sinusoidal vibration, the controller 16 will generate a sinusoidal cancellation signal having an amplitude and phase such that the resulting motion of the mount 40 isolates the supporting structure 12 from the vibrating structure 14. The cancellation controller 16 is commercially available and can, for example, be purchased from Active Noise and Vibration Technologies, Inc., 3811 East Weir Avenue, Phoenix, Ariz. 85040. As a person having ordinary skill in the art would appreciate, the number and positioning of the vibration sensors may vary with different applications and controllers.
The mount 40 is comprised of a fluidic driver 42 coupled to an elastomeric air spring 86 having a rigid base 87. The fluidic driver 42 has a housing 44 encompassing an inlet member 46 mounted atop a stack 60 of fluidic laminae, (see FIG. 4). The member 46 has an inlet port 48 coupled to the air supply 18 via supply conduit 26, and an outlet port 58 coupled to the air supply 18 via a return conduit 28. An electroacoustic transducer 30 is mounted in a chamber 50 within the member 46. An inlet conduit 52 places the transducer 30 in fluidic communication with a hole 61 in the first lamina of the stack 60. Wires 34 and 36 couple the transducer 30 to the controller 16. The electroacoustic transducer 30 receives the electrical cancellation signal from the controller 16 and converts this signal into an acoustical signal.
The stack 60 of fluidic laminae is configured and arranged as a plurality of stages 1,2,3 . . . N in series. Each of the stages 1,2,3 . . . N includes one or more fluidic proportional amplifiers 62 in parallel arrangement. In the preferred embodiment, the stack 60 has four stages in series arrangement. The first stage having a single amplifier 62, the second stage having two amplifiers 62 in parallel arrangement, the third stage having four amplifiers 62 in parallel arrangement, and the fourth stage having six amplifiers 62 in parallel arrangement. For clarity FIG. 2 only depicts a single fluidic amplifier in each stage. As one skilled in the art would appreciate, the number of stages and/or the number of fluidic amplifiers must be selected so that the amplitude of the acoustic signal exiting the last stage matches the amplitude of the vibrations emanating from the vibrating structure 14.
FIG. 2 illustrates the configuration and arrangement of laminae in the stack 60 in the form of a fluidic circuit diagram. For purposes of clarity reference numerals are only indicated for the first stage. Each of the stages 1,2,3 . . . N, has an air supply port 63, a first and second control ports 64 and 66, a first and second output port 68 and 70 and a vent 72. The input port 63 is in fluid communication with the supply conduit 26 and the flow therebetween is controlled by a capillary 74. The first control port 64 is fluidly coupled to the transducer 30 and the second control port 66 is fluidly coupled to the supply conduit 26 downstream of the capillary 74. A needle valve 76 controls the flow to the second control port 66, and a needle valve 77 controls the flow to the first control port 64. The first and second output ports 68 and 70 are coupled to the first and second input ports of the next stage, with the final stage having one of its output ports 68 in fluid communication with the air spring 86 via an exit conduit 43. The other output port 70 and the vent 72 are disposed in fluid communication with the return conduit 28.
To fully appreciate what occurs within each of the stages 1,2,3 . . . N, a typical fluidic proportional amplifier 62 is depicted, schematically in the form of a fluidic lamina in FIG. 3. In the amplifier 62 the supply pressure Ps in the supply port 63 is converted to velocity in the form of a jet of fluid 80 issuing from a nozzle 82. The jet of fluid 80 travels from the exit of the nozzle 82, across a vent region 84, to a splitter 86, and then to the first and second output ports 68 and 70. The first and second control ports, 64 and 66 respectively, are located immediately downstream of the nozzle 82, perpendicular to the jet 80, and opposite each other. The jet 80 is easily deflected laterally by the control pressures Pc1 and Pc2 which are a small fraction of the supply pressure Ps. If the control pressures Pc1 and Pc2 are equal, the jet 80 is not deflected and divides equally at the the splitter 86. The pressures, Po1 and Po2, recovered at each output port 68 and 70 are then the same. If the control pressures Pc1 and Pc2 are unequal, the differential pressure between the two control pressures will cause the jet 80 to deflect away from the control port with the higher pressure. Deflection of the jet 80 causes the output port that receives a larger portion of the jet to recover more pressure. The difference in recovered pressure (Po2-Po1) is proportional to the degree of deflection of the jet 80 which is in turn proportional to the difference in control pressures (Pc1-Pc2).
In the embodiment depicted in FIG. 1, the elastomeric air spring 86 has a single active chamber 88 which receives the jet 80 through the exit conduit 43 of the stack 60. The chamber 88 is active in that it expands and contracts in response to being filled and vented of air due to fluctuations in the jet 80. Importantly, in order for the air spring 86 to expand and contract sufficiently to counter the dynamic forces of the vibrating structure 14 at high frequencies, its interior surface must be exposed to a substantially uniform pressure distribution in all directions. This means that standing waves must not be allowed to form either within the interior volume of the air spring 86 or within the conduit 43 which places the interior of the mount 86 in fluid communication with the discharge of the fluidic driver 42. Because the wavelength of an acoustical signal is inversely proportional to its frequency, it has been found that the formation of such waves can be prevented if the interior of the air spring 86 is configured so that its largest, linear dimension 85 is smaller than the wavelength of the acoustical signal at the highest frequency at which the cancellation mount will be operating for a particular application. Preferably, the dimension 85 is about a tenth or less than this wavelength. The air spring 86 is commercially available and can be purchased, for example, from Firestone Industrial Products Company, 1700 Firestone Blvd., Noblesville, Ind. 46060-3023.
Alternately, a dual chamber air spring 90 can be used, (see FIG. 5). The dual chamber air spring 90 has an active chamber 92 separated from a passive chamber 94 by a reaction mass 96. The chamber 92 functions like chamber 88 but has a smaller volume, while the chamber 94 is passive in that the volume of air within the chamber 94 remains substantially constant. An orifice 97 within the reaction mass 96 places the chambers 92 and 94 in fluid communication with each other and prevents the fluctuations in the active chamber 92 from affecting the air in the passive chamber 94. Preferably, the reaction mass 96 is coupled to the air spring 90 by a clamp 99. Because the dual chamber air spring 90 has a smaller active volume than the air spring 86, it does not require as large a force to cause it to expand, and therefore it can be driven by a smaller fluidic drive. Another advantage to the dual chamber air spring 90 is that in the event of a failure in the cancellation system 10, the passive chamber 94 will still provide some dampening of the vibrations emanating from the vibrating structure 14 due to the spring's elasticity and the compressibility of the air held therein. As in the chamber 88, to avoid standing waves, the largest, linear dimension 95 of the active chamber 92 is sized to be smaller than the wavelength of the acoustical signal at the highest frequency at which the cancellation mount will be operating for a particular application. Preferably, the dimension 95 is about a tenth or less than this wavelength.
In operation, the sensors 20 and 21 detect a vibration and transmit a vibration signal to the controller 16. In response, the controller 16 generates a cancellation signal. The transducer 30 receives the cancellation signal and converts it into an acoustic signal. This acoustic signal causes the difference in control pressures (Pc1-Pc2) in the fluidic driver 42 to fluctuate synchronously with the acoustic signal, which in turn causes the jet 80 to deflect synchronously with the cancellation signal. As the jet 80 is deflected, the air spring 86 is alternately filled and vented with air so that the air spring 86 expands and contracts to match the amplitude of the detected vibration, but sufficiently out of phase with this vibration so as to effectively cancel it. For example, as a vibration forces the vibrating structures 14 toward the supporting structure 12 the fluidic driver 42 pumps air into the air spring 86 so that it expands sufficiently to counter this movement.
Because the fluidic driver 42 has no mechanically moving parts, it does suffer from high distortion at frequencies greater than 100 Hz. Consequently, the vibration cancellation mount 40 is readily capable of cancelling vibrations having frequencies anywhere in the audio frequency spectrum so long as the interior dimensions of the mount 40 are sufficiently small so as not to generate a standing wave therein at the highest frequency of interest.
Various modifications and alterations to the above described system will be apparent to those skilled in the art. Accordingly, the foregoing detailed description of the preferred embodiment of the invention should be considered exemplary in nature and not as limiting to the scope and spirit of the invention as set forth in the following claims. | A vibration cancellation mount for use in a vibration cancellation system is provided that includes a fluidic driver providing a modulated air stream to an elastomeric air spring. The pressure of the air stream is caused to fluctuate by an acoustical cancelling signal generated by an electroacoustic transducer electrically coupled to cancellation controller. As this pressure varies the air spring is filled and vented so that it responds at the same frequency and phase as the cancellation signal and thereby cancels the vibrations emanating from a vibrating structure mounted thereto. By employing a fluidic driver, the vibration cancellation mount is not frequency limited and can cancel vibrations having frequencies anywhere in the audio frequency spectrum. | 5 |
FIELD OF THE INVENTION
[0001] The invention is in the field of thermosensitive carriers for the targeted, local delivery of drugs or diagnostic agents. The invention relates to lipidomimetic compounds, and particularly pertains to carriers such as liposomes, suitable for the temperature-responsive release of materials contained therein, and to the localized delivery of drugs and/or imaging agents by means of temperature-responsive release carriers.
BACKGROUND OF THE INVENTION
[0002] Many diseases that are mostly localized in a certain tissue are treated with systemically administered drugs. A well-known example of standard cancer therapy is a systemic chemotherapy coming along with significant side effects for the patient due to undesired biodistribution and toxicity. The therapeutic window of these drugs is usually defined by the minimal required therapeutic concentration in the diseased tissue on the one hand, and the toxic effects in non-targeted organs, e.g. liver, spleen, on the other.
[0003] Localized treatment by, for example, local release of cytostatics from nanocarriers promises a more efficient treatment and a larger therapeutic window compared to standard therapeutics. Localized drug delivery is also important if other therapeutic options such as surgery are too risky as is often the case for liver cancers. Localized drug delivery can also become the preferred treatment option for many indications in cardiovascular disease (CVD), such as atherosclerosis in the coronary arteries.
[0004] Medical imaging technology, such as magnetic resonance imaging (MRI) or ultrasound imaging, can not only be used for treatment planning, but also to control local drug delivery under image guidance. Focused ultrasound is the method of choice to induce local drug delivery, since it offers several advantages. This technique is non-invasive, can be focused on the diseased tissue and shows only very limited adverse effects on the surrounding tissue. Ultrasound can provide two kinds of trigger for drug delivery. First, the target tissue can be heated in a controlled way with a precision of about half a degree centigrade in a temperature range from body temperature up to 100° C. Second, the ultrasound waves are strong pressure oscillations that provide a stimulus for drug delivery based on mechanical forces.
[0005] The skilled person faces several challenges in providing carrier systems for the release of materials such as drugs or imaging compounds. Thus, e.g., the carrier system needs to be designed such that it can be loaded with a sufficient amount of said materials. Particularly if the material to be released comprises drugs, the carrier system should be sensitive to an external stimulus, such as (local) changes in temperature or pressure which allow for quick and localized release of a drug. Moreover, the drug delivery process needs to be under full control, i.e. the drug release at the site of treatment must be measurable in vivo, the amount and rate of drug release should serve as an input parameter for the determination of the subsequent stimulus application, hence drug delivery could be controlled in an image-guided feedback loop.
[0006] A significant improvement in the efficacy of liposomal drug therapies can be obtained by triggering the release of drugs by means of an external stimulus. One approach to trigger the release of encapsulated molecules is the use of temperature-sensitive liposomes. 1 In this case, the release of the drug occurs above the melting phase transition temperature (Tm) of the liposome membrane. At Tm, structural changes in the lipid membrane occur as it transfers from a gel-like to the liquid state phase. This transition leads to a distinct increase in the permeability of the membrane for solutes and water. The incorporation of phosphatidylcholines, such as lyso-PC, acetylated MPPC, and platelet activation factor (PAF), in the bilayer of liposomes has a pronounced effect on the properties of the liposomes. In 1988, Bratton et al. demonstrated that these lipids can be utilized to decrease the Tm of dipalmitoylphosphatidylcholine (DPPC)-based liposomes.2 Needham et al. have designed low temperature-sensitive liposomes (LTSLs) composed of lyso-PC/DPPC/DPPE-PEG2000 that release encapsulated doxorubicin (ThermoDox®) in a matter of seconds in response to mild hyperthermic conditions (39-42° C.).3 The quick release of aqueous solutes from the interior of these temperature-sensitive systems at temperatures close to the Tm was ascribed to the formation of transient pores. These pores are thermodynamically stable in the presence of micelle-forming phospholipids, such as lyso-PC and PEGylated phospholipids. Moreover, the transient pore formation has been ascribed to the accumulation of lysolipids by lateral diffusion within the lipid bilayer. Preclinical experiments with lyso-PC (R═C15H31, FIG. 1 ) based LTSLs loaded with doxorubicin in combination with an externally applied regional temperature increase clearly showed an improved efficacy of temperature-induced drug delivery.3,4 Instead of relying on liposomal accumulation in the tumor, hyperthermia was applied during the first hour after injection of the temperature-sensitive liposomal formulation of doxorubicin. This cytostatic drug was rapidly released in the microvasculature of the tumor and subsequently taken up by the tumor cells. Although lyso-PC based LTSLs loaded with doxorubicin have been successfully applied for drug delivery in combination with needle-based RF ablation, the stability of the liposomal formulation in plasma at 37° C. is suboptimal, showing up to 40% release of doxorubicin in 1 hour.
[0007] In the field of thermosensitive carriers for the local delivery, in a subject, of therapeutic and/or diagnostic agents, a need exists for providing carriers that are capable of longer circulation times, less leakage of their active contents at normal human body temperature (37° C.), and slower clearance from the system.
[0008] A reference addressing the foregoing desire is Lars H. Lindner et al., Clinical Cancer Research, 2004, Volume 10, Issue 6, pages 2168-2178. Herein liposomes are prepared on the basis of a third component, in addition to DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) and DSPC (1,2-distearoyl-sn-glycero-3-phosphocholine). Said third component is DPPGOG (1,2-dipalmitoyl-sn-glycero-3-phospho ceroglycerol). The resulting three-component liposomes exhibit less leakage at 37° C. and a slower clearance from circulation.
[0009] The solution presented by Lindner et al. results in structurally more complex liposomes, and is limited to phospholipids. It would be desired to provide a synthetic tool to obtain thermosensitive liposomes that show an at least similar performance in avoiding leakage at 37° C., and an at least equally slow clearance, yet on the basis of a less complex liposome structure. Moreover, it would be desired to provide a synthetic tool to provide thermosensitive liposomes exhibiting a still slower clearance than the liposomes disclosed by Linder et al.
SUMMARY OF THE INVENTION
[0010] In order to better address the aforementioned desires, in one aspect, the invention presents a compound of formula I,
[0000]
[0000] wherein:
G represents a group satisfying formula II:
[0000] HO—CH 2 —{CH(OH)—CH 2 —O} m —CH 2 —{C(═O)—O—CH 2 } q formula II
[0000] each n independently is an integer from 1-30;
m is an integer from 1-10;
q is 0 or 1.
[0011] In another aspect, the invention relates to a thermosensitive carrier comprising a lipid bilayer shell enclosing a cavity, wherein the lipid bilayer comprises one or more compounds as defined above.
[0012] In a further aspect, the invention is the use of a compound of formula I as defined above, as an additive to a lipid bilayer shell of a thermosensitive carrier.
[0013] In a still further aspect, a thermosensitive carrier is presented for the local administration of a therapeutic or diagnostic agent, said carrier comprising a lipid bilayer shell enclosing a cavity, said shell and/or said cavity comprising the agent, wherein the lipid bilayer comprises a compound of formula I as defined above.
[0014] In yet another aspect, the invention relates to any of the foregoing carriers for use in the in vivo release of a substance contained therein, respectively to treatment and imaging methods comprising administering any of the foregoing carriers to an animal, preferably a human, and affecting the in vivo release of a substance contained therein.
BRIEF DESCRIPTION OF THE FIGURES
[0015] FIG. 1 shows a Cryo TEM image of temperature-sensitive liposomes containing 1 15,3 (mentioned below) in the lipid bilayer and doxorubicin and [Gd(HPDO3A)(H 2 O)] in the aqueous lumen.
[0016] FIG. 2 presents graphs showing the encapsulation of doxorubicin in the lumen of the TSL containing 1 15,3 over time.
[0017] FIG. 3 is a graph for a TSL containing 1 15, 3 in 50% fetal bovine serum (FBS) at 37° C. and 42° C. showing the release of doxorubicin at elevated temperatures.
[0018] FIG. 4 shows the fluorescence of TSLs containing 1 15,3 in 50% FBS during a linear temperature increase from 25° C. to 55° C. (heating ramp 0.5° C./min).
DETAILED DESCRIPTION OF THE INVENTION
[0019] It is to be understood that the invention is not limited to the embodiments and formulae as described hereinbefore. It is also to be understood that in the claims the word “comprising” does not exclude other elements or steps. Where an indefinite or definite article is used when referring to a singular noun e.g. “a” or “an”, “the”, this includes a plural of that noun unless something else is specifically stated.
[0020] The invention relates to carriers comprising a lipid bilayer shell. Particularly, such shells enclose a cavity, and are semipermeable, typically comprising phospholipids. The carriers include microcarriers, having a particle size of the order of a diameter of several to tens of microns, and nanocarriers, having a particle size of the order of tens to hundredths of nanometers. In the context of the invention, the carriers are hereinafter referred to as liposomes.
[0021] Liposomes are generally spherical vesicles comprising a bilayer membrane enclosing a cavity, or lumen. The bilayer can be made up of at least one phospholipid and may or may not comprise cholesterol. Liposomes can be composed of naturally-derived phospholipids with mixed lipid chains (like egg phosphatidylethanolamine), or of pure surfactant components like dioleoylphosphatidylethanolamine (DOPE). The term liposomes, as used in the description of the invention, includes lipid spheres usually denoted micelles.
[0022] A typical example of a semipermeable shell is also found in semipermeable membranes comprising a phospholipid bilayer. A phospholipid bilayer is the most permeable to small, uncharged solutes. Liposomes can be made on the basis of a phospholipid bilayer.
[0023] In a broad sense, the invention is based on the judicious insight to provide, rather than a further phospholipid component that becomes a constituent part of the lipid bilayer of a liposome, a lipidomimetic compound that can be separately incorporated into the lipid bilayer. The compounds particularly can be mixed into the lipid bilayer of a thermosensitive carrier such as a thermosensitive liposome, with the effect of prolonging the circulation time of the carrier.
Lipidomimetic Compounds
[0024] The invention, in one aspect, pertains to the lipidomimetic compounds themselves. These compounds satisfy formula (I) above. Preferably, the compounds are selected from the group consisting of the below compounds of formula III, formula IV, and combinations thereof.
[0000]
[0025] Herein, the integers m and n have the aforementioned meaning. Preferably, m is 2-6, more preferably 2-4 and most preferably 2 or, 3. Preferably each n independently is 8-24, more preferably each n independently is 12-18, and most preferably each n independently is 13, 15, or 17.
[0026] In a preferred embodiment, the compound satisfies formula V below,
[0000]
[0000] wherein G has the aforementioned meaning and r and s each independently are integers from 1-30 and the difference (r-s) is relatively small, i.e. below 10, preferably 0 to 5, and more preferably 1-3.
[0027] The compounds of the invention can be incorporated into the lipid bilayer of a thermosensitive carrier. They are generally incorporated by mixing them into the lipids of which the carriers are made. They are preferably present in a mole percentage of from 5 to 50 of the lipid bilayer, preferably 10%-30%.
[0028] The incorporation of the lipidomimetic compounds of the invention in the phospholipid bilayer of a thermosensitive liposome, allows rapid and quantitative release of drugs at a pre-defined temperature. This temperature-induced transition can also be utilized to release incorporated imaging probes (e.g. T 1 , T 2 , CEST MRI contrast agents) upon heating. Moreover, the incorporation of lipidomimetics can be utilized to tune the transmembrane water exchange rate in order to maximize the MR contrast enhancement between body temperature and hyperthermia, which is important in the field of MR image-guided drug delivery. Furthermore, the lipidomimetics do not exhibit a charge, which will positively influence the zeta potential of the liposomes, as a result of which the zeta potential is less negative than is the case with lipids comprising a phosphate group as in Linder et al.
[0029] The resulting liposomes are capable of showing a similar long or even longer circulation behaviour as the aforementioned liposomes based on DPPGOG.
Phospholipids
[0030] Preferred lipid bilayers (which can be made of lipids in general) are based on phospholipids.
[0031] Phospholipids are known and generally refer to phosphatidylcholine, phosphatidyl-ethanolamine, phosphatidylserine and phosphatidyl-inositol. In the invention it is preferred to employ phosphatidylcholine.
Thermosensitive Carriers
[0032] The invention concerns carriers that are thermosensitive. This means that the physical or chemical state of the carrier is dependent on its temperature.
[0033] Any thermosensitive carrier that can package a molecule of interest and that is intact at body temperature (i.e. 37° C.) but destroyed at any other, non-body temperature that can be tolerated by a subject may be used. Carriers of the invention include but are not limited to thermosensitive micro- and nanoparticles, thermosensitive polymersomes, thermosensitive liposomes, thermosensitive nanovesicles and thermosensitive nanospheres.
[0034] Thermosensitive nanovesicles generally have a diameter of up to 100 nm. In the context of this invention, vesicles larger than 100 nm, typically up to 5000 nm, are considered as microvesicles. The word vesicle describes any type of micro- or nanovesicle. Vesicles, such as liposomal vesicles, typically include a cavity which may contain any substance of interest. In the invention this is preferred, as outlined above.
[0035] Thermosensitive polymersomes include but are not limited to any polymer vesicle, including microvesicles and nanovesicles.
[0036] Thermosensitive liposomes include but are not limited to any liposome, including those having a prolonged half-life, e.g. PEGylated liposomes.
[0037] Thermosensitive liposomes for use in the invention ideally retain their structure at about 37°, i.e. human body temperature, but are destroyed at a higher temperature, preferably only slightly elevated above human body temperature, and preferably also above pyrexic body temperature. Typically about 42° C. is a highly useful temperature for thermally guided drug delivery.
[0038] The required heat to raise the temperature of the thermosensitive drug carriers so as to promote the destruction of the thermosensitive carriers may be used. Heat can be applied in any physiologically acceptable way, preferably by using a focused energy source capable of inducing highly localized hyperthermia. The energy can be provided through, e.g., microwaves, ultrasound, magnetic induction, infrared or light energy.
[0039] Thermosensitive liposomes are known in the art. Liposomes according to the present invention may be prepared by any of a variety of techniques that are known in the art. See, e.g., U.S. Pat. No. 4,235,871; Published PCT applications WO 96/14057; New RRC, Liposomes: A practical approach, IRL Press, Oxford (1990), pages 33-104; Lasic, D. D., Liposomes from physics to applications, Elsevier Science Publishers, Amsterdam, 1993; Liposomes, Marcel Dekker, Inc., New York (1983).
[0040] Entrapment of a drug or other substance within liposomes of the present invention may also be carried out using any conventional method in the art. In preparing liposome compositions of the present invention, stabilizers such as antioxidants and other additives may be used as long as they do not interfere substantially with the purpose of the invention.
Drug Carriers
[0041] In one aspect, the invention relates to a carrier suitable for the localized delivery of a biologically active agent, such as a drug. Hereinafter, the term “biologically active agent” will be referred to, in short, as “drug” and the carrier as a “drug carrier.” A drug carrier in the context of the present invention refers to any material in or on which a bio-active agent can be contained so as to be capable of being released in the body of a subject.
[0042] The drug carrier is to be introduced into the body of a person to be subjected to MRI. This will be e.g. by injection in the blood stream, or by other methods to introduce the carrier into body fluid.
[0043] A drug is a chemical substance used in the treatment, cure, prevention, or diagnosis of a disease or disorder, or used to otherwise enhance physical or mental well-being. The guided delivery foreseen with the present invention will mostly be useful therapeutic agents (i.e. drugs in a strict sense, intended for therapy or prevention of diseases or disorders), but also for agents that are administered for diagnostic purposes. Although other bio-active agents, i.e. those that are not therapeutic or diagnostic, such as functional food ingredients, will not generally be subjected to guided and/or monitored delivery, such could be done using the present invention if desired.
[0044] The most optimal use of the invention is attained in the case of targeted therapeutics, i.e. drugs that are intended for targeted delivery, as such delivery will by nature benefit most from the monitoring made available by the invention. This pertains, e.g., to agents in the treatment of tumors to be delivered on site, to agents in the treatment or prevention of cardiovascular disorders, such as atherosclerosis in the coronary arteries, or to antithrombotic agents (e.g. for locally resolving blood cloths) or agents that require passing the blood-brain barrier such as neuromodulators as can be used in the treatment of neural conditions such as epilepsy, Alzheimer's disease, Parkinson's disease, or stroke. Benefits from the guidance and monitoring of targeted drug delivery are also applicable to targeted diagnostic agents. Similarly as with targeted therapeutics, here too cancer is an area where site-specific delivery can be of importance.
[0045] Bio-active agents suitable for use in the present invention include biologically active agents including therapeutic drugs, endogenous molecules, and pharmacologically active agents, including antibodies; nutritional molecules; cosmetic agents; diagnostic agents; and additional contrast agents for imaging. As used herein, an active agent includes pharmacologically acceptable salts of active agents.
[0046] The drug carriers of the present invention can comprise either hydrophilic or hydrophobic bioactive agents. A hydrophilic bioactive agent could be encapsulated in the aqueous compartment of the carrier, whereas hydrophobic bioactive agents could be incorporated in hydrophobic domains of the carrier, for instance in the lipid bilayer of liposomes. Nucleic acids, carbohydrates and, in general, proteins and peptides are water soluble or hydrophilic. For instance, bioactive agents which are small molecules, lipids, lipopolysaccharides, polynucleotides and antisense nucleotides (gene therapy agents) are also envisaged. Such biologically active agents, which may be incorporated, thus include non-peptide, non-protein drugs. It is possible within the scope of the present invention to incorporate drugs of a polymeric nature, but also to incorporate drugs of a relatively small molecular weight of less than 1500 g/mol, or even less than 500 g/mol.
[0047] Accordingly, compounds envisaged for use as bioactive agents in the context of the present invention include any compound with therapeutic or prophylactic effects. It can be a compound that affects or participates in tissue growth, cell growth, cell differentiation, a compound that is able to invoke a biological action such as an immune response, or a compound that can play any other role in one or more biological processes. A non-limiting list of examples includes antimicrobial agents (including antibacterial, antiviral agents and anti-fungal agents), anti-viral agents, anti-tumor agents, thrombin inhibitors, antithrombogenic agents, thrombolytic agents, fibrinolytic agents, vasospasm inhibitors, calcium channel blockers, vasodilators, antihypertensive agents, antimicrobial agents, antibiotics, inhibitors of surface glycoprotein receptors, antiplatelet agents, antimitotics, microtubule inhibitors, anti secretory agents, actin inhibitors, remodeling inhibitors, anti metabolites, antiproliferatives (including antiangiogenesis agents), anticancer chemotherapeutic agents, anti-inflammatory steroid or non-steroidal anti-inflammatory agents, immunosuppressive agents, growth hormone antagonists, growth factors, dopamine agonists, radiotherapeutic agents, extracellular matrix components, ACE inhibitors, free radical scavengers, chelators, antioxidants, anti polymerases, and photodynamic therapy agents.
[0048] Relatively small peptides may be referred to by the number of amino acids (e.g. di-, tri-, tetrapeptides). A peptide with a relatively small number of amide bonds may also be called an oligopeptide (up to 50 amino acids), whereas a peptide with a relatively high number (more than 50 amino acids) may be called a polypeptide or protein. In addition to being a polymer of amino acid residues, certain proteins may further be characterised by the so called quaternary structure, a conglomerate of a number of polypeptides that are not necessarily chemically linked by amide bonds but are bonded by forces generally known to the skilled professional, such as electrostatic forces and Vanderwaals forces. The term peptides, proteins or mixtures thereof as used herein is to include all above mentioned possibilities.
[0049] Usually, the protein and/or peptide are selected on the basis of its biological activity. Depending on the type of polymer chosen, the product obtainable by the present process is highly suitable for controlled release of proteins and peptides. In a particular embodiment, the protein or peptide is a growth factor.
[0050] Other examples of peptides or proteins or entities comprising peptides or proteins, which may advantageously be contained in the loaded polymer include, but are not limited to, immunogenic peptides or immunogenic proteins, which include, but are not limited to, the following:
[0051] Toxins such as diphtheria toxin and tetanus toxin.
[0052] Viral surface antigens or parts of viruses such as adenoviruses, Epstein-Barr Virus, Hepatitis A Virus, Hepatitis B Virus, Herpes viruses, HIV-1, HIV-2, HTLV-III, Influenza viruses, Japanese encephalitis virus, Measles virus, Papilloma viruses, Paramyxoviruses, Polio Virus, Rabies, Virus, Rubella Virus, Vaccinia (Smallpox) viruses and Yellow Fever Virus.
[0053] Bacterial surface antigens or parts of bacteria such as Bordetella pertussis, Helicobacter pylori, Clostridium tetani, Corynebacterium diphtheria, Escherichia coli, Haemophilus influenza, Klebsiella species, Legionella pneumophila, Mycobacterium bovis, Mycobacterium leprae, Mycrobacterium tuberculosis, Neisseria gonorrhoeae, Neisseria meningitidis, Proteus species, Pseudomonas aeruginosa, Salmonella species, Shigella species, Staphylococcus aureus, Streptococcus pyogenes, Vibrio cholera and Yersinia pestis.
[0054] Surface antigens of parasites causing disease or portions of parasites such as Plasmodium vivax (malaria), Plasmodium falciparum (malaria), Plasmodium ovale (malaria), Plasmodium malariae (malaria), Leishmania tropica (leishmaniasis), Leishmania donovani ), leishmaniasis), Leishmania branziliensis (leishmaniasis), Trypanosoma rhodescense (sleeping sickness), Trypanosoma gambiense (sleeping sickness), Trypanosoma cruzi (Chagas' disease), Schistosoma mansoni (schistosomiasis), Schistosomoma haematobium (schistomiasis), Schistosoma japonicum (shichtomiasis), Trichinella spiralis (trichinosis), Stronglyloides duodenale (hookworm), Ancyclostoma duodenale (hookworm), Necator americanus (hookworm), Wucheria bancrofti (filariasis), Brugia malaya (filariasis), Loa loa (filariasis), Dipetalonema perstaris (filariasis), Dracuncula medinensis (filariasis), and Onchocerca volvulus (filariasis).
[0055] Immunoglobulins such as IgG, IgA, IgM, Antirabies immunoglobulin, and Antivaccinia immunoglobulin.
[0056] Antitoxin such as Botulinum antitoxin, diphtheria antitoxin, gas gangrene antitoxin, tetanus antitoxin.
[0057] Antigens which elicit an immune response against foot and mouth disease.
[0058] Hormones and growth factors such as follicle stimulating hormone, prolactin, angiogenin, epidermal growth factor, calcitonin, erythropoietin, thyrotropic releasing hormone, insulin, growth hormones, insulin-like growth factors 1 and 2, skeletal growth factor, human chorionic gonadotropin, luteinizing hormone, nerve growth factor, adrenocorticotropic hormone (ACTH), luteinizing hormone releasing hormone (LHRH), parathyroid hormone (PTH), thyrotropin releasing hormone (TRH), vasopressin, cholecystokinin, and corticotropin releasing hormone; cytokines, such as interferons, interleukins, colony stimulating factors, and tumor necrosis factors: fibrinolytic enzymes, such as urokinase, kidney plasminogen activator; and clotting factors, such as Protein C, Factor VIII, Factor IX, Factor VII and Antithrombin III.
[0059] Examples of other proteins or peptides are albumin, atrial natriuretic factor, renin, superoxide dismutase, alpha 1-antitrypsin, lung surfactant proteins, bacitracin, bestatin, cyclosporine, delta sleep-inducing peptide (DSIP), endorphins, glucagon, gramicidin, melanocyte inhibiting factors, neurotensin, oxytocin, somostatin, terprotide, serum thymide factor, thymosin, DDAVP, dermorphin, Met-enkephalin, peptidoglycan, satietin, thymopentin, fibrin degradation product, des-enkephalin-alpha-endorphin, gonadotropin releasing hormone, leuprolide, alpha-MSH and metkephamid.
[0060] Anti-tumor agents such as altretamin, fluorouracil, amsacrin, hydroxycarbamide, asparaginase, ifosfamid, bleomycin, lomustin, busulfan, melphalan, chlorambucil, mercaptopurin, chlormethin, methotrexate, cisplatin, mitomycin, cyclophosphamide, procarbazin, cytarabin, teniposid, dacarbazin, thiotepa, dactinomycin, tioguanin, daunorubicin, treosulphan, doxorubicin, tiophosphamide, estramucin, vinblastine, etoglucide, vincristine, etoposid, vindesin and paclitaxel.
[0061] Antimicrobial agents comprising:
[0062] Antibiotics such as ampicillin, nafcillin, amoxicillin, oxacillin, azlocillin, penicillin G, carbenicillin, penicillin V, dicloxacillin, phenethicillin, floxacillin, piperacillin, mecillinam, sulbenicillin, methicillin, ticarcillin, mezlocillin, Cephalosporins: cefaclor, cephalothin, cefadroxil, cephapirin, cefamandole, cephradine, cefatrizine, cefsulodine, cefazolin, ceftazidim, ceforanide, ceftriaxon, cefoxitin, cefuroxime, cephacetrile, latamoxef, and cephalexin. Aminoglycosides such as amikacin, neomycin, dibekacyn, kanamycin, gentamycin, netilmycin, tobramycin. Macrolides such as amphotericin B, novobiocin, bacitracin, nystatin, clindamycin, polymyxins, colistin, rovamycin, erythromycin, spectinomycin, lincomycin, vancomycin Tetracyclines such as chlortetracycline, oxytetracycline, demeclocycline, rolitetracycline, doxycycline, tetracycline and minocycline. Other antibiotics such as chloramphenicol, rifamycin, rifampicin and thiamphenicol.
[0063] Chemotherapeutic agents such as the sulfonamides sulfadiazine, sulfamethizol, sulfadimethoxin, sulfamethoxazole, sulfadimidin, sulfamethoxypyridazine, sulfafurazole, sulfaphenazol, sulfalene, sulfisomidin, sulfamerazine, sulfisoxazole and trimethoprim with sulfamethoxazole or sulfametrole.
[0064] Urinary tract antiseptics such as methanamine, quinolones(norfloxacin, cinoxacin), nalidixic acid, nitro-compounds (nitrofurantoine, nifurtoinol) and oxolinic acid.
[0065] Drug for anaerobic infections such as metronidazole.
[0066] Drugs for tuberculosis such as aminosalicyclic acid, isoniazide, cycloserine, rifampicine, ethambutol, tiocarlide, ethionamide and viomycin.
[0067] Drugs for leprosy such as amithiozone, rifampicine, clofazimine, sodium sulfoxone and diaminodiphenylsulfone (DDS, dapsone).
[0068] Antifungal agents such as amphotericin B, ketoconazole, clotrimazole, miconazole, econazole, natamycin, flucytosine, nystatine and griseofulvin.
[0069] Antiviral agents such as aciclovir, idoxuridine, amantidine, methisazone, cytarabine, vidarabine and ganciclovir.
[0070] Chemotherapy of amebiasis such as chloroquine, iodoquinol, clioquinol, metronidazole, dehydroemetine, paromomycin, diloxanide, furoatetimidazole and emetine.
[0071] Anti-malarial agents such as chloroquine, pyrimethamine, hydroxychloroquine, quinine, mefloquine, sulfadoxine/pyrimethamine, pentamidine, sodium suramin, primaquine, trimethoprim and proguanil.
[0072] Anti-helminthiasis agents such as antimony potassium tartrate, niridazole, antimony sodium dimercaptosuccinate, oxamniquine, bephenium, piperazine, dichlorophen, praziquantel, diethylcarbamazine, pyrantel parmoate, hycanthone, pyrivium pamoate, levamisole, stibophen, mebendazole, tetramisole, metrifonate, thiobendazole and niclosamide.
[0073] Anti-inflammatory agents such as acetylsalicyclic acid, mefenamic acid, aclofenac, naproxen, azopropanone, niflumic acid, benzydamine, oxyphenbutazone, diclofenac, piroxicam, fenoprofen, pirprofen, flurbiprofen, sodium salicyclate, ibuprofensulindac, indomethacin, tiaprofenic acid, ketoprofen and tolmetin.
[0074] Anti-gout agents such as colchicine and allopurinol.
[0075] Centrally acting (opoid) analgesics such as alfentanil, methadone, bezitramide, morphine, buprenorfine, nicomorphine, butorfanol, pentazocine, codeine, pethidine, dextromoramide, piritranide, dextropropoxyphene, sufentanil and fentanyl.
[0076] Local anesthetics such as articaine, mepivacaine, bupivacaine, prilocalne, etidocaine, procaine, lidocaine and tetracaine.
[0077] Drugs for Parkinson's disease such as amantidine, diphenhydramine, apomorphine, ethopropazine, benztropine mesylate, lergotril, biperiden, levodopa, bromocriptine, lisuride, carbidopa, metixen, chlorphenoxamine, orphenadrine, cycrimine, procyclidine, dexetimide and trihexyphenidyl.
[0078] Centrally active muscle relaxants such as baclofen, carisoprodol, chlormezanone, chlorzoxazone, cyclobenzaprine, dantrolene, diazepam, febarbamate, mefenoxalone, mephenesin, metoxalone, methocarbamol and tolperisone.
[0079] Corticosteroids comprising:
[0080] Mineralocorticosteroids such as cortisol, desoxycorticosterone and fluorohydrocortisone.
[0081] Glucocorticosteroids such as beclomethasone, betamethasone, cortisone, dexamethasone, fluocinolone, fluocinonide, fluocortolone, fluorometholone, fluprednisolone, flurandrenolide, halcinonide, hydrocortisone, medrysone, methylprednisolone, paramethasone, prednisolone, prednisone and triamcinolone (acetonide).
[0082] Androgens comprising:
[0083] Androgenic steroids used in therapy such as danazole, fluoxymesterone, mesterolone, methyltestosterone, testosterone and salts thereof.
[0084] Anabolic steroids used in therapy such as calusterone, nandrolone and salts thereof, dromostanolone, oxandrolone, ethylestrenol, oxymetholone, methandriol, stanozolol methandrostenolone and testolactone.
[0085] Antiandrogens such as cyproterone acetate.
[0086] Estrogens comprising estrogenic steroids used in therapy such as diethylstilbestrol, estradiol, estriol, ethinylestradiol, mestranol and quinestrol.
[0087] Anti-estrogens such as chlorotrianisene, clomiphene, ethamoxytriphetol, nafoxidine and tamoxifen.
[0088] Progestins such as allylestrenol, desogestrel, dimethisterone, dydrogesterone, ethinylestrenol, ethisterone, ethynadiol diacetate, etynodiol, hydroxyprogesterone, levonorgestrel, lynestrenol, medroxyprogesterone, megestrol acetate, norethindrone, norethisterone, norethynodrel, norgestrel, and progesterone.
[0089] Thyroid drugs comprising:
[0090] Thyroid drugs used in therapy such as levothyronine and liothyronine
[0091] Anti-thyroid drugs used in therapy such as carbimazole, methimazole, methylthiouracil and propylthiouracil.
[0092] Apart from bioactive agents which are water soluble, other water-soluble compounds can be incorporated such as anti-oxidants, ions, chelating agents, dyes, imaging compounds.
[0093] Preferred therapeutic agents are in the area of cancer (e.g. antitumor) and cardiovascular disease.
[0094] Methods of preparing lipophilic drug derivatives which are suitable for nanoparticle or liposome formulation are known in the art (see e.g., U.S. Pat. No. 5,534,499 describing covalent attachment of therapeutic agents to a fatty acid chain of a phospholipid). Drugs in the present invention can also be prodrugs.
[0095] The drug may be present in the inner, the outer, or both of the compartments of the carrier, e.g. in the cavity and/or in the shell of a liposome. The distribution of the drug is independent of the distribution of any other agents comprised in the drug carrier, such as a paramagnetic chemical shift reagent or a paramagnetic agent. A combination of drugs may be used and any of these drugs may be present in the inner, the outer, or both of the compartments of the drug carrier, e.g. in the cavity and/or in the shell of a liposome.
Imaging Agents
[0096] In another aspect, the invention relates to carriers that are suitable as imaging agents, preferably for MRI. To this end, the carrier comprises (in the cavity, in the shell, or on the surface thereof) a substance capable of inducing contrast enhancement. These substances include T 1 and/or T 2 contrast enhancers as well as CEST MRI contrast enhancers.
[0097] Almost all current MRI scans are based on the imaging of bulk water molecules, which are present at a very high concentration throughout the whole body in all tissues. If the contrast between different tissues is insufficient to obtain clinical information, MRI contrast agents (CAs), such as low molecular weight complexes of gadolinium, are administered. These paramagnetic complexes reduce the longitudinal (T 1 ) and transverse relaxation times (T 2 ) of the protons of water molecules. Also manganese acts as a T 1 contrast agent. The carrier can comprise contrast enhancers for 1 H MRI, for 19 F MRI, or both. In the invention also an all-in-one concept can be realized of 19 F MRI in combination with T 1 , T 2 , and preferably also with CEST contrast, in 1 H MRI.
CEST MRI
[0098] The invention, in a preferred embodiment, also relates to CEST MRI contrast enhancement. This method serves to generate image contrast by utilizing Chemical Exchange-dependent Saturation Transfer (CEST) from selected, magnetically pre-saturated protons to the bulk water molecules determined by MRI.
[0099] If used in CEST MRI, preferred carriers of the invention, i.e. the thermosensitive carriers that have a semipermeable shell enclosing a cavity, contribute to an optimal CEST contrast enhancement. For, the advantage of these carriers is that the CEST contrast enhancement can be conducted on the basis of a paramagnetic chemical shift agent contained in the cavity, in interaction with a pool of protons or other MRI analytes also present in the cavity.
[0100] Although the invention, in this preferred embodiment, relates to the application of any CEST-type contrast enhancement to thermosensitive drug release, it is preferred to make use of more advanced CEST methods as have become available.
[0101] CEST in combination with a paramagnetic chemical shift reagent (ParaCEST) is a method, in which the magnetization of a pool of paramagnetically shifted protons of a CEST contrast agent is selectively saturated by the application of radio frequency (RF) radiation. The transfer of this saturation to bulk water molecules by proton exchange leads to a reduced amount of excitable water protons in the environment of the CEST contrast agent. Thus a decrease of the bulk water signal intensity is observed, which can be used to create a (negative) contrast enhancement in MRI images.
[0102] An approach to obtain a high CEST efficiency is based on utilizing the large number of water molecules of a solution containing a paramagnetic shift reagent (e.g. Na[Tm(dotma)(H 2 O)]), wherein “H 4 dotma” stands for α,α′,α′,α′″-tetramethyl-1,4,7,10-tetraacetic acid and dotma represents the respective fourfold deprotonated tetraanionic form of the ligand, to provide a pool of protons that are chemically shifted and that, therefore, can selectively be saturated by an RF pulse. If this system is encapsulated in a carrier, e.g. a liposome, the magnetic saturation can be transferred to the bulk water molecules at the outside of the carriers, which are not chemically shifted (LipoCEST). The amount of magnetization transfer and hence the extent of contrast enhancement are determined by the rate of the diffusion of water through the shell of the carrier, e.g. a phospholipid membrane, as well as by the amount of water within the carrier.
[0103] The optimum water exchange rate is directly correlated with the chemical shift difference between the proton pool inside of the carrier and the bulk water outside of the carrier. The paramagnetic shift that is induced on the water molecules inside the liposomes consists of two main contributions: chemical shift resulting from a direct dipolar interaction between the water molecules and the shift reagent (δ dip ), and chemical shift caused by a bulk magnetic susceptibility effect (δ bms ). The overall paramagnetic shift is the sum of these two contributions:
[0000] δ=δ dip +δ bms (1)
[0104] δ bms is zero for spherical particles, but it can be significant for anisotropic particles. The aspherical particles experience a force in a magnetic field, which causes them to align with the magnetic field lines. In the case of liposomes, this effect is further increased, if they bear paramagnetic molecules associated with the phospholipid membrane.
[0105] A reference on CEST using aspherical liposomes is Terreno, E. et al. Angew. Chem. Int. Ed. 46, 966-968 (2007).
[0106] In the invention, a paramagnetic shift reagent can be comprised in any manner in or on the carrier. It is preferred to have the shift reagent in sufficient interaction with a pool of protons by comprising both the reagent and the pool in the cavity of the carrier.
[0107] The paramagnetic chemical shift reagent or reagents can basically be any paramagnetic agent suitable to render the relatively large number of water molecules of a solution or dispersion in which it is contained, into a pool of protons that are chemically shifted regarding their MR resonance frequency, with respect to the surrounding protons of the bulk water molecules. As the liposomes comprise a shell that fundamentally allows exchange of protons with their direct environment, the saturation caused by a selective RF pulse will be transferred to the environment of the loaded thermosensitive drug carriers. Thus, upon conducting magnetic resonance imaging, the direct environment of the thermosensitive drug carriers will show a decreased signal intensity as compared to other bulk water molecules, and thus allows to detect the direct environment of the contrast agents due to a decreased signal intensity. The paramagnetic chemical shift reagent is to comprise a paramagnetic compound, i.e. any compound having paramagnetic properties. Preferably the paramagnetic compound comprises a paramagnetic metal ions, e.g. metal ions complexed by chelate ligands. Paramagnetic metal ions are known to the skilled person, and do not require elucidation here. E.g., early and late transition metals, explicitly including chromium, manganese, iron, as well as lanthanides, such as gadolinium, europium, dysprosium, holmium, erbium, thulium, ytterbium.
[0108] The paramagnetic chemical shift reagent is to comprise a chelating structure capable of strongly binding to the paramagnetic metal and allowing the metal to interact with water, or with another suitable source of protons. With respect to suitable chelating structures, reference is made to P. Caravan et al., Chem. Rev., 99, 2293-2352 (1999). Preferably the water is at least transiently coordinated to the metal of the paramagnetic reagent. With respect to paramagnetic shift mechanisms, reference is made to J. A. Peters et al., Prog. Nucl. Magn. Reson. Spectr., 28, 283-350 (1999). In one embodiment, the chelating structure itself also comprises exchangeable protons, e.g. hydroxyl, amine, or amide protons.
[0109] Suitably, the paramagnetic chemical shift reagent comprises a lanthanide ion coordinated with a chelating structure, e.g. macrocylic lanthanide(III) chelates derived from 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (H 4 dota), 1,4,7,10-tetraazacyclododecane-α,α′,α″,α″′-tetramethyl-1,4,7,10-tetraacetic acid (H 4 dotma), and related ligands that allow for an axially coordinated water molecule in the paramagnetic reagent. In this respect reference is made to Aime et al., Angew. Chem. Int. Ed., 44, 5513-5515 (2005). A number of the same, similar or different chelating units may be combined in a dendrimeric or polymeric structure providing dendritic or polymeric chemical shift reagents. A general advantage of using dendritic or polymeric paramagnetic compounds is that high effective concentrations of the paramagnetic metal complex can be achieved, without increasing the osmolarity of the solution as much as it would be the case when using mononuclear paramagnetic compounds. Here reference is made to E. Terreno, A. Barge, L. Beltrami, G. Cravotto, D. D. Castelli, F. Fedeli, B. Jebasingh, S. Aime, Chemical Communications, 2008, 600-602.
[0110] Preferably, the paramagnetic chemical shift reagent is water-soluble. Suitable chemical shift reagents are known to the person skilled in the art. The CEST contrast agents do not require any specific chemical shift reagent, as long as the shift reagent and the pool of protons have a sufficient interaction to result in a pool of chemically shifted protons.
[0111] Preferably, the paramagnetic shift reagent is a metal complex comprising a metal ion and a ligand that is based on a multidentate chelate ligand. More preferably, the interaction of the chemical shift reagent with the pool of protons is provided in the form of coordination. Thus it is preferred for the metal complex to have at least one coordination site of the metal left open for the coordination of at least one water molecule.
[0112] Examples of suitable water-soluble chemical shift reagents are [Ln(hpdo3a)(H 2 O)] (1), [Ln(dota)(H 2 O)] − (2), [Ln(dotma)(H 2 O)] − (3), [Ln(dotam)(H 2 O)] 3+ (4), and [Ln(dtpa)(H 2 O)] 2− (5), including derivatives thereof and related compounds, with Ln being a lanthanide ion.
[0113] Preferably the paramagnetic chemical shift reagent is a lanthanide complex such as in formulae I-5 below:
[0000]
[0000] wherein the lanthanide is Eu 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , and preferably is Tm 3+ or Dy 3+ .
[0114] The paramagnetic chemical shift reagent is typically comprised in the agent in an amount of from 1 mM to 2000 mM, preferably of from 10 mM to 1000 mM, and more preferably of from 50 mM to 200 mM.
[0115] The foregoing metal-containing compounds may be dissolved, emulsified, suspended or in any other form distributed homogeneously or inhomogeneously in the cavity, i.e. the inner compartment of the liposome. It may alternatively be linked to the outer compartment of the liposome by at least one covalent or non-covalent bond, or any combination of those. Furthermore the same or at least one different metal-containing compound may be present simultaneously in any of the compartments.
[0116] It can be envisaged that the paramagnetic agent and the drug are one and the same, if the drug itself comprises an appropriate metal.
[0117] Further contrast enhancement agents
[0118] The contrast agents of the invention may comprise T 1 , T 2 or T 2 * reducing agents. In this respect reference is made to Aime et al., Journal of the American Chemical Society, 2007, 129, 2430-2431. Also, an all-in-one concept can be realized of T 1 , T 2 or T 2 * and CEST contrast agents.
[0119] The chemical shift difference between the internal and the bulk water protons of the thermosensitive drug carriers, can be further enhanced by providing the thermosensitive drug carrier's membrane with a further paramagnetic agent, which is not necessarily a chemical shift reagent. Thus, the orientation of the aspherical carrier in the magnetic field is affected and the aforementioned bulk susceptibility effect is enhanced. The further paramagnetic agent is preferably an amphiphilic compound comprising a lanthanide complex (on the more polar side of the amphiphilic compound), and having an apolar tail which has a tendency to preferably integrate in and align with the lipid bilayer at the thermosensitive drug carrier's surface based on hydrophobic molecular interactions. These amphiphilic paramagnetic complexes can e.g. be:
[0000]
Combined 19 F and 1 H MR Contrast Enhancement
[0120] With the invention a suitable combination of 19 F and 1 H MR can be realized in various ways.
[0121] Thus, a dual or multiple-label MR contrast can be generated by utilizing a CEST mechanism and/or 19 F MR. Alternatively, multiple MR contrasts may be generated through the modification of the longitudinal relaxation time (T 1 ), or the transverse relaxation time (T 2 ) of the imaged analyte (typically the protons of water) by a metal-containing compound present in the carrier. Any of these contrast enhancing mechanisms may further be used in any combination thereof.
[0122] The dual/multiple labeled MRI contrast, depending on the physical state of the carrier, is monitored either in a subsequent or interleaved manner with conventional MR equipment—or simultaneously, using sequence combinations on dual-tuned spectrometer systems e.g. at 1 H and 19 F MR resonance frequencies.
[0123] In this respect the invention also relates to the use of simultaneous dual nuclei MR imaging in monitoring and/or guiding drug delivery.
[0124] The combination of a CEST and a 19 F contrast agent in a thermo-sensitive liposome offers the opportunity to monitor the drug release process independently and simultaneously by means of CEST and 19 F MRI. Simultaneous monitoring of the two different MR signals is mediated by corresponding dual-label MR techniques. This approach leads to several possible advantages. Thus, the spatial distribution of the drug-loaded particles can be assessed prior to drug release by means of CEST MRI; the 1 H CEST and the 19 F MR signals scale with the amount of released drug, which allows for quantitative control of the delivered drug dose in vivo using a feedback loop; the release of drugs from the carrier at the diseased site can be induced by a local stimulus, such as heating in the case of thermosensitive liposomes using e.g. RF or ultrasound; the CEST MR contrast enhancement can be switched on and off at will.
19 F MRI Contrast Agents
[0125] MR detectable 19 F does not naturally occur in the body, i.e. 19 F MRI will thus be necessarily based on the use of added 19 F contrast agents.
[0126] Contrast agents for 19 F MRI preferably have a large number of magnetically equivalent fluoro-groups (the sensitivity scales linearly with the number of magnetically equivalent F atoms per molecule). With a view to the desired combination with CEST MRI, the 19 F MR contrast agents used are preferably water-soluble, and particularly are preferably charged molecules so as to have as high a water-solubility as possible. With a view to application in phospholipid shells, the preferred 19 F contrast agents do not significantly bind, or are not significantly associated with phospholipids. With a view to their release in the human or animal body, the 19 F contrast agents are preferably of low toxicity and high biocompatibility.
[0127] Preferred 19 F contrast agents are charged per-F analogs of aliphatic hydrocarbons.
[0128] The invention will be illustrated with reference to the following, non-limiting examples and the accompanying non-limiting Figures.
Example 1
Synthesis of (2S)-9,13,17,18-tetrahydroxy-5-oxo-4,7,11,15-tetraoxaoctadecane-1,2-diyl dipalmitate 1 15,3 . See scheme 1
[0129]
[0130] Triester 1 15,3 was made by esterification of (R)-3-hydroxypropane-1,2-diyl dipalmitate (108) with acid derivative 107 followed by acidic deprotection of intermediate triester 109. Acid derivative 107 is a derivative of triglycerol of which the backbone of the glycerol units were introduced by the addition of solketal (101) to 2-((allyloxy)methyl)oxirane (102). Product 103 obtained in this way was oxidised to epoxide 104 and the epoxide ring was opened by benzylalcohol to form 105. After protection of the remaining hydroxyl groups as tetrahydropyranyl ether in 10 and removal of the benzylic group alcohol 106 was obtained that was converted in acid derivative 107 by reaction with bromoacetic acid.
Example 2
Synthesis of 3-(3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy)propane-1,2-diyl distearate (2 17,2 ) see scheme 2
[0131]
[0132] Product 103 containing the backbone to form a triglycerol derivative was made as shown in scheme 1. After protection of the hydroxyl group as a tetrahydropyranyl ether and epoxidation of the allyl group, compound 110 was obtained of which the epoxide ring was opened by cesium stearate to form mono ester 111. After esterification of the remaining hydroxyl group of 111 with stearic acid followed by deprotection with acid, product 2 17,2 was obtained.
Example 3
[0133] Temperature-sensitive liposomes containing lipidomimetics (1 n,R ) have been engineered for the triggered release of MRI contrast agents, such as [Gd(hpdo3a)(H 2 O)], and drugs, such as doxorubicin. Temperature-sensitive liposomal formulations were prepared composed of DPPC:DSPC:1 15,3 =50:20:30 (molar ratio). The lipids were dissolved in a solution of chloroform/methanol (4:1 v/v) and the solvent was evaporated under reduced pressure until a thin and homogenous lipid film was formed, which was further dried overnight under a nitrogen flow. Hydration of the film was performed at 60° C. with a 120 mM (NH 4 ) 2 SO 4 buffer (pH=5.4) containing 250 mM [Gd(HPDO3A)(H 2 O)]. The suspension was extruded at 60° C. through a 400 nm filter (2 times), 200 nm filter (2 times) and 100 nm filter (5 times). After extrusion, the extraliposomal buffer (containing [Gd(HPDO3A)(H 2 O)]) was replaced by HEPES Buffered Saline (HBS), pH 7.4 (20 mM HEPES, 137 mM NaCl) by gel filtration through a PD-10 column (GE Healthcare). DOX solution in HBS (5 mg/mL) was added to the liposomes at a 20:1 phospholipid to DOX weight ratio and incubated at 37° C. After the incubation, the extraliposomal DOX was removed by passing the liposomes through another PD-10 column. The T m and the hydrodynamic diameter of the liposomes were determined by differential scanning calorimetry (DSC) and dynamic light scattering (DLS), respectively. The liposomes containing 1 15,3 in their lipid bilayer displayed a hydrodynamic radius of 111 nm (after extrusion through a 200 nm PC filter) and a T m of 41.9° C. | Disclosed are lipidomimetic compounds of formula I (I) wherein: G represents a group satisfying formula II: HO—CH 2 —{CH(OH)—CH 2 -0} m -CH 2 —{C(=0)-0-CH 2 }) q — formula II each n independently is an integer from 1-30; m is an integer from 1-10; q is 0 or 1. These compounds can be added to the lipid bilayer of thermosensitive liposomes, for the purpose of aiding in the prevention of leakage of the liposomes' contents at 37° C., and retarding clearance from circulation. | 2 |
FIELD AND BACKGROUND OF THE INVENTION
This invention relates to a clamp connection and release device. More particularly, the invention is for a clamp connection and release device for inline connections for cables, plugs and sockets, electrical connections, as well as hydraulic and pneumatic connections. These connections are generally referred to as couplings.
There are many instances where it is necessary to connect couplings, for subsequent easy release, in order to form an electric or other connection between, for example, a switch or power source and a device which it activates. In one application, when a trailer is connected to a truck or tractor, it is not only necessary to ensure the physical connection between the truck and trailer, but, additionally, electrical or other components in the trailer, which must be operated by the operator in the truck, need to be secured. Therefore, all lighting, air conditioning, hydraulic and electrical connections must be established between the truck and trailer for proper and safe operation.
In conventional systems, it is typical for a truck to have a socket or outlet conveniently located, usually at the back thereof, the socket or outlet being provided with connectors of various types. Such connectors may be of an electrical type, such as those required to connect the truck with lighting or air conditioning systems in an attached trailer, or of an hydraulic type, to connect the truck's systems with that of the trailer's. An example of such a coupling is the braking system. When the trailer is physically connected to the truck so as to be drawn thereby, a plug or corresponding device from the trailer is releasably inserted into the plug or outlet located on the truck, so as to establish the necessary electrical, hydraulic or other (such as pneumatic) connections, as appropriate. Thus, the main physical connection of the truck to the trailer is conventionally established by what is typically described as a multiple pole electrical plug and socket, and, thereafter, the various systems of the truck and trailer are connected for appropriate communication between truck and trailer.
When inserting the plug or other type of connector on the trailer into the socket or outlet of the truck, it is, of course, important that the connection be a very secure one so as to be able to withstand the normal motion, vibrations and sudden movements which may occur under typical, and even severe, driving conditions. For this reason, the plug connection from the trailer to the socket or outlet of the truck is usually a very firm one, often requiring a significant amount of force to disconnect the two. Moreover, the connections may be located at positions which are difficult to access, making maneuverability by the operator difficult for the purposes of separating the plug from the socket.
SUMMARY OF THE INVENTION
According to one aspect of the invention, there is provided a clamp for an inline connector having a male and a female component, the clamp comprising: a first sleeve member having a peripheral portion defining an opening for receiving and holding the male or female component; a second sleeve member adjacent the first sleeve member, the second sleeve member having an opening therein which is adjacent the opening in the first sleeve member; a handle having a first end pivotally connected to the first sleeve member for rotation about the pivotal connection; a bracket member pivotally connected to the second sleeve member at one end thereof and pivotally connected to the handle at another end thereof; wherein rotation of the handle about its pivotal connection to the first sleeve member moves the first sleeve member and the second sleeve member relative to each other between a first position where the first sleeve member and the second sleeve member are closer to each other and a second position where the first sleeve member and the second sleeve member are further apart from each other.
Preferably, the first sleeve member is a ring member and defines a circular opening for receiving and holding the male or female component, and the second sleeve member is of a cylindrical shape and defines a circular opening adjacent the circular opening of the ring member.
The handle may comprise a pair of parallel end portions each of which connect at one end thereof pivotally to the first sleeve member, a pair of tapering portions extending from the end portions, and a pair of parallel handle portions extending from the tapering portions, the handle portions being connected to each other at ends thereof remote from the tapering portions by a U-shaped member. Preferably, the first sleeve member has a pair of threaded bores therein each of which registers with one of the apertures, and a bolt connects the end portion to the first sleeve member by passing through the aperture of the end portion and threadedly engaging the threaded bore in the first sleeve member.
The tapering portions may be downwardly angled with respect to the handle portions, and the end portions are downwardly angled with respect to the tapering portions.
Preferably, the bracket member comprises a pair of parallel first end portions each of which connect at one end thereof pivotally to the second sleeve member, a pair of tapering portions extending from the end portions, and a pair of parallel second end portions extending from the tapering portions. Conveniently, each first end portion of the bracket member has an aperture therein, the second sleeve member has a pair of threaded bores therein each of which registers with one of the apertures, and a bolt connects the first end portion to the second sleeve member by passing through the aperture of the first end portion and threadedly engaging the threaded bore in the second sleeve member. The tapering portions may be downwardly angled with respect to the second end portions, and the first end portions are linear with respect to the tapering portions.
According to another aspect of the invention, there is provided a clamp comprising: a housing member defining an opening for receiving and holding a component; an abutment member adjacent the housing member; a handle having a first end pivotally connected to the housing member; a bracket member pivotally connected to the abutment member at one portion thereof and pivotally connected to the handle at another portion thereof; wherein rotation of the handle about its pivotal connection to the housing member moves the housing member and the abutment member relative to each other between a first position and a second position where the housing member and the abutment member are further apart from each other than in the first position.
According to yet a further aspect of the invention, there is provided a method for connecting and disconnecting an inline coupling having a male and female component, the method comprising: locating a first sleeve member, having a peripheral portion defining an opening for receiving and holding the male or female component, adjacent a second sleeve member, the second sleeve member having an opening therein adjacent the opening in the first sleeve member; pivotally connecting a handle having a first end to the first sleeve member for rotation about the pivotal connection; pivotally connecting a bracket member to the second sleeve member at one end thereof and to the handle at another end thereof; and rotating the handle about its pivotal connection to the first sleeve member to move the first sleeve member and the second sleeve member relative to each other between a first position where the first sleeve member and the second sleeve member are closer to each other and a second position where the first sleeve member and the second sleeve member are further apart from each other.
The clamp connector and release device facilitates connection and easy release between a pair of registering connectors, such as a plug and a socket, thereby providing an inline connection which can be established and released as needed.
The clamp of the invention has particular application when used between a truck and trailer, whereby the various systems and devices on a trailer, such as lighting, air conditioning, braking and other systems, may be connected to the truck so that they can be operated from the truck. The clamp of the invention may establish inline connections of electrical, hydraulic or pneumatic type, and is designed so as to facilitate the connection, and, most importantly, allow ease or efficiency with respect to the release, since the plug and socket connection may often be tight fitting and require a significant amount of force to separate.
While the invention has as an important application in the connection of systems between a truck and trailer, the invention is not to be construed as being limited in this regard. The clamp of the invention may be useful and applicable in any situation where a plug may be connected to a socket, since the clamp of the invention significantly facilitates ease of separation so that the plug can be released or withdrawn from the socket.
In one aspect, the invention comprises a sleeve and associated ring which can be moved towards or away from each other, by the appropriate turning or movement of a handle, so that when the ring and sleeve portion are separated, the plug or connector will be removed from the socket.
It will be appreciated that the clamp of the invention can be used to establish a connection, as well as to disconnect, the plug or connector end of a cable, tube, or the like, irrespective of its connector characteristics. In other words, the clamp may be connected to a plug end, socket end, or any other type or combination of these elements.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the clamp connector and release device of the invention, shown in the closed or connect position;
FIG. 2 is a perspective view of the clamp shown in FIG. 1, in the disconnect position;
FIG. 3 is a top view of the handle used in the clamp of the invention shown in FIG. 1 of the drawings;
FIG. 4 is a side view of the handle which is shown in FIG. 3 of the drawings;
FIG. 5 is a top view of the bracket used in the clamp of the invention shown in FIG. 1 of the drawings;
FIG. 6 is a side view of the bracket shown in FIG. 5 of the drawings;
FIG. 7 is a side view of the sleeve and ring of the clamp of the invention shown in FIG. 1 of the drawings;
FIG. 8 is a cross-section through the sleeve and clamp of the invention shown in FIG. 7 of the drawings;
FIG. 9 is an end view of the sleeve and ring of the clamp of the invention shown in FIG. 1 of the drawings;
FIG. 10 is a cross-section of the sleeve and ring of the clamp shown in FIG. 9 of the drawings;
FIG. 11 is a side view of the clamp of the invention shown in the closed or connect position; and
FIG. 12 is a side view of the clamp of the invention shown in FIG. 11 of the drawings, in the disconnect position.
DETAILED DESCRIPTION OF THE INVENTION
Reference is now made to the drawings accompanying this application, which show various views of the clamp connector and release device of the invention, in different views, as well as the elements and components which make up the clamp.
With particular reference to FIGS. 1 and 2 of the drawings, a perspective view of a clamp 10 of the invention is shown in each of these Figures, with FIG. 1 showing the clamp 10 in a closed position, when a plug and socket are connected, and with FIG. 2 showing the clamp 10 in an open position, when a plug and socket are disconnected, the clamp 10 having been maneuvered so as to disconnect the plug from the socket.
The clamp 10 comprises a sleeve 12 , a ring 26 , a handle 60 and a bracket 96 , all arranged and connected with respect to each other as will be described.
The clamp 10 comprises the sleeve 12 which is of substantially cylindrical shape, the sleeve 12 having an outer surface 14 , an inner surface 16 , a leading end 18 and an inner end 20 . The sleeve 12 has two substantially diametrically opposed holes 22 and 24 (see also FIGS. 8 to 10 ), each of the holes 22 having a threaded inner bore for receiving a bolt, as will be described below.
The clamp 10 further comprises the ring 26 , the ring 26 having an outer surface 28 , an inner surface 30 , an inner end 32 , and a trailing end 34 . The ring 26 is about circular in shape, and is configured so as to be coaxial with the sleeve 12 . In the closed position of the clamp 10 , as shown in FIG. 1 of the drawings, the outer surface 14 of the sleeve 12 , and the outer surface 28 of the ring 26 , form a substantially continuous surface, and are of approximately the same diameter. Likewise, the inner surface 16 of the sleeve 12 , and the inner surface 30 of the ring 26 , are of substantially the same diameter, and define a flush, continuous surface when in the closed position, as illustrated in FIG. 1 of the drawings.
The ring 26 has a pair of substantially diametrically opposed holes 36 and 38 , each of which has an internal bore for receiving a bolt (see again FIGS. 8 to 10 ), as will be described more fully below.
In the embodiments shown in the drawings, the inner end 20 of the sleeve 12 , as well as the inner end 32 and trailing end 34 of the ring 26 , are approximately normal to the axis of both the sleeve 12 and ring 26 respectively. However, in the embodiment shown, the leading edge 18 of the sleeve 12 is cut obliquely with respect to the axis of the sleeve 12 , and is, in use, designed to engage or abut a correspondingly shaped surface surrounding a plug or socket. It will, however, be appreciated that while an oblique leading end 18 of the sleeve 12 is shown in FIGS. 1 and 2 of the drawings, the particular angle, and even shape, of the leading edge 18 will be determined and configured so as to properly engage the surface surrounding a plug or socket with which the clamp 10 is used. While it may be preferable, in certain circumstances, to shape the leading end 18 of the sleeve 12 according to the surface which it engages, such a shaping is not required by the invention, and any shaped leading end 18 which will engage the surface surrounding the plug or socket in a manner to allow the proper functioning of the clamp 10 will suffice.
At the top 40 of the sleeve 12 , there is provided a cut-out portion 42 which is of rectangular shape. The ring 26 has, also at its top 44 a groove or recess 46 which is provided in a portion of the ring 26 . The recess 46 is cut from the inner surface 30 of the ring 26 , through only a portion of the thickness of the ring 26 , such that the outer surface 28 of the ring 26 at the top 44 thereof is not affected by the recess 46 .
In the assembled form, to be discussed more fully below, the cut-out portion 42 registers with the recess 46 so as to provide a continuous channel 48 , best seen in FIG. 11 of the drawings (but also illustrated in FIGS. 8 to 10 ), when the sleeve 12 and ring 26 are adjacent each other.
It will be noted that the leading edge 18 of the sleeve 12 is layered in its upper half. Thus, the leading end 18 comprises an oblique surface 50 which forms a continuation of the leading edge 18 in the lower half, and a perpendicular surface 52 , which is substantially parallel to the inner surface 20 of the sleeve 12 . This may facilitate a connection which could operate with both an angled and a perpendicular shaped connector. However, the leading end 18 may be any shape, as necessary, and may also typically be squared off in its entirety.
The clamp 10 further comprises a handle 60 designed to connect to the ring 26 . The handle 60 , best illustrated in FIGS. 3 and 4 of the drawings, comprises a pair of parallel end portions 62 and 64 , a pair of tapering mid-portions 66 and 68 , and a pair of parallel handle portions 70 and 72 . The ends of the handle portions 70 and 72 remote from the parallel end portions 62 and 64 are connected to each other by a U-shaped portion 74 so that the handle 60 constitutes a single unit. The parallel end portions 62 and 64 have apertures 76 and 78 , the purpose of which will be described below, while the handle portions 70 and 72 include apertures 80 and 82 , also to be described more fully below.
It will be seen from FIG. 4 of the drawings that the handle 60 is not straight or linear in construction. The tapering mid-portions 66 and 68 are configured at angle α with respect to the handle portions 70 and 72 , so as to depend downwardly from these handle portions 70 and 72 , while the parallel end portions 62 and 64 are at angle β with respect to the tapering mid-portions 66 and 68 . The construction of the handle 60 so as to have the handle portions, tapering mid-portions and parallel end portions, configured at these angles facilitates operation of the release function of the clamp 10 , to be described more fully below.
In use, the handle 60 is connected to the ring 26 . The distance defined between the parallel end portions 62 and 64 is slightly greater than the outer diameter of the ring 26 . The apertures 76 and 78 in the parallel end portions 62 and 64 are located so that they register and correspond with the holes 36 and 38 in the ring 26 . A bolt 86 (seen in FIGS. 4, 11 and 12 ) extends through each of unthreaded apertures 76 and 78 in the parallel end portions 62 and 64 , and engages with the internally threaded holes 36 and 38 located in the ring. The connection established is such that the handle 60 is able to pivot or rotate about the bolt 86 so that rotational movement of the handle 60 relative to the ring 26 is possible.
The clamp 10 of the invention further comprises a bracket 96 , best illustrated in FIGS. 5 and 6 of the drawings. The bracket 96 comprises parallel end portions 98 and 100 , each of which contains an aperture 102 and 104 respectively. The bracket 96 comprises a pair of tapering mid-portions 106 and 108 , and a pair of end portions 110 and 112 , each of the end portions having an aperture 114 and 116 respectively. With reference to FIG. 6 of the drawings, it will be noted that the tapering mid-portion 106 is at an angle θ with respect to the end portion 110 . In side view, the tapering mid-portion 106 and parallel end portion 100 are linear, or form a continuous line.
The distance between the parallel end portions 98 and 100 is sufficient so as to straddle both the ring 26 and sleeve 12 , as well as the parallel end portions 62 and 64 of the handle 60 . This can best be seen in FIGS. 1 and 2 of the drawings. The bracket 96 is connected to the sleeve 12 by passing a bolt 122 (see FIGS. 6, 11 and 12 ) through each of apertures 102 and 104 , the apertures 102 and 104 being aligned with or registering with the holes 24 and 22 respectively in the sleeve 12 . A bolt 122 passes through each of the apertures 102 and 104 , and is secured within the threaded bore of the holes 22 and 24 so as to firmly secure the bracket 96 to the sleeve 12 of the clamp 10 . It should be noted that the bolts 122 securing the bracket 96 to the sleeve 12 are constructed such that the bracket 96 is capable of relative movement with respect to the sleeve 12 , so that it can rotate or pivot about the bolt 122 .
The bracket 96 is also connected to the handle 60 . In this regard, it will be noted that the apertures 80 and 82 in the handle 60 register with the apertures 116 and 114 respectively in the bracket 96 , and the handle 60 and bracket 96 are thereby connected by passing a bolt 124 (seen in FIGS. 11 and 12) through apertures 80 and 116 respectively, and another bolt 124 through apertures 82 and 114 respectively. The bolts 124 secure the bracket 96 and handle 60 together such that both the bracket 96 and handle 60 are capable of pivotal or rotational movement relative to each other about the bolts 124 when in the secured position.
The clamp 10 of the invention is intended to facilitate the connection and disconnection between a plug and socket, or to otherwise axially connect electrical, hydraulic or pneumatic components in line, in a cable. It will be seen in FIG. 11 of the drawings that a cable 130 is, in use, secured to the inner surface 30 of the ring 26 . The cable 130 has at one end 132 thereof a series of electrical pins, in this particular example, which will connect to a plug or socket in line. The plug or socket, represented in phantom lines by reference numeral 136 in FIG. 11 of the drawings, has a series of female pin receivers 138 intended to receive pins 134 at the end 132 of the cable 130 . The plug or socket 136 is connected through appropriate wiring or cable connections to controls, switches, or other device(s) as desired, which may be located in the truck. On the other hand, the cable 130 , including the various pins 134 , may be located in the trailer being drawn by the truck, and the various electrical pins 134 will branch out to connect to devices in the trailer, such as lighting, air conditioning or the like.
The operation of the clamp 10 of the invention, to be described, facilitates the connection and disconnection between the cable 130 , and the plug 136 .
Reference is now made to FIGS. 11 and 12 of the drawings. It will be seen in FIG. 11 that the sleeve 12 and ring 26 are adjacent each other. In this position, the entire clamp 10 is moved forward so that the plug 136 enters the sleeve 12 , and an axial connection is formed between the end 132 of the cable and the plug 136 . In this way, an electrical coupling is established between the pins 134 and the pin receiver apertures 138 . A secure connection is made between the cable 130 and the plug 136 so that even severe truck motions and vibrations will not result in the inadvertent disconnection which could result in a dangerous situation.
The clamp 10 of the invention functions in its most useful form when it is desired to disconnect the end 132 of the cable 130 from the plug 136 . Since the axial connection is usually a very firm one, in order to withstand the movement and vibration of machines and vehicles, it is often difficult to pull out the cable 130 from the plug 136 . Moreover, the access of an operator may be limited, making it even more difficult to maneuver the cable 130 from the plug 136 .
In the clamp 10 of the invention, simple removal of the cable 130 can be achieved as follows. Reference is made to FIG. 12 of the drawings, which shows the handle in the raised position. As the handle 60 is raised, or rotated in the direction indicated by arrow A, from the position shown in FIG. 11 to the position shown in FIG. 12, the handle 60 and bracket 96 pivot relative to each other about the bolt 124 . Further, the handle 60 , as it moves, pivots about the bolt 86 on the ring 26 , and the bracket 96 pivots about bolt 122 on the sleeve 12 . Due to the shape and configuration of the handle 60 and bracket 96 , as well as their connection with respect to each other, movement of the handle 60 from the position shown in FIG. 11 to the position shown in FIG. 12 results in the ring 26 moving away from the sleeve 12 , to create a gap 138 therebetween. The movement of the ring 26 away from the sleeve 12 causes the cable 130 to be pulled back and away from the plug 136 , effecting the disconnection. Thus, a simple movement of the handle 60 , and the configuration of the clamp 10 , provides a mechanical advantage to the user whereby the ring 26 is pulled back from the sleeve 12 , requiring much less force, and easy maneuverability, in separating the cable 130 from the plug 136 .
It will be appreciated that the reverse operation may also apply, enabling the cable 130 to be connected to the plug 136 by operating the handle 60 so as to close the gap 138 between the ring 126 and the sleeve 12 . In an embodiment of the invention, this connection operation may be facilitated by a simple hooking or engagement of the sleeve 12 to the surrounding portions of the plug 136 .
In the embodiment shown, the leading edge 18 of the sleeve 12 is oblique or angled, and would typically engage a correspondingly angled housing or portion surrounding the plug 136 to enhance proper connection. As mentioned above, this leading edge 18 may be constructed so as to have any number of oblique angles, as the situation requires, or may simply be flat. In another alternative, this leading edge 18 may have a specific form and shape which matches that of the housing surrounding the plug 136 to which it will be connected.
The cut-out portion 42 in the sleeve 12 , and the recess 46 in the ring 26 , preferably register with each other to form the channel 48 as shown, and would typically be used to ensure that the cable 130 is properly centered and/or located within the clamp 10 so that when the clamp 10 is used to connect the cable to a plug or socket, the pins 134 and recesses 138 therefor will correctly match. Thus, the cable 130 may include a projection, shown in FIG. 11 in phantom lines and identified by reference numeral 140 . FIG. 11 also shows the cut-out portion 42 and recess 46 in the sleeve 12 and ring 26 respectively.
While the clamp 10 of the invention has as an important application thereof the important function of connecting systems between a truck and trailer, the clamp of the invention is certainly not limited to such use. Any inline or axial connection between a plug and socket could benefit from the use of the clamp of the invention. Further, the clamp of the invention could be used for hydraulic, pneumatic or other types of connections and disconnections, and its function is not to be construed as being limited to electrical connections.
Additionally, where the cable, plug and/or socket have other than a circular shape, the sleeve 12 and ring 26 may be appropriately shaped so as to conform to the particular cable and connection arrangement for which it will be used. For example, if the clamp is used in an ordinary household outlet, the sleeve 12 and/or ring 26 may be rectangularly shaped so as to receive a standard residential plug. The clamp can also be used to connect axial cables such as TV or other forms of inline cable, where it is often difficult and cumbersome to separate conventional connections. The clamp of the invention allows increased force to be applied in separating a plug from a socket, but since the force will be appropriately applied by the separation of the sleeve 12 and ring 26 so that the components will not be damaged or broken, the additional force will not be harmful.
The invention is not limited to the precise construction or details described hereabove, and variations within the scope of the claims may be made. | A clamp for an inline connector having a male and a female component comprises a first sleeve having a peripheral portion defining an opening for receiving and holding the male or female component. A second sleeve is provided adjacent the first sleeve and has an opening therein which is adjacent the opening in the first sleeve. A handle having a first end is pivotally connected to the first sleeve for rotation about the pivotal connection. A bracket is pivotally connected to the second sleeve member at one end thereof and pivotally connected to the handle at another end thereof. Rotation of the handle about its pivotal connection to the first sleeve moves the first sleeve and the second sleeve relative to each other between a first position where the first sleeve and the second sleeve are closer to each other and a second position where the first sleeve and the second sleeve are further apart from each other. | 8 |
BACKGROUND OF THE INVENTION
This invention relates to air separation and in particular to an integrated method of separating air and generating power, and integrated plant for performing such a method.
A gas turbine comprises an air compressor, a combustion chamber and an expander. In operation, air is compressed in the compressor and is used to support combustion of a fuel gas in the combustion chamber. The resulting gaseous combustion products are then expanded in the expander or turbine with the performance of external work. This work may be the generation of electricity. Thus, the gas turbine may form part of a power station with the rotors of the compressor and expander and an alternator all mounted on the same shaft.
Commercial processes for the separation of air first require its compression. It is known to bleed compressed air from the air compressor of a gas turbine to feed an air separation plant. In a conventional air separation process, air is compressed, is purified by the removal of components such as water vapor and carbon dioxide that are less volatile than its main components, cooled to a temperature suitable for its separation by rectification, and then rectified in a so-called double rectification column having a higher pressure and a lower pressure stage. The oxygen product is typically withdrawn from the lower pressure stage as a vapor and warmed to ambient temperature by heat exchange with the incoming air. The lower pressure stage is conventionally operated at a pressure a little above atmospheric pressure so that the oxygen product is obtained at about atmospheric pressure. In some schemes, oxygen product from the air separation plant is used in the generation of the fuel gas that is burned in the combustion chamber of the gas turbine. Such processes typically require the oxygen to be produced at elevated pressure. Although the necessary pressure can be created by compressing the oxygen, U.S. Pat. No. 4,224,045 discloses that there are advantages in terms of the operating efficiency of the air separation process to operate the lower stage of the double rectification column at pressures well above atmospheric pressure. Further, the compressor of a gas turbine typically has an outlet pressure in the order of 10 to 20 atmospheres which is in excess of that required by the air separation process when the oxygen is taken from the lower pressure stage of the double rectification column at a pressure a little above atmospheric. Accordingly, it is typically desirable to operate the higher pressure stage of the double rectification column at substantially the same pressure as the outlet pressure of the compressor of the gas turbine.
Not only is oxygen then produced at a pressure well above atmospheric pressure, so is a nitrogen product. There are a number of proposals in the art including U.S. Pat. No. 4,224,045 for taking a stream of this relatively high pressure nitrogen product, warming it to about ambient temperature by heat exchange with the incoming air to about ambient pressure, further compressing the stream, further raising the temperature of the stream in a second stage of heat exchange with the incoming air so as to remove heat of compression from such air and then introducing the nitrogen into the combustion chamber or expander of the gas turbine. Accordingly, the nitrogen helps to power the gas turbine and therefore compensates for the loss of the air taken for separation from the air compressor of the gas turbine. Other examples of such processes are given in U.S. Pat. No. 4,557,735 and U.S. Pat. No. 4,806,136. One practical example of the above-described method is in the gasification of coal and is discussed in a paper entitled "Air Separation Integration for GCC Plants", by Olson, Jr, Anand and Jahnke, Tenth EPRI Conference on Coal Gasification Power Plants, 16 to 18 October 1991, San Francisco. In the integrated process described in this paper, nitrogen from the air separation plant is saturated with water vapor before being introduced into the turbine. We believe one purpose of this moisturizing is to provide additional returning mass to the turbine so as better to compensate for the air from the compressor of the turbine that by-passes the combustion chamber and flows into the air separation plant.
There is increasing interest in using pure oxygen or oxygen-enriched air together with coal in processes which form iron by the reduction of iron ore. It has for example been proposed to inject coal together with oxygen or oxygen-enriched air into the tuyeres of a conventional blast furnace thereby reducing the demand of these processes for coke and hence reducing the need for the operation of coke ovens which are viewed as providing environmentally harmful waste products. See for example a paper entitled "Oxy-coke Injection at Cleveland Ironworks". D A Campell et al, 2nd European Ironmaking Congress, Glasgow, September 1991, pp 233-246. Alternative processes using both oxygen and coal, such as the COREX process, eliminate the need for coke altogether. Such processes produce a fuel gas as a by-product, although the fuel gas does not have the high calorific value of one produced by the direct gasification of coal. Indeed, current proposals for enhancing the operation of a blast furnace by use of oxygen and coal typically produce a fuel gas by-product having a calorific value of less than 5 MJ/m 3 . Nonetheless, sufficient fuel gas is generated to make worthwhile its combustion for the generation of power. Thus, the fuel gas can be burned in a combustion chamber of a gas turbine and air taken from the compressor of the gas turbine for separation to form an elevated pressure oxygen product that is introduced into the blast furnace.
There is however a problem in introducing nitrogen into a gas turbine that employs a low calorific value fuel gas in its combustion chamber. The turbine has only a limited capacity for the return of pre-heated nitrogen and so only a part of the heat in the bleed air stream can be used for heating nitrogen. In addition, current gas turbine generally have fuel gas handling systems not able to handle gas at a temperature above 300° C. Accordingly, it is desirable to keep the temperature of any nitrogen stream introduced into the combustion chamber of the gas turbine at or below 300° C., and therefore a further limit is placed on the transfer of heat to such a nitrogen stream.
There is therefore a need for a method and apparatus which enables integrated air separation-gas turbine technology to be used when the fuel gas supplied to the gas turbine is of low calorific value, its source being for example a blast furnace. The invention aims at providing a method and plant that meet this need.
SUMMARY OF THE INVENTION
According to the present invention there is provided an integrated method of separating air and generating power, comprising:
a) compressing air without removing at least part of the heat of compression thereby generated;
b) dividing the compressed air flow into a major stream and a minor stream;
c) cooling the compresse minor air stream by heat exchange with a pressurized stream of water;
d) separating the minor air stream into oxygen and nitrogen;
e) moisturization a stream of compressed low grade fuel gas by introducing into it said pressurized stream of water downstream of the heat exchange between the stream of water and the minor air stream;
f) burning said moisturized fuel stream utilizing said major air stream to support its combustion; and
g) expanding with the performance of external work the combustion gases from the burning of the gaseous fuel stream; the work performed comprising the generation of said power.
The invention also provides integrated plant for separating air and generating power, comprising a gas turbine comprising an air compressor, combustion chamber and an expander; a heat exchanger having a first inlet communicating with an outlet from the air compressor and a second inlet communicating with a source of pressurized water, whereby in operation an air stream withdrawn from the compressor is able to be heat exchanged with a pressurized stream of water; means for separating the heat exchanged air into oxygen and nitrogen; means for moisturizing a compressed low grade fuel gas with said heat exchanged pressurized stream of water; and power generation means adapted to be driven by the gas turbine, wherein the combustion chamber communicates with an outlet from the air compressor and with said means for moisturizing the low grade compressed fuel stream and is able in operation to employ air from the compressor to support combustion of the fuel gas to provide hot gaseous combustion products for expansion in the expander.
By the term "low grade fuel gas" as used herein is meant a fuel gas having a calorific value of less than 12 MJ/m 3 .
The method and plant according to the invention find particular use when the source of the low grade gaseous fuel stream is a blast furnace. There is an increasing trend in the iron and steel industry to operate blast furnaces with coal (in addition to coke) and with an air blast enriched in oxygen. The resulting gas mixture comprises nitrogen, carbon monoxide, carbon dioxide and hydrogen. The precise composition of this gas depends on a number of factors including the degree of oxygen enrichment. Typically, however, it has a calorific value in the range of 3 to 5 MJ/m 3 . It is possible to operate the combined power recovery and air separation method according to the invention in conjunction with alternative processes for reducing iron ore to iron that produce a low grade fuel gas as a by-product.
The low grade fuel gas stream is typically produced at an elevated temperature, laden with particulate contaminants and includes undesirable gaseous constituents such as hydrogen cyanide, carbon oxysulphide and hydrogen sulphide. Processes and apparatuses for removing such contaminants are well known and produce a clean fuel gas at a temperature at or near to ambient. Such a process or processes may if desired be used to treat low grade fuel gas upstream of its introduction into the combustion chamber in accordance with the invention.
The stream of low grade fuel gas is preferably compressed to a pressure in the range of 10 to 25 atmospheres absolute upstream of its introduction into the combustion chamber. The precise pressure selected depends on the operating pressure of the combustion chamber. A compressor or compressors used for this purpose preferably have means associated therewith for removing the heat of compression at intermediate stages. A greater efficiency of compression is able to be achieved when the fuel gas compressor or compressors are operated with partial removal of the heat of compression than when they are not.
The compressed low grade fuel gas stream is preferably moisturized with the stream of pressurized water by countercurrent contact of the two streams with one another in a liquid-gas contact column. The column typically includes a packing in order to effect the contact between the liquid and the gas. Operation of such means enables the fuel gas to be saturated with water vapor at the operating pressure of the combustion chamber.
If desired, the moisturized stream of low grade fuel gas may be further heated intermediate the gas-liquid contact column and the combustion chamber so as to evaporate any droplets of liquid water carried out of the column in entrainment in the fuel gas and to increase overall efficiency.
Oxygen generated by the separation of the air is preferably used in the process which generates the low grade fuel gas. For example, it can be used to enrich the air supply to a blast furnace in oxygen.
The air is preferably separated by being rectified. The rectification of the air is preferably performed in a double column comprising a higher pressure stage and a lower pressure stage. There is preferably a condenser-reboiler associated with the two said stages of the double column so as to provide reboil for the lower pressure stage and reflux for both stages. The lower pressure stage preferably has an operating pressure (at its top) in the range of 3 to 6 atmospheres absolute depending on the desired supply pressure for the oxygen. Operation of the lower pressure stage in this range makes possible more efficient separation of the air than that possible at the more conventional operating pressures in the range of 1 to 2 atmospheres absolute. Typically, the pressure at which the higher pressure stage of the rectification column operates is a little below the outlet pressure of the air compressor of the gas turbine. If there is a condenser-reboiler linking the two stages of the rectification column, the operating pressure of the lower pressure stage depends on that of the higher pressure stage and thus places a limitation on the pressure at which the lower pressure stage can be operated.
The nitrogen product may be liquefied if there is not a use for it on the site of the gas turbine. Liquid nitrogen finds use in a wide range of chemical, metallurgical and industrial processes. Alternatively, if the nitrogen is produced at pressure, it may be preheated to a temperature typically in the range of 200° to 600° C. and then expanded with the performance of external work in an expander other than that of the gas turbine.
A hot gaseous stream of combustion products is typically exhausted from the expander of the gas turbine at a temperature in the range of 450° to 600° C. and a pressure in the order of 1 atmosphere absolute. It is desirable to recover the heat available in this stream. Accordingly, it may be used to raise steam. If desired, the steam may be expanded in a further turbine with the performance of external work, for example the generation of electrical power.
Alternatively or in addition, an exhaust stream from the expander of the gas turbine may be used to preheat air supplied to a blast furnace. Such air is conventionally heated to a temperature of over 1000° C. by passage through stoves which are heated by the combustion of fluid fuel. A part of the fluid fuel may be low grade fuel gas from the blast furnace. By preheating the air, it is possible to make a saving in the fuel that is used to heat the stoves. Either the rate of consumption of high grade fuel can be reduced, thereby offering a direct cost saving, or a reduction may be made in the rate at which low grade fuel gas from the blast furnace is supplied for the purposes of heating the blast air, thereby making possible an increase in the rate at which the low grade fuel gas is supplied to the gas turbine forming part of the plant according to the invention.
The method according to the present invention is particularly advantageous when operated in association with a blast furnace. It is preferred that at least 20% of the compressed air is taken for air separation. There is sufficient heat available in such a compressed air stream for the fuel gas produced by the blast furnace to be saturated in water vapor. At conventional gas turbine operating pressures, it is possible to enhance the rate of power generation while maintaining the fuel gas temperature at a level (i.e. below 300° C.) which is readily acceptable to the gas turbine. Moreover, at the operating pressure of the gas turbine the low grade fuel gas can accept water at a sufficient rate to enable a substantial degree of cooling to be provided for the minor stream of air. On the contrary, the rate at which a suitable gas turbine can optimally accept nitrogen would be so low that were that nitrogen used to extract heat from the minor air stream, its resulting temperature would be above that recommended for use in a gas turbine.
BRIEF DESCRIPTION OF THE DRAWINGS
A method and plant according to the invention will now be described by way of example with reference to the accompanying drawings, in which:
FIG. 1 is a flow diagram illustrating an integrated plant comprising a blast furnace, a gas turbine and an air separation unit; and
FIG. 2 is a flow diagram illustrating apparatus for utilizing a gas stream exhausted from the gas turbine shown in FIG. 1.
DETAILED DESCRIPTION
Referring to FIG. 1 of the drawings, the illustrated plant includes a gas turbine 2 comprising an air compressor 4, a combustion chamber 6 and an expansion turbine 8. The rotor (not shown) of the compressor 4 is mounted on the same shaft as the rotor (not shown) of the turbine 8 and thus the turbine 8 is able to drive the compressor 4. The compressor 4 draws in a flow of air and compresses it to a chosen pressure in the range of 10 to 20 atmospheres absolute. The compressor 4 has no means associated therewith for removing heat of compression. The compressed air thus leaves the compressor 4 at a temperature typically in the order of 400° C. This compressed air stream is divided into a major and a minor stream. Typically, the minor stream comprises from 20 to 35% of the total air flow in the kind of plant illustrated in FIG. 1 of the drawings. The major stream is supplied to the combustion chamber 6 and is employed to support combustion of a fuel gas also supplied to the combustion chamber 6. The resulting hot stream of combustion gases flows into the expansion turbine 8 and is expanded therein to a pressure a little above atmospheric pressure. The expansion turbine 8 as well as driving the compressor 4 also drives an alternator 10 which is used in the production of electrical power.
The minor stream of compressed air flow through a heat exchanger 12 in which it is cooled to ambient temperature or a temperature a little thereabove by countercurrent heat exchange with a circulating stream of pressurized water. The pressurized stream of water flows in a circuit comprising, in sequence, starting from an inlet 14 for introducing make-up water, a pump 16 intermediate the colder end of the heat exchanger 12 and the inlet 14, the heat exchanger 12 itself, and a liquid-gas contact column 18 having an inlet 20 at its top for pressurized, heated water and an outlet 22 at its bottom. The water leaving the bottom of the column 18 through the outlet is united with make-up water introduced through the inlet 14, thus completing the circuit. In operation of the plant shown in FIG. 1, the pump 16 raises the pressure of the water to a value in the range of 20 to 25 bars. The water is then heated to a temperature in the order of 200° C. by countercurrent heat exchange in the heat exchanger 12 with the minor air stream from the compressor 4. The pump 16 provides a flow of pressurized water through the heat exchanger 12 that is adequate to ensure that the pressurized water remains in the liquid phase throughout its passage through the heat exchanger 12 even though the temperature of the air taken from the compressor 4 is typically in the range of 350° to 450° C. If desired, this air stream may be precooled upstream of its passage through the heat exchanger 12.
Downstream of the heat exchanger 12 the pressurized water flows to the inlet 20 of the liquid-gas contact column 18. The column 18 has a packing 24 for effecting contact between a descending flow of pressurized hot water and a rising flow of fuel gas introduced at the bottom of the column 18 beneath the packing 24 through an inlet 26. As the fuel gas descends the column 18 passing through the packing 24 so it is gradually heated by contact with the hot pressurized water flow. In addition, water is transferred from the liquid phase to the gas phase and the fuel gas is as a result moisturized. The fuel leaves the column 18 through an outlet 28 at the top at a temperature in the order of 150° C. and a pressure in the order of 15 to 20 atmospheres absolute and is saturated with water vapor. The fuel gas stream then flows to the combustion chamber 6 of the gas turbine 2. (If desired, the fuel gas stream may be raised in temperature to 200° C. by being heated in a further heat exchanger (not shown) intermediate the column 18 and the combustion chamber 6.) Water flows out of the column 18 through the outlet 22 and is then mixed with make-up water from the inlet 14. There is thus a continuous flow of water around the circuit comprising the pump 16, the heat exchanger 12 and column 18.
Downstream of the heat exchanger 12 the minor air stream flows into a plant 30 for separating air by rectification. The plant may for example be of the kind described with reference to and shown in FIG. 1 of EP-A-0 384 688.
A stream of oxygen product and a stream of nitrogen product are withdrawn from the plant 30. The stream of oxygen product is compressed to a pressure of about eight bar absolute in an oxygen compressor 32. The compressed oxygen stream is used to enrich in oxygen an air blast which is supplied to a blast furnace 36. Alternatively, or in addition, the oxygen can be supplied directly to the tuyeres (not shown) of the blast furnace 36.
The blast furnace 36 is used to reduce iron ore to make iron by reaction with a solid carbonaceous fuel. The necessary heat for the reaction is generated by the reaction of the oxygen enriched air with the carbonaceous fuel. As a result of the reactions that take place in the blast furnace, a gas mixture comprising carbon monoxide, hydrogen, carbon dioxide, nitrogen and argon is produced. It typically has a calorific value in the order of 3 to 5 MJ/m 3 depending on the degree of enrichment of the air blast. The gas mixture leaving the top of the blast furnace will also typically contain traces of oxides of sulphur and other undesirable gaseous substances, be laden with particulate contaminants, and be at a temperature above ambient. The gas mixture is treated in a plant 38 of conventional kind to cool it to ambient temperature, and to remove undesirable gaseous impurities of particulate contaminants.
The resulting purified fuel gas stream from the plant 38 is then compressed in a compressor 40 and raised to a pressure such that after passage through the packed column 18 it is able to enter the combustion chamber 6 at the required elevated pressure. The resulting compressed fuel gas is the source of the gas entering the packed column 18 through the inlet 26.
If desired, not all the fuel gas leaving the clean-up plant 38 need flow to the compressor 40. Instead, some can be used for heating purposes on the site of the blast furnace 36. For example, some of the fuel gas can be burned to generate heat for preheating the air blast flowing to the blast furnace 36.
An alternative or additional method for preheating the air supplied to the blast furnace 36 is shown in FIG. 2. Like part shown in FIGS. 1 and 2 are identified by the same reference numerals.
A hot gas stream leaving the expander 8 of the gas turbine 2 at a temperature in the range of 450° to 600° C. and a pressure in the order of 1 atmosphere absolute flows into a heat exchanger 42 in which it is cooled by countercurrent heat exchange with a compressed air stream. The compressed air stream is created by operating an air compressor 44 separate from the air compressor 4 of the gas turbine 2. The air compressor 44 raises the pressure of the air to a level suitable for its introduction into the blast furnace 36. This pressure is typically in the range of 4 to 5 atmospheres absolute. This compressed air stream is heated to a temperature in the order of 500° C. by passage through the heat exchanger 42 as aforesaid. The resulting preheated air stream then flows through a series of stoves 46 in which it is heated to a temperature in the range of 1000° to 1200° C. Pre-heating of the air is able to make possible considerable savings in the rate at which fuel needs to be burnt in order to provide heating for the stoves. The hot air leaving the stoves is then introduced into the blast furnace 36.
Typically, approximately half the flow of exhaust gas out of the expander 8 is needed to raise the temperature of the blast air to 500° C. The remainder of the exhaust gas may for example be used for steam raising.
The operation of the plant shown in FIGS. 1 and 2 is further illustrated by the following example.
A fuel gas stream flows from the compressor 40 to the column 18 at a rate of 63.3 kg/s, having a temperature of 130° C. and a pressure of 20 bar. It has the following approximate composition by volume:
CO 26.4%; CO2 24.8%; N2 43.1%; H2 5.7% and a calorific value of 4.2 MJ/Nm3.
Water is added to the fuel in the column 18 at a rate of 7.1 kg/s and the resulting moisturized fuel gas leaves the column 18 at a temperature of 150° C. and a pressure of 19 bar. The temperature of the moisturized fuel gas stream is then raised to 200° C. in a heat exchanger (not shown) and flows into the combustion chamber 6 at a pressure of 16 bar and a temperature of 200° C. The gas turbine 2 may be a SIEMENS V64.3 gas turbine. Such moisturization of the fuel gas is able to enhance the power output of the gas turbine 2 from 59 to 62 MW. Typically, in this example, air is bled for separation from the compressor 4 at a rate of 43.1 kg/s, a pressure of 15.6 bar and a temperature of 400° C. Nitrogen product at a pressure of 4.8 bar is produced at a rate of 34.4 kg/s. Oxygen product is produced at a rate of 8.7 kg/s and is fed by the compressor 32 to the blast furnace 36 at a pressure of 8 bar. | In a process integration, particularly with a blast furnace, low grade fuel gas produced by the furnace is compressed and moisturized. The moisturized fuel is burnt using a major part of a compressed air stream to support its combustion. The resulting combustion gases are then expanded with the generation of power. The minor part of the air is separated into oxygen and nitrogen. Oxygen is used in the blast furnace. | 8 |
FIELD OF THE INVENTION
The invention relates to a device for retrofitting a work station such that the work surface can be automatically vertically adjusted to accommodate workers of different heights.
BACKGROUND OF THE INVENTION
There are at least 10 million video display terminals (hereinafter referred to as VDT's) in use across the country, and it is predicted that there will be at least 40 million VDT's by the end of this decade. While VDT's are used for a variety of tasks, they are used most intensively by a range of office workers who may spend the entire day key-punching and processing information. VDT's have been instrumental in increasing productivity and efficiency for virtually every major industry, and will continue to play a central role in this country's economy.
However, as the number of VDT's in the work place has risen, so have the health complaints associated with their use. Surveys indicate that a majority of full-time VDT users report high frequencies of health problems. Among other problems, recent studies confirm that VDT users have higher incidences of problems such as eye strain, headaches, insomnia, back and neck strain and fatigue.
As these health concerns have been recognized as legitimate and serious, steps are being taken in at least twenty states to introduce legislation to institute health and safety protections for VDT users. While questions have been raised regarding whether VDT's emit harmful radiation, studies show that the radiation levels emitted by the VDT's are well below levels naturally found in the environment. Thus, it is generally concluded that radiation is not the primary cause the physical problems discussed above. In contrast, numerous studies have indicated that operator injury such as carpal tunnel syndrome and tenosynovitis, which are cumulative trauma injuries, are caused by improper VDT workstation design.
In particular, the conventional VDT workstations is designed such that the work surfaces cannot be adjusted to accommodate people of different height. Shorter people must arch their body and elevate their arms in order to properly operate the keyboard and view the display terminal. In contrast, taller people have to hunch over to access the keyboard and view the terminal. Accordingly, the conventional VDT work stations have resulted in a high frequency of health-related problems.
FIG. 1 illustrates the conventional video display terminal work station. As shown in FIG. 1, the conventional work station includes a plurality of interconnected panels 1 having a plurality of elongate vertically extending support rails 2. Each of the support rails 2 includes a plurality of slots disposed along the vertical length thereof. Support brackets 3, having a plurality of teeth protruding therefrom, are secured to the support rails 2 by inserting the teeth of the support brackets into the complimentary corresponding slots of the support rails 2. The work surface 4 is supported by a pair of the supporting brackets 3.
Thus, while the conventional work surface is vertically adjustable, such vertical adjustment can only occur by disassembling the table top from the brackets and vertically adjusting the location of the support brackets on the support rails. Accordingly, to vertically adjust the conventional work surface it is necessary to remove all items therefrom, including the video display terminal. It is therefore not practical to adjust the height of the work surface on an hourly or daily basis to accommodate a change in shift of workers of different heights. Therefore, rapid, automatic, vertical adjustment of the work surface is not possible resulting in an unhealthy working environment.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a retrofitting device for retrofitting an existing work station such that the work surface can be rapidly and automatically vertically adjustable.
It is a further object to provide a retrofitting device for retrofitting an existing work station such that the work surface can be vertically adjusted while the video display terminal is disposed thereon.
A further object is to provide an inexpensive retrofitting device for retrofitting a standard work station with a vertically adjustable work surface without requiring a redesign of the existing work station.
These and other objects which will become apparent from the ensuing description of the preferred embodiment of the invention are accomplished according to the present invention by a vertically adjustable, retrofittable work station adapted to be mounted to an existing wall panel. The retrofittable work station comprises a pair of horizontally spaced, vertically oriented support rails secured to the panel, a work surface, a first pair of elongate, vertically oriented, rails horizontally displaced from one another and adapted to be individually and stationarily mounted to the support rails, a second pair of elongate, vertically oriented, rails individually slidably mounted to the first pair of rails, means for individually mounting the support brackets and thus the work surface to the second pair of rails, a first elongate, horizontally oriented, channel member interconnecting the first pair of rails and a driving mechanism coupled between the first and second channel members for selectively displacing the channel members towards or away from each other to attendantly vertically displace the work surface. To allow for retrofit, the first pair of stationary rails have a plurality of teeth extending therefrom which are shaped and arranged in the same manner as the teeth which extend from the support bracket. In this manner, the stationary rails can be secured to the existing support rails. In addition, the second pair of slidably mounted rails have a plurality of slots corresponding to the slots in the existing support rails such that the existing support bracket can be secured to the slidable rails to thereby provide an automatically vertically adjustable work surface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the conventional VDT workstation;
FIG. 2 is a front view of the vertically adjustable, retrofittable workstation of the present invention;
FIG. 3 is a side view of the vertically adjustable workstation of the invention;
FIGS. 4, 5 and 6 are sectional views taken along the lines IV--IV, V--V and VI--VI of FIG. 2, respectively;
FIGS. 7, 8 and 9 are sectional views taken along the lines of VII--VII, VIII--VIII, and IX--IX of FIG. 2, respectively; and
FIG. 10 is a sectional view taken along the line X--X of FIG. 2.
DESCRIPTION OF PREFERRED EMBODIMENTS
As discussed above and as shown in FIG. 1, the conventional work station includes a plurality of panels 1 interconnected by support rails 2 having slots disposed therein for receiving the correspondingly shaped teeth of the support bracket 3 for supporting the work surface 4. The retrofittable device of the invention is a vertically adjustable unit which is designed to be mounted on the existing support rails 2 and to support the existing support bracket 3 for supporting the work surface 4 in a vertically adjustable manner.
Particularly, as shown in FIGS. 2 and 3, the retrofittable device of the invention comprises a pair of stationary rails 5 adapted to be mounted on the existing support rails 2, a pair of slidable rails 6 individually slidably disposed on the stationary rails 5, a slidable channel 7 connecting each of the slidable rails 6, a fixed channel 8 connecting each of the stationary rails 5, a support bracket 3 for supporting the work surface 4 and a driving mechanism coupled to the slidable 7 and fixed channel 8 for selectively displacing the channels towards or away from each other to attendantly vertically displace the work surface 4.
Referring to FIG. 3, the stationary rails 5 are vertically extending elongate members for securing the retrofittable device to the support rails 2 of the existing panel. In cross-section, the stationary rails 5 are substantially G-shaped as shown in FIGS. 5 and 6. Secured to each of the stationary rails 5 is an elongate securing plate 9 extending the length of the stationary rail 5. As shown in FIG. 3 the securing plate 9 has a plurality of engaging teeth 10 extending therefrom along the vertical length of the stationary rail 5. The teeth are shaped and arranged to correspond to the shape and arrangement of the teeth extending from the existing support bracket 3. Thus, the teeth 10 of the securing plates 9 are insertable into the slots 11 of the existing vertical support rails 2 in the same manner that the support brackets 3 are conventionally insertable into the slots 11 of the support rails so as to allow for the stationary rails 5, and hence the retrofittable device, to be easily mounted to the existing rails 2.
The slidable rails 6 are also G-shaped in cross-sections to correspond to the shape of the stationary rails 5 such that slidable rails 6 are individually slidably accommodated in the stationary rails 5 in the manner shown in FIGS. 3, 5 and 6. To allow for sliding movement between the slidable rails 6 and the stationary rails 5, a pair of sliding bushings 12 are secured to each of the slidable rails 6 at upper and lower portions thereof. Each of the bushings 12 comprise a pair of L-shaped substantially frictionless members 13,14 which are interconnected such that one of the frictionless members 13 is disposed on the inside of the G-shaped slidable rail 6 which the other frictionless member 14 is disposed on the outside of the G-shaped slidable rail 6. The frictionless members 13,14 are connected by dowel pins 15, screws or the like to the slidable rails 6. Thus, the frictionless members are fixedly attached to the slidable rails 6 so as to slide therewith relative to the stationary rails 5 to allow for smooth vertical adjustment of the slidable rails 6.
As shown in FIGS. 2 and 3, each of the slidable rails 6 has a plurality of slots 16 disposed along the length thereof. The slots 16 are shaped and arranged in the same manner as the slots 11 provided in the existing support rails 2. Accordingly, the existing support brackets 3 can be secured to the slidable rails 6 in the conventional manner by inserting the teeth 17 of the support brackets 3 into the complimentary slots 16 of the slidable rails 6.
The slidable channel 7 and fixed channel 8 respectively interconnect the slidable rails 6 and the stationary rails 5, as illustrated in FIG. 2. That is, the slidable rails 6 are interconnected by the slidable channel 7 and the stationary rails 5 are interconnected by the fixed channel 8. The channels 7,8 are dimensioned in length such that the overall width of the retrofittable device corresponds to the standard distance between existing support rails 2 in conventional work stations. For example, the distance between the support rails in standardized work stations is either 48 or 64 inches. Correspondingly, the channels are dimensioned such that the distance between the stationary rails is either 48 inches or 64 inches such that the retrofittable device can be used to retrofit any standard size work station.
The cross-sectional shape of each of the channels 7,8 is in the form of a "W" resulting in a high bending strength with a minimal weight. The slidable channel 7 and stationary channel 8 are respectively connected to the slidable rails 6 and the stationary rails 5 in the manner shown in FIGS. 2, 5 and 6. Specifically, each of the stationary rails 5 and slidable rails 6 include a pair of U-shaped connector links 18 extending perpendicularly therefrom. Referring to FIG. 4, the slidable rail 6 and stationary rail 5 are respectively secured to the slidable channel 7 and fixed channel 8 by respectively securing the pair of connector links 18 to the outer correspondingly U-shaped portions 19 of the W-shaped channels using screws or the like.
As shown in FIGS. 1 and 3, the support brackets 3 are substantially L-shaped members having a plurality of teeth 17 protruding therefrom. The teeth 17 are engageable with the slots 16 of the slidable rails 6 such that the support brackets 3 extend perpendicularly from the slidable rails 6 away from the existing panel 1 to support the work surface 4 thereon.
Having fully described the overall structure of the retrofittable device, the driving and guide mechanism for selectively displacing the channels toward or away from each other to attendantly displace the work surface will be described hereinafter.
Referring to FIGS. 2 and 7-10, the driving/guide mechanism generally includes a slide plate 20, a drive screw 21 and a motor 22 secured to the slidable channel 7 as well as a drive nut 23 and a bearing bracket 24 fixedly attached to the fixed channel 8. The slide plate 20 is a substantially U-shaped plate which is fixedly secured to the slidable channel 7 at the top end of the slide plate 20 and which extends vertically downwardly therefrom. The slide plate 20 includes two flanges 25 on opposing side thereof to which linear bearings 28 are individually attached. In particular, the linear bearings 28 are substantially rectangular in cross-section and include a slot extending longitudinally thereto in which the flanges are respectively secured. The linear bearings 28 are individually secured to the flanges 25 using a plurality of dowel pin 29 inserted into aligned holes in the linear bearing and the flange, as shown in FIG. 9. Of course, the linear bearing could be secured to the flange by any suitable manner. The linear bearings 28 are in sliding engagement with the bearing bracket in the manner described hereinafter.
The motor 22 is fixedly secured to the slidable channel 7 and includes the rotatable drive screw 21 extending vertically downwardly therefrom. The drive screw 21 is threadedly engaged with the drive nut 23 which is fixedly secured to the stationary channel 8 in the following manner.
A substantially U-shaped vertically extending cover 26 is secured to the stationary channel as shown in FIGS. 2, 9 and 10. The cover 26 extends downwardly a sufficient distance to cover the drive mechanism. Secured to the interior portion f the cover is a U-shaped inner bracket 27 for securing the drive nut 23 and the bearing bracket 24. Specifically, the drive nut 23 is secured to the interior portion of the inner bracket 27 using screws or the like. The drive nut 23 is oriented such that the axis of the threaded hole extends in the vertical direction to receive the drive screw 21.
The bearing bracket 24 is secured to the inner bracket 27 as shown in FIG. 8. The bearing bracket 27 is substantially C-shaped and extends in the vertical direction. The outer portions of the bearing bracket are dimensioned to slidably receive the linear bearings 28 individually secured to the flanges 25 of the slide plate 20 in the manner described hereinabove. In this manner, the slide plate 20, in sliding contact with the bearing bracket 24, distributes the torsional force resulting from the torque of the drive screw to prevent any distortion of the device.
Accordingly, upon rotation of the drive screw, the slidable channel, and attendantly the slidable rails and the work surface, moves in the vertical direction to thereby adjust the elevation of the work surface.
A top cover 30 is provided above the work surface, as shown in FIG. 3. Specifically, the top cover 30 is connected at opposing lateral sides to the top of each slidable rail 6 and extends downwardly just below the work surface 4. Disposed on the top cover is the elevation adjustment switch 31 for selectively operating the motor to vertically displace the work surface to the desired elevation. Also disposed on the upper cover are the necessary VDT hook-up connections 32 as well as an electrical outlet 33. In addition, a lower skirt is disposed below the work surface to cover the portion of the drive mechanism which is not covered by the cover 26.
Having fully described the details of the invention, the retrofit procedure will be described hereinafter. Referring to FIG. 1, the desk top 11 and the existing support brackets 3 are removed from the existing vertical support rails 2. Thereafter, as illustrated in FIG. 3, the retrofittable device is attached to the existing rail 2 by securing the engagement teeth 10 of each of the stationary rails 5 into the slots of the existing support rails 2.
While the desk top can be automatically adjusted by a distance of twelve inches using the automatic drive mechanism, the retrofittable device can be secured at any elevation along the existing rails. For instance, the standard table top height is 30 1/4". Thus, it may be desirable to attach the retrofittable device to the existing rails such that the table top can be adjusted six inches in both the up and down direction with respect to the standard 30 1/4" table top height; thus, the table top can be automatically adjusted from 24 1/4" to 36 1/4".
Having secured the retrofittable device to the existing panel 1, the existing support brackets 3 are attached to the slidable rails 6 of the retrofittable device in the same manner that the support brackets 3 and normally attached to the existing rails 2. That is, the engagement teeth 17 of the existing support brackets 3 are inserted into the slots 16 of the slidable rails 6 so as to be securely attached thereto. It should be noted that the support brackets 3 can be attached at various elevations along the slidable rails 6 providing an additional adjusting feature. Once the support brackets are attached to the sliding brackets, the table top 4 is placed on top of the support brackets 3 in the usual manner.
Although the present invention describes the preferred embodiment of the invention, it should be understood that numerous modifications and adaptations may be resorted to without departing from the spirit of the invention. For instance, an emergency cut-off switch may be provided to prevent accidental vertical movement of the work surface.
Thus, the retrofittable work station according to the invention provides a solution to the problems associated with the conventional work stations discussed hereinabove. While the conventional work stations included substantially fixed, non-adjustable work surfaces resulting in stress related health problems for the VDT users, the invention provides a retrofittable work station having an automatically adjustable work surface to accommodate users of various heights to thereby provide a comfortable, substantially stress free working environment. | A vertically adjustable, retrofittable work station including a first pair of vertically oriented, spaced rails (5) having engaging teeth (10) protruding therefrom so as to be stationarily mounted on an existing wall panel (1) of a conventional work station, a second pair of vertically oriented rails (6) individually, slidably, interlockingly disposed in the first pair of rails (5), a pair of support brackets (3) having engaging teeth (17) protruding therefrom so as to be individually mounted on the second pair of rails (6), a work surfaces (4) supported by the support brackets (3), a pair of interconnecting channels (7, 8) for respectively interconnecting the first and second pairs of rails (5,6), and a drive mechanism coupled between the interconnecting channels to move the channels toward or away from each other so as to attendantly displace the work surface (4). | 0 |
BACKGROUND OF THE INVENTION
[0001] The invention relates to various mechanisms which are operated by applying tension or compression with actuating cables and more particularly to latch mechanisms, such as some aircraft latches which are cable actuated latches. One of the drawbacks of utilizing cable actuation for various mechanisms is that for some systems, particularly those in which the cables are hidden, such as behind panels or covers, it is not immediately ascertainable that a cable has failed. In such cases, manipulation of a handle or lever may provide a false indication that the apparatus has been manipulated as desired, when in fact the cable failure has prevented actuation of the mechanism. In the case of latches, a handle might be manipulated such that the handle indicates that the latch is open or closed, when the latch has not been activated because of a cable failure. In some cases, particularly with aircraft devices, it is imperative that the status of the device be immediately ascertainable, such as whether the device has been manipulated as desired.
SUMMARY OF THE INVENTION
[0002] Embodiments of the disclosed apparatus detect a cable out condition for cable actuated mechanisms, providing an immediate indication to the operator of a problem with a cable. In a dual cable system, if one of the cables has failed the handle is prevented from achieving either the open position or the closed position. An embodiment of the apparatus comprises an activation handle for operating the particular mechanism, where the activation handle has a first position which indicates a first condition and a second position which indicates a second condition. The disclosed apparatus may be utilized with mechanisms which are actuated by parallel cables, including mechanisms which are actuated by the application of tension in the cables (“pull”) or compression (“push”).
[0003] In the case of a latch, the activation handle has a latch open position and a latch closed position, corresponding with the desired latch operation. It is to be appreciated that the disclosed apparatus may be used for latches which are opened by application of tension, or closed by operation of tension, thus the indications on the figures of “open” and “closed” are for illustrative purposes only. The apparatus further comprises means for operationally attaching parallel actuating cables to the activation handle, such that the activation handle may apply a uniform tension or compression to the cables. Such means may comprise a yoke mechanism which is pivotally attached to an activation rod, which in turn is connected to the activation handle. The yoke mechanism has a first side and a second side, with a first cable attached to the first side and a second cable attached to the second side. The yoke mechanism has a first stop member attached to the first side of the yoke mechanism and a second stop member attached to the second side of the yoke mechanism. The apparatus has a stationary first shoulder which is placed such that it will engage the first stop member if the first cable fails, because a failed cable will cause the yoke mechanism to pivot and operation of the activation handle drives a portion of the first stop member into the first stationary shoulder, stopping further motion of the activation handle. Likewise, if the second cable fails, the yoke mechanism will pivot in the opposite direction and a portion of the second stop member will be pulled into the stationary second shoulder and further motion of the activation handle will be stopped.
DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 shows a right side perspective view of an embodiment of the invention.
[0005] FIG. 2 shows a left side perspective view of an embodiment of the invention.
[0006] FIG. 3 shows a front view of an embodiment of the invention.
[0007] FIG. 4 shows a rear perspective view of an embodiment of the invention.
[0008] FIG. 5 shows a left side view of an embodiment of the invention.
[0009] FIG. 6 shows a front view of an embodiment of the invention.
[0010] FIG. 7 shows a sectioned view taken along line 7 - 7 of FIG. 6 .
[0011] FIG. 8 shows a perspective view of an embodiment of the invention, with the cable attachment mechanism shown in exploded detail.
[0012] FIG. 9 shows a perspective view of an embodiment of a shaft utilized in embodiments of the disclosed apparatus.
[0013] FIG. 10 shows a perspective view of an embodiment of a spindle utilized in embodiments of the disclosed apparatus.
[0014] FIG. 11 shows a perspective view of an embodiment of a sleeve utilized in embodiments of the disclosed apparatus.
[0015] FIG. 12 shows a perspective view of an embodiment of a bushing utilized in embodiments of the disclosed apparatus.
[0016] FIG. 13 shows an embodiment of the invention with cables attached.
[0017] FIG. 14 shows the embodiment of FIG. 13 and how the device locks out in the event of a cable failure.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0018] Referring now to the Figures, an embodiment of the disclosed apparatus 10 is depicted. An embodiment of the apparatus 10 has a handle assembly 12 , a housing 14 , an operating rod assembly 16 , and a cable attachment assembly 18 . References made below to the top, bottom, or sides of the apparatus 10 will be with respect to the orientation of the apparatus as depicted in FIG. 1 , although it is to be appreciated that the apparatus will function in any orientation. It is also noted that the embodiments of the apparatus 10 shown in the Figures include the labels “closed” and “open” and generally refer to the utilization of the device with latches, particularly aircraft latches. Thus, for the embodiment depicted in FIG. 1 , the rotation and shifting of the handle assembly 12 in a downward direction would result in a latch attached to the apparatus with parallel cables to be in the “open” position. However, the same apparatus might be utilized to close a latch by the same handle movement.
[0019] It is to be further appreciated that the apparatus 10 may be employed with other types of mechanisms besides latches. Any mechanism which is actuated by cables, either by push-pull actuation or by application of tension or compression, is a potential candidate for use in combination with the disclosed apparatus.
[0020] Handle assembly 12 may comprise a grip member 20 which is attached to a D-handle 22 . Handle assembly 12 further comprises a trigger 24 which is maintained in position biased apart from grip member 20 by biasing means, such as spring 26 . Handle assembly 12 is attached to spindle 28 , to which trigger 24 is attached by rivet 30 . Spindle 28 , shown in greater detail in FIG. 10 , slides over shaft 54 to which grip member 20 is attached by rivet 34 or other fastening means. Trigger 24 freely travels over shaft 54 until rivet 34 reaches the top of a slot 62 in shaft 54 , at which point trigger 24 initiates movement in shaft 54
[0021] Housing 14 has integral mounting means such as attachment plate 36 , which maintains housing 14 in a stationary position during the operation of the apparatus 10 . As shown in the figures, housing 14 has at least a first selection slot 38 and a second selection slot 40 , which are generally oriented normal to the long axis of the housing. The selection slots 38 , 40 are connected to one another by linking slot 42 . This configuration provides at least two positions for engagement of lock screw 44 within housing 14 . For the embodiment shown in the figures, when the lock screw 44 engages the first selection slot 38 , the apparatus being actuated by the cables is in the closed position Likewise, when the lock screw 38 engages the second selection slot 40 , the operated apparatus is in the open position. Of course, additional selection slots may be located within housing 14 , providing a variety of intermediate positions between selection slots 38 , 40 as required by the functioning of the particular apparatus being actuated by the apparatus 10 . Linking slot 42 is generally oriented along the long axis of housing 14 as shown in the figures. As shown in the figures, housing 14 may comprise a generally rectangular shape having a long axis coinciding with the long axis of the shaft 54 which slides within housing 14 . Housing 14 further comprises a handle end 32 and a cable end 46 . The cable end 46 of the housing 14 may comprise a first shoulder 48 and a second shoulder 50 , which are utilized as described in greater detail below.
[0022] The operating rod assembly 16 is utilized to transmit the linear motion of the handle assembly 12 to cables 52 , and interacts with housing 14 to lock the operating rod assembly in various positions with respect to housing 14 , such that a desired tension is maintained in cables 52 for manipulation of the mechanism actuated by the cables. As shown in the sectional view of FIG. 7 , the operating rod assembly comprises a shaft 54 having a portion of the shaft slidingly disposed within housing 14 . Shaft 54 comprises a handle end 56 , a cable end 58 , and an intermediate section 60 which slides within housing 14 . Shaft 54 further comprises a slot 62 which allows trigger 24 free travel as it is pulled toward grip member 20 . Operating rod assembly 16 may further comprise a sleeve 64 , as shown in detail in FIG. 11 , which encircles a portion of shaft 54 . A guide bushing 66 is set within housing 14 , where the guide bushing guides the operating rod assembly 16 through the housing 14 , where the guide bushing has slots 68 , 70 and 72 which are respectively aligned with the selection slots 38 , 40 and linking slot 42 of the housing. Lock screw 44 is made up through an opening in sleeve 64 and attached into opening 74 of shaft 54 .
[0023] As best shown in FIG. 8 , cable attachment assembly 18 is attached to the cable end 58 of shaft 54 . Attached to the cable end 58 of the shaft is rod bushing 76 . Inserted within the end of rod bushing 76 and pinned and/or riveted in place is connector 78 . Pivotally attached to the top of connector 78 are links 80 , or yoke members, which pivot about shaft 82 , which may comprise a rivet, fastener or similar member, which is inserted in opening 84 of connector 78 . Pivotally attached to links 80 are stop arms 86 , where a first stop arm is attached to one side of connector 78 and a second stop arm is attached to the opposite side by rivets 88 or like device. Each stop arm 86 has a top 90 and a bottom 92 . A length is defined between the top 90 and the bottom 92 , and a slot 94 extends along a portion of the length. A rivet 96 , fastener, or like device is inserted through a portion of the slot 94 of each stop arm 86 , where the rivet 96 is inserted through rod bushing 76 , such that the stop arms 86 are free to slide along the rivet 96 for the length of the slots, such that each stop arm 86 may slide with respect to the rivet 96 . The bottom 92 of each stop arm 86 has shoulder stop contact surface 98 .
[0024] As shown in FIG. 13 , cables 52 are attached to links 80 . FIG. 13 shows the apparatus in a static condition in which, because of equivalent tension in cables 52 , the links 80 are in a balanced position, with the load evenly applied to shaft 82 . In order to operate the apparatus 10 , trigger 24 must be pulled toward grip member 20 . Once trigger 24 is pulled a sufficient length to initiate movement in the operating rod assembly 16 , grip member 20 and trigger 24 are rotated in a direction which moves lock screw 44 from selection slot 38 into linking slot 42 . Handle assembly 12 is then pulled away from housing 14 a sufficient distance to place lock screw 44 adjacent to selection slot 40 , at which point grip member 20 and trigger 24 are rotated in a direction to move lock screw 44 into selection slot 40 .
[0025] FIG. 14 depicts what occurs in the event of a cable failure. As illustrated in FIG. 14 , one of the cables 52 has failed. If this occurs, during the sequence described above, as the handle assembly 12 is pulled away from the housing 14 , the links 80 pivot downward on the side of the cable failure, causing the stop arm 86 to slide with respect to rivet 96 , causing shoulder stop contact surface 98 to come into engaging contact with first shoulder 48 , or second shoulder 50 , depending upon which cable fails. Once shoulder contact surface 98 comes into engaging contact with first shoulder 48 or second shoulder 50 , further movement of the shaft 82 is stopped, and the lock screw is prevented from engaging selection slot 40 , and the handle assembly 12 will not be moveable any further. Thus, the operator of the apparatus is provided an affirmative indication of a cable failure and the cables cannot be moved so as to actuate the particular mechanism.
[0026] While the above is a description of various embodiments of the present invention, further modifications may be employed without departing from the spirit and scope of the present invention. Thus the scope of the invention should not be limited according to these factors, but according to the following appended claims. | A handle apparatus utilized for actuating mechanisms with a pair of parallel cables detects a cable out condition, and prevents further activation of the actuated mechanism. The apparatus has a yoke mechanism which is pivotally attached to an activation rod, which in turn is connected to an activation handle. The yoke mechanism has a first side and a second side, with one of the cables attached to the first side and the other cable attached to the second side. The yoke mechanism has a first stop member attached to the first side of the yoke mechanism and a second stop member attached to the second side of the yoke mechanism. The apparatus has stationary shoulders which are placed such that the stationary shoulders will engage the stop members if either cable fails. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the continuous production of isophthalodinitrile. More in particular the present invention relates to a process for the continuous production of isophthalodinitrile by amidation and simultaneous dehydration of the dimethyl ester of isophthalic acid in vapor phase on a fixed bed of a dehydration catalyst.
2. Prior Art
The possibility of producing phthalodinitriles starting from the esters of the corresponding acids is long known; for example the UK Pat. No. 737.409 claims the synthesis of phthalodinitrile from a dialkyl phthalate by reaction with ammonia in vapor phase on a catalytic dehydration bed at a temperature comprised between 300° and 600° C.
While in the case of the preparation of terephthalodinitrile, it is possible to obtain a very good yield (approximately 97.5% of theoretical), in the case of isophthalodinitrile, due to the lesser stability of the product, a considerably lower yield is obtained which is fully unsatisfactory for industrial production. More in particular said patent exemplifies the preparation of isophthalodinitrile from diethyl isophthalate by reaction with ammonia in vapor phase on a silica gel bed at a temperature of 450° C.; the high temperature used, however, merely allows a fully unsatisfactory yield (61%).
It is also known (DTAS 1.279.020) to synthesize terephthalodinitrile starting from the dimethyl ester of terephthalic acid by reaction with ammonia in vapor phase on a dehydrating alumina bed at markedly more moderate temperatures, i.e. at 350°-360°. The nitrile which is obtained after being purified, by washing with methyl alcohol, from the colored impurities and by the terephthaldiamide polluting the reaction crude, has melting points (220°-222° C.) and yields (95-97%) very close to the theoretical values. When however one tries to apply said conditions indicated in DTAS 1.279.020 to the synthesis of isophthalodinitrile, the conversion is not as satisfactory (75-80%). Moreover the catalyst is contaminated by degradation products so as to rapidly reduce its activity.
SUMMARY OF THE INVENTION
The aim of the present invention is therefore to solve the previously described problems and to provide an improved process, industrially advantageous, for the production of isophthalodinitrile at such a degree of purity that it can be used directly, without any preliminary purification process, as raw material in the synthesis of tetrachloroisophthalodinitrile, according to the direct chlorination process of nitrile in vapor phase on a catalytic bed.
The studies of the Applicant have been therefore aimed at seeking such operating conditions as to prevent the excessive decomposition both of the raw material and of the reaction product; an improved process has thus been provided which allows the synthesis of isophthalodinitrile starting from dimethyl isophthalate, conjugated with very high yields and purities, mainly characterized by suitable reaction temperatures together with high ammonia/ester molar ratios, in the presence of a dehydrating catalytic bed.
More in particular it has been observed that it is necessary to perform a rigorous control of the temperature profile in the reactor; in fact an excessively high temperature in the lower part of the reactor determines significant decompositions of the raw material, while an excessively low temperature in the finishing phase (terminal part of the reactor) determines a non-completion of the reaction and the consequent permanence, in the final product, of high percentages of the intermediate products isophthalamide and/or cyanobenzamide, to the full detriment of the purity and of the yields in isophthalodinitrile.
An object of the present invention is therefore a process for the preparation of isophthalodinitrile by amidation and simultaneous dehydration of a dialkyl ester of isophthalic acid in vapor phase on a fixed bed of a dehydration catalyst, characterized in that the dimethyl ester of the isophthalic acid is caused to vaporize continuously in a flow of inert gas of preheated recycling gas, and sent, separately or together with a preheated flow of excess ammonia with respect to the theoretically required amount, into a fixed bed of a dehydration catalyst kept at a thermal condition variable between the temperature of the base, lower than 310° C., and that of the head at a temperature comprised between 350° and 450°.
In operating with these temperature conditions it is also important to observe a rather high molar ratio between ammonia and dimethyl isophthalate: good results have been obtained by mixing ≧12 preferably ≧15 more preferably ≧30 moles of ammonia with one of ester. The contact times may vary rather widely between 0.1 and 100 sec, preferably from 1 to 10 sec.
As dehydration catalyst it is possible to use active alumina, but other known catalysts are suitable for use. In particular it has been observed that it is possible to further improve the catalytic activity of alumina, with even more satisfactory results in synthesis, by impregnating it with an active component based on borophosphate.
Isophthalodinitrile which forms in the above described conditions is subsequently recovered, by cooling from the reaction mixture, in the form of powder, while the gases and vapors which are released (N 2 , CH 3 OH, H 2 O, NH 3 ) are subject to continuous elimination and are possibly partly recycled. Alternately the ammonia can be separated by means of an appropriate system from most of the water and of the methyl alcohol which form in the reaction, and can thus be recycled.
The dinitrile of isophthalic acid thus collected by desublimation appears as white crystalline powder, and the titres, despite the absence of specific purification treatments, are very high (≧98%), and so are the yields, calculated with respect to the dimethyl isophthalate (≧95%).
A further advantage, consequent to the low initial temperatures of the process, has been observed in relation to the possible presence of methylamine among the byproducts of reaction. The formation of this substance by amination of methanol in the presence of dehydration catalysts is in fact always possible and is proportionally facilitated by the increase in the temperature: by operating in the range of temperatures according to the invention its amount is contained to levels which do not comprise the process.
The isophthalodinitrile obtained by means of the process according to the invention constitutes a further object of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples are given to illustrate more specifically the present invention without thereby constituting any limitative character.
EXAMPLE 1
Dimethyl isophthalate (0.0737 M/h) vaporized in a flow of hot nitrogen (0.3688 M/h) is fed to the base of a fixedbed reactor, having a diameter of 4 cm and a length of approximately 20 cm loaded with 162 g (approximately 210 cc) of activated alumina in the form of microspheres with diameter comprised between 1.5 and 2 mm.
Gaseous ammonia (3.3796 M/h) is simultaneously sent to the base of the catalytic layer. The two feed currents, before mixing, are approximately heated so as to keep the bottom of the catalytic bed, externally heated by electric resistors, at the temperature of 280° C. The NH 3 /ester molar ratio is kept at 45.9.
The gases and vapors in output from the top of the reactor kept at the temperature of 360° C. are cooled in a collecting container at room temperature.
Therein the isophthalodinitrile desublimates in the form of crystalline powder, while the gases and the vapors which escape (N 2 , NH 3 , CH 3 OH, H 2 O) are sent to a water-shower elimination system.
After 7 hours and 30 minutes of reaction, the solid is collected, dried in a stove at 70° C. 69.2 g of ivory-white powder are obtained.
IR and GC analyses confirm that this is isophthalodinitrile at a high degree of purity (98.5%).
The yield, calculated with respect to dimethyl isophthalate, is therefore 96.2%.
EXAMPLE 2
A comparison example is given, using the same reactor previously described and the reaction conditions described in example 2 of the DTAS patent No. 1.279.020: dimethyl isophthalate and ammonia are fed (NH.sub. 3/ester molar ratio 10) at the base of the catalytic bed with flow-rates respectively of 0.0393 M/h and 0.3930 M/h and are caused to react at the uniform temperature of 350° C.
After 5 hours 37 minutes 19.8 g of product are collected which, despite an abundant washing performed with water before drying, has a brownish color and a nitrile titre of 86.4%, and the molar yield, calculated with respect to the ester, is only 65%.
EXAMPLE 3
With the same apparatus and the same methods of example 1, dimethyl isophthalate (0.0644 M/h vaporized in a flow of nitrogen (0.3688 M/h) and ammonia gas (3.3796 M/h) are continuously fed so that the reaction temperature is comprised between 280° C. (reactor bottom) and 360° C. (reactor head). The NH 3 /ester molar ratio is kept at 52.5.
In this case alumina with borophosphate added (in the measure of approximately 20%) obtained by impregnation of the microspheres with an ammonical and equimolecular solution of boric and phosphoric acid, drying and thermal activation at 400° C. for a few hours, is used as catalytic system. 69 g of white powder are collected after 7 hours 30 minutes. The titre in isophthalodinitrile is higher than 99% and similarly the molar yield, calculated with respect to the ester, is greater than 99%.
EXAMPLE 4
In a semi-pilot apparatus, the reactor whereof is constituted by a steel tube having an inner diameter of 43 mm, a height of 1000 mm, externally heated with air and loaded with approximately 1.5-1 of 1.5-3 mm diameter alumina spheres, the gaseous current of the reagents is sent from below upwards setting a temperature profile between 300°0 C. in input and 360° in output.
Thus a current of dimethyl isophthalate (1.1M/h) vaporized at 225° C. with a current of hot nitrogen (3.5M/h) makes contact with a mixture of ammonia (15M/h) and nitrogen (20.5M/h) such that the ammonia/isophthalate molar ratio is 13.5 and the concentration of ammonia in the reagent gases is 37.5%. The contact between ammonia and isophthalate occurs at the inlet of the fixed bed and the temperature after mixing is 300° C.
After 2.6 seconds of permanence on the dehydrating catalytic bed, the gases exit from the reactor at 360° C. and go to a desublimator where they are cooled down to 70°.
A pale yellow, needle-like and extremely fine product is separated which, without desiccation and purifications, has a purity of 99.7% with an isophthalodinitrile yield of 96.5%.
EXAMPLE 5
In the same apparatus and with the same temperatures and the same methods described in example 4, 2M/h dimethyl isophthalate, 8M/h vaporization nitrogen and 65M/h ammonia are fed with a molar ratio of 32.5, a concentration of ammonia in the gases of 86.6 and a permanence time of 1.5 seconds.
A product is obtained with a 99% purity and a 96.1% yield of isophthalodinitrile with a specific productivity of 164 g/h·dm 3 of catalytic bed.
EXAMPLE 6
In the same apparatus and with the same methods described in examples 4 and 5, but at a temperature of output from the reactor of 380°-390° C., 2M/h of dimethyl isophthalate, 8M/h of vaporization nitrogen and 30M/h of ammonia are fed, with an NH 3 /ester molar ratio of 15, a concentration of ammonia in the gases of 75% and a permanence time of 2.6 seconds.
A product is obtained having a purity of 99.2% and an isophthalodinitrile yield of 95.8%, with a specific productivity of 163.5 g/h ·dm 3 of catalytic bed. | The present invention relates to a process for the continuous production of isophthalodinitrile by amidation and simultaneous dehydration of the dimethyl ester of isophthalic acid in vapor phase on the fixed bed of a dehydration catalyst. | 2 |
This application is a Continuation of U.S. application Ser. No. 14/439,459, filed Apr. 29, 2015, which claims priority to International Patent Application No. PCT/CN2013/085966, filed Oct. 25, 2013, which claims priority to Chinese patent Application No. 201210424253.2, filed Oct. 30, 2012. The entirety of the aforementioned applications is incorporated herein by reference.
FIELD
The present disclosure generally relates to a drive circuit for an LED light source module, particularly relates to a circuit for an AC directly-driven LED light source module, and more particularly relates to a LED dimming drive circuit compatible with a silicon-controlled dimmer.
BACKGROUND
LEDs, as newly emerged solid light sources, have the prospect of becoming a new generation of light source with advantages such as energy conservation, environmental protection, long service life and the like. It is known that an LED is driven by a DC voltage. However, AC power is generally supplied in daily life. Therefore, for the LED to normally emit light, a power converter is required to implement the functions of rectification and voltage reduction. Introduction of a power converter may bring about many negative effects. Firstly, service life of the power converter is far shorter than that of the LED, so service life of a light-emitting device may be shortened. Secondly, the power converter may reduce efficiency of the light-emitting device. Thirdly, in a low-power application, the power converter may cause reduction of the power factor and increase of the total harmonic current. In order to fully utilize the advantages of the LED, an LED light-emitting device directly driven by an AC power is developed.
In conventional technical solutions of LED driving, in combination with a traditional silicon-controlled dimmer, only the traditional function of luminance adjustment is considered, but the adjustability of color temperature and hue of the LED is not taken into consideration. In addition, in most of the conventional technical solutions of LEDs driven by the AC power, multiple LED components are coupled in reverse parallel or based on a topology of a rectification bridge circuit, to meet the driving requirements of the AC power. However, the AC power is subjected to fluctuation according to a specific frequency cycle. Since the LED has its own switch-on voltage, when the transient voltage exceeds the switch-on voltage, the LED may be unintentionally switched on and emit light. Otherwise, the LED may be cut-off and does not emit light. Such circuit causes low light-emitting efficiency for the LED, and in addition, when the AC voltage fluctuates, the LED may flicker.
SUMMARY
An objective of the present disclosure is to provide a circuit for an AC directly-driven LED light source module, and in particular, a dimming drive circuit compatible with a silicon-controlled dimmer.
According to one aspect of the present disclosure, an AC dimming drive circuit for an LED is provided, including: a rectification unit and a first-stage LED DC drive circuit including a first voltage sampling unit, a first switch unit, and a first LED light source module, wherein the rectification unit receives an AC voltage, and rectifies the received AC voltage and outputs a DC voltage; the rectification unit outputs, through a first output terminal of the rectification unit, the output DC voltage to an input terminal of the first LED light source module and a first terminal of the first voltage sampling unit, an output terminal of the first LED light source module is coupled to a first input terminal of the first switch unit, a voltage division terminal of the first voltage sampling unit is coupled to a second input terminal of the first switch unit; and a second terminal of the first voltage sampling unit, an output terminal of the first switch unit, and a second output terminal of the rectification unit are grounded; the first switch unit receives, through the first LED light source module, a first switch-on voltage, and receives, through the voltage division terminal of the first voltage sampling unit, a first switch-off voltage; and when the first switch-on voltage rises to reach a first switch-on voltage threshold of the first switch unit, the first switch unit is conducted and the first LED light source module continuously emits light; and when the received first switch-off voltage rises to reach a first switch-off voltage threshold of the first switch unit, the first switch unit is switched off such that the first LED light source module stops emitting light.
The first switch-off voltage threshold is adjusted by setting an internal parameter of the first switch unit.
The AC dimming drive circuit for an LED further comprises:
an input protection unit, an input terminal of the input protection unit being coupled to the AC voltage and an output terminal of the input protection unit being coupled to an input terminal of the rectification unit.
The first LED light source module comprises:
a plurality of LED light-emitting units coupled in series;
a plurality of LED light-emitting units coupled in parallel; or
a plurality of LED light-emitting units coupled partly in series and partly in parallel.
The first voltage sampling unit comprises:
a first resistor, one terminal of the first resistor being coupled to the first output terminal of the rectification unit; and
a second resistor, one terminal of the second resistor being coupled to the other terminal of the first resistor and acting as the voltage division terminal of the first voltage sampling unit, and the other terminal of the second resistor being grounded.
A switch-off time of the first switch unit is adjusted by setting resistances of the first resistor and the second resistor.
The first switch unit comprises a third resistor, a fourth resistor and a fifth resistor, a first Zener diode and a second Zener diode, and a first field-effect transistor and a second field-effect transistor, wherein
one terminal of the third resistor is coupled to the voltage division terminal;
a negative terminal of the first Zener diode is coupled to the voltage division terminal, and a positive terminal of the first Zener diode is grounded;
a gate of the first field-effect transistor is coupled to the other terminal of the third resistor, and a source of the first field-effect transistor is grounded;
a drain of the first field-effect transistor, one terminal of the fourth resistor, one terminal of the fifth resistor, and a negative terminal of the second Zener diode are coupled to one another;
the other terminal of the fifth resistor is coupled to a gate of the second field-effect transistor; and a drain of the second field-effect transistor, the other terminal of the fourth resistor, and a negative terminal of the first LED light source module are coupled to one another; and
a positive terminal of the second Zener diode and a source of the second field-effect transistor are grounded.
Further, the AC dimming drive circuit for an LED further comprises a silicon-controlled dimmer, coupled in series between an AC live wire and the rectification unit.
Further, the AC dimming drive circuit for an LED further comprises a silicon-controlled dimmer, coupled in series between an AC live wire and the input protection unit.
According to another aspect of the present disclosure, an AC dimming drive circuit for an LED is provided, including: a rectification unit and N stages of LED DC drive circuits, an i th stage of LED DC drive circuit including an i th voltage sampling unit, an i th switch unit, and an i th LED light source module, N being a natural number greater than 1, and i=2, 3, . . . , N; wherein
the rectification unit receives an AC voltage, and rectifies the received AC voltage and outputs a DC voltage;
a first terminal of the i th voltage sampling unit and an input terminal of the i th LED light source module are both coupled to a first output terminal of the rectification unit if i is equal to 1, and both coupled to an output terminal of an i−1 th LED light source module if i is not equal to 1; a second terminal of the i th voltage sampling unit is grounded, and a voltage division terminal of the i th voltage sampling unit is coupled to a second input terminal of the i th switch unit;
a first input terminal of the i th switch unit is coupled to an output terminal of the i th LED light source module, and an output terminal of the i th switch unit and a second output terminal of the rectification unit are grounded;
the i th switch unit receives, through the i th LED light source module, an i th switch-on voltage, and receives, through the voltage division terminal of the i th voltage sampling unit, an i th switch-off voltage; and
when the i th switch-on voltage rises to reach an i th switch-on voltage threshold of the i th switch unit, the i th switch unit is conducted and the first to the i th LED light source modules continuously emit light, and meanwhile an input terminal and an output terminal of the (i+1) th to the N th stage LED DC circuits are short circuited; and when the received i th switch-off voltage rises to reach an i th switch-off voltage threshold of the i th switch unit, the i th switch unit is switched off, and if i is less than N, an (i+1) th switch-on voltage of an (i+1) th switch unit is caused to rise to reach an (i+1) th switch-on voltage threshold, such that the first to (i+1) th LED light source modules emit light, and if i is equal to N, the first to N th LED light source modules are caused to stop emitting light.
Each LED light source module has a different or the same color temperature and hue, wherein
an internal parameter of the voltage sampling unit in each stage of LED DC drive circuit is set such that a switch-off time of the switch unit in each stage of LED DC drive unit is different to control a corresponding LED light source module.
The i th LED light source module comprises:
a plurality of LED light-emitting units coupled in series;
a plurality of LED light-emitting units coupled in parallel; or
a plurality of LED light-emitting units coupled partly in series and partly in parallel.
Further, the AC dimming drive circuit for an LED comprises an input protection unit, an input terminal of the input protection unit being coupled to the AC voltage and an output terminal of the input protection unit being coupled to an input terminal of the rectification unit.
Each voltage sampling unit comprises:
a first resistor, one terminal of the first resistor being coupled to the first output terminal of the rectification unit; and
a second resistor, one terminal of the second resistor being coupled to the other terminal of the first resistor and acting as a voltage division terminal of each voltage sampling unit, and the other terminal of the second resistor being grounded.
Switch-off time of the switch unit in each stage of LED DC drive circuit is regulated by setting resistances of the first resistor and the second resistor.
Each switch unit comprises a third resistor, a fourth resistor and a fifth resistor, and a first Zener diode and a second Zener diode, and a first field-effect transistor and a second field-effect transistor, wherein
one terminal of the third resistor is coupled to a voltage division terminal of the corresponding voltage sampling unit;
a negative terminal of the first Zener diode is coupled to the voltage division terminal, and a positive terminal of the first Zener diode is grounded;
a gate of the first field-effect transistor is coupled to the other terminal of the third resistor, and a source of the first field-effect transistor is grounded;
a drain of the first field-effect transistor, one terminal of the fourth resistor, one terminal of the fifth resistor, and a negative terminal of the second Zener diode are coupled to one another;
the other terminal of the fifth resistor is coupled to a gate of the second field-effect transistor; and a drain of the second field-effect transistor, the other terminal of the fourth resistor, and a negative terminal of the corresponding LED light source module are coupled to one another; and
a positive terminal of the second Zener diode and a source of the second field-effect transistor are grounded.
Further, the AC dimming drive circuit for an LED further comprises a silicon-controlled dimmer, coupled in series between an AC live wire and the rectification unit.
Further, the AC dimming drive circuit for an LED further comprises a silicon-controlled dimmer, coupled in series between an AC live wire and the input protection unit.
In the present disclosure, when the transient value of the AC voltage reaches the switch-on voltages of the LED light source modules, the switch unit is conducted and the LED light source modules start emitting light; and when the transient value of the AC voltage exceeds a preset switch-off voltage, the switch unit is switched off, and the corresponding next-stage LED light source module also starts emitting light. When the silicon-controlled dimmer is tuned via a knob, the conduction angle of the silicon-controlled dimmer changes, such that the LED light source modules having different color temperatures or hues independently or collaboratively emit light, thereby implementing adjustable color temperature or hue of the entire circuit. When the AC power fluctuates, within a normal range of operating voltage, that is, between the switch-on voltage and the preset switch-off voltage of the LED light source module, only switch-on time point and switch-off time point change, and the LED light source modules still emit light. Therefore, when the AC power is subjected to fluctuation, the device does not flicker.
The present disclosure has the following advantages: the dimming drive circuit directly driving the LED module using an AC voltage is compatible with a traditional silicon-controlled dimmer, and the luminance, color temperature, or hue may be adjusted with no need of separately deploying wires; the circuit is simple in structure, small in size, light in weight, and low in cost; the input protection unit improves reliability and safety of the device, enhances electromagnetic interference resistant capabilities, and reduces electromagnetic interference caused by the power grid. The sampling resistor network controls switch-on and switch-off of the switch unit. A suitable switch-off voltage is preset, such that the AC power directly drives the LED device not to flicker in case of voltage fluctuation. Moreover, when a transient voltage of the AC power is over-high, the switch unit is switched off, and the LED light source module does not emit light, thereby improving the efficiency of the power and reducing power loss. In the meantime, this also prevents the LED light source module from being damaged due to a large current, and thus prolongs service life of the device.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a schematic diagram of an AC dimming drive circuit for an LED according to an embodiment of the present disclosure;
FIG. 2 is a schematic diagram of an AC dimming drive circuit for an LED according to an embodiment of the present disclosure;
FIG. 3 is a schematic diagram of an AC dimming drive circuit for an LED according to an embodiment of the present disclosure;
FIG. 4 is an exemplary circuit diagram of the AC dimming drive circuit for an LED as illustrated in FIG. 1 ;
FIG. 5 is a schematic diagram of an AC dimming drive circuit for an LED according to another embodiment of the present disclosure; and
FIG. 6 is an exemplary circuit diagram of the AC dimming drive circuit for an LED according to the embodiment as illustrated in FIG. 5 .
DETAILED DESCRIPTION
To make the objectives, technical solutions, and advantages of the present disclosure more apparent, the present disclosure is described in detail with reference to the accompanying drawings and preferred embodiments. However, it should be noted that some details set forth in the description are merely for thorough and better understanding of one or more aspects of the present disclosure, and the aspects of the present disclosure may also be implemented without such particular details.
FIG. 1 is a schematic diagram of an AC dimming drive circuit for an LED according to an embodiment of the present disclosure. As illustrated in FIG. 1 , the AC dimming drive circuit includes a rectification unit 12 , a first voltage sampling unit 14 , a first switch unit 16 , and a first LED light source module 18 . The rectification unit 12 includes four diodes which form a rectification circuit of a bridge arrangement. Alternatively, the rectification unit 12 may also be a rectification unit of another circuit arrangement. The rectification unit 12 receives an AC voltage and rectifies the received AC voltage. The rectification unit 12 outputs, through a first output terminal, i.e. a positive terminal, of the rectification unit, a DC voltage resulted from the rectification to an input terminal of the first LED light source module 18 and a first terminal of the first voltage sampling unit 14 . An output terminal of the first LED light source module 18 is coupled to a first input terminal of the first switch unit 16 , and a voltage division terminal of the first voltage sampling unit 14 is coupled to a second input terminal of the first switch unit 16 . A second terminal of the first voltage sampling unit 14 , an output terminal of the first switch unit 16 , and a second output terminal, i.e. a negative terminal, of the rectification unit 12 are grounded. The first switch unit 16 receives, through the first LED light source module 18 , a first switch-on voltage, and receives, through the voltage division terminal of the first voltage sampling unit 14 , a first switch-off voltage. When the first switch-on voltage rises to reach a first switch-on voltage threshold of the first switch unit 16 , the first switch unit 16 is conducted and the first LED light source module 18 continuously emits light. When the received first switch-off voltage rises to reach a first switch-off voltage threshold of the first switch unit 16 , the first switch unit 16 is switched off such that the first LED light source module 18 stops emitting light. In the present disclosure, the output voltage of the voltage division terminal is adjusted by setting an internal parameter of the first voltage sampling unit 14 , and a switch-off time is adjusted by adjusting the first switch-off voltage threshold of the first switch unit 16 .
In the present disclosure, the LED light source module comprises a plurality of LED light-emitting units coupled in series, a plurality of LED light-emitting units coupled in parallel, or a plurality of LED light-emitting units coupled partly in series and partly in parallel. The LED light source module may have different color temperatures or the same color temperature, or may have different hues or the same hue.
Optionally, as illustrated in FIG. 1 , to protect the entire circuit, the AC dimming drive circuit further includes an input protection unit 10 . An input terminal of the input protection unit 10 is coupled to the AC voltage and an output terminal of the input protection unit 10 is coupled to an input terminal of the rectification unit 12 . It may be understood by those skilled in the art that the input protection unit is not necessary. The input protection unit 10 provides a basic protection function for the entire circuit, and constitutes of a voltage dependent resistor, a thermistor, and a fuse; and when being applied to a special environment, the input protection unit 10 may further include a common mode choke and a gas discharge tube.
Further, the AC dimming drive circuit further includes a first AC wiring terminal and a second AC wiring terminal. The AC voltage is input to the input protection unit 10 via the first AC wiring terminal and the second AC wiring terminal.
FIG. 2 is a schematic diagram of an AC dimming drive circuit for an LED according to an embodiment of the present disclosure. In FIG. 2 , a silicon-controlled dimmer 11 is coupled in series between the AC live wire and the rectification unit 12 .
FIG. 3 is a schematic diagram of an AC dimming drive circuit for an LED according to an embodiment of the present disclosure. In FIG. 3 , the silicon-controlled dimmer 11 is coupled in series between the AC live wire and the input protection unit 10 .
FIG. 4 is an exemplary circuit diagram of the AC dimming drive circuit for an LED as illustrated in FIG. 1 . As illustrated in FIG. 4 , the input protection unit 10 constitutes of a fuse and a voltage dependent resistor VR. As described above, the AC dimming drive circuit may not include the input protection unit 10 . The first voltage sampling unit 14 constitutes of a first resistor R 1 and a second resistor R 2 . The first switch unit is formed of two field-effect transistor MOSFETs, three resistors, and two Zener diodes. The first AC wiring terminal is coupled to a terminal of the fuse and serves as an AC live wire terminal L; and the second AC wiring terminal is coupled to one terminal of the voltage dependent resistor VR and an AC input terminal of the rectification bridge of the rectification unit, and serves as an AC zero wire terminal N. The other terminal of the fuse is coupled to the other terminal of the voltage dependent resistor VR and the other AC terminal of the rectification bridge of the rectification unit 12 . A positive output terminal of the rectification bridge is coupled to one terminal of the first resistor R 1 , and is also coupled to a positive terminal of the first LED light source module, and a negative output terminal of the rectification bridge is grounded. The other terminal of the first resistor R 1 is coupled to one terminal of the second resistor R 2 , a negative terminal of the first Zener diode DZ 1 , and one terminal of the third resistor R 3 . The other terminal of the third resistor R 3 is coupled to a gate of the first field-effect transistor M 1 . A drain of the first field-effect transistor M 1 , one terminal of the fourth resistor R 4 , one terminal of the fifth resistor R 5 , and a negative terminal of the second Zener diode DZ 2 are coupled to one another. The other terminal of the fifth resistor R 5 is coupled to a gate of the second field-effect transistor M 2 . A drain of the second field-effect transistor M 2 , the other terminal of the fourth resistor R 4 , and a negative terminal of the first LED light source module are coupled to one another. The other terminal of the second resistor R 2 , a positive terminal of the first Zener diode DZ 1 , a positive terminal of the second Zener diode DZ 2 , a source of the first field-effect diode M 1 , and a source of the second field-effect transistor M 2 are grounded.
In the embodiments as illustrated in FIG. 4 , the AC dimming drive circuit is coupled to the AC electric grid via a plug. The AC voltage passes through the input protection unit, and is rectified via the rectification unit to a DC voltage and then provided to the first voltage sampling unit, the first switch unit, and the first LED light source module. In each AC cycle, the voltage output from the rectification bridge rises from zero. When the voltage rises to the first switch-on voltage of the first switch unit, the first field-effect transistor M 1 is switched off, the second field-effect transistor M 2 is conducted, and the first LED light source module starts emitting light. As the input voltage rises, the current passing through the first LED module increases. When the voltage output from the voltage division terminal of the first sampling unit is less than a preset switch-off voltage threshold, the voltage output from the voltage division terminal of the first voltage sampling unit is not sufficient to cause the first field-effect transistor M 1 to be conducted. Thus, M 1 remains switched off, the second field-effect transistor M 2 remains conducted, and the first LED light source module continuously emits light. When the voltage continues to rise to cause the voltage output from the voltage division terminal of the first voltage sampling unit to exceed a preset first switch-off voltage threshold, the first field-effect transistor M 1 becomes conducted, the second field-effect transistor M 2 is switched off, and the first LED light source module does not emit light, thereby protecting the first LED light source module from being impacted by a large current. As described above, the conduction time of the first field-effect transistor M 1 may be adjusted by setting resistances of the first resistor R 1 and the second resistor R 2 in the first voltage sampling unit, thereby adjusting the first switch-off voltage threshold. Optionally, in the above embodiments, the switch tubes are implemented as the field-effect transistors M 1 and M 2 . For those skilled in the art, the switch tubes in the present disclosure may be implemented as bipolar junction transistors BJTs or other switch elements having equivalent functions instead of the field-effect transistors. It may be understood by those skilled in the art that when the field-effect transistor is conducted (i.e., the first switch unit is conducted), the voltage drop between the drain and the source is very small, that is, the field-effect transistor is almost in a short-circuit state.
FIG. 5 is a schematic diagram of an AC dimming drive circuit for an LED according to another embodiment of the present disclosure. Similar to the embodiment as illustrated in FIG. 1 , the AC dimming drive circuit includes a rectification unit 12 , a first voltage sampling unit 14 , a first switch unit 16 , and a first LED light source module 18 . The first voltage sampling unit 14 , the first switch unit 16 , and the first LED light source module 18 form a first-stage LED DC dimming drive circuit. Further, the AC dimming drive circuit according to this embodiment further includes: a second-stage LED DC dimming drive circuit including a second voltage sampling unit 20 , a second switch unit 22 , and a second LED light source module 24 ; and a third-stage LED DC dimming drive circuit including a third voltage sampling unit 26 , a third switch unit 28 , and a third LED light source module 30 . In this embodiment, the second voltage sampling unit 20 , the second switch unit 22 , and the second LED light source module 24 are respectively the same as the first voltage sampling unit 14 , the first switch unit 16 , and the first LED light source module 18 ; and similarly, the third voltage sampling unit 26 , the third switch unit 28 , and the third LED light source module 30 are respectively the same as the first voltage sampling unit 14 , the first switch unit 16 , and the first LED light source module 18 .
FIG. 6 is an exemplary circuit diagram of the AC dimming drive circuit for an LED according to the embodiment as illustrated in FIG. 5 . As illustrated in FIG. 6 , a first terminal of the second voltage sampling unit 20 and an input terminal of the second LED light source module 24 are both coupled to an output terminal of the first LED light source module 18 . A second terminal of the second voltage sampling unit 20 is grounded, and a voltage division terminal of the second voltage sampling unit 20 is coupled to a second input terminal of the second switch unit 22 . A first input terminal of the second switch unit 22 is coupled to an output terminal of the second LED light source module 24 , and an output terminal of the second switch unit 22 is grounded. Similar to the first-stage LED DC drive circuit, the second switch unit 22 receives, through the second LED light source module 24 , a second switch-on voltage, and receives, through the voltage division terminal of the second voltage sampling unit 20 , a second switch-off voltage. When the first switch-on voltage reaches a first switch-on voltage threshold, the first switch unit is conducted, and the first LED light source module emits light; and meanwhile input terminals and output terminals of the second LED DC drive circuit and the third LED DC drive circuit are short circuited. Thereby, the second LED light source module does not emit light. After the first switch unit is short circuited, the second switch-on voltage gradually rises. When the second switch-on voltage rises to reach a second switch-on voltage threshold of the second switch unit 22 , the second switch unit 22 is conducted and the second LED light source module 24 and the first LED light source module both continuously emit light. When the received second switch-off voltage rises to reach a second switch-off voltage threshold of the second switch unit 22 , the second switch unit 22 is switched off such that the second LED light source module 24 stops emitting light.
Similar to the second-stage LED DC dimming drive circuit being coupled to the first-stage LED DC dimming drive circuit, a third-stage LED DC dimming drive circuit is coupled to the second-stage LED DC dimming drive circuit. Specifically, a first terminal of the third voltage sampling unit 26 and an input terminal of the third LED light source module 28 are both coupled to an output terminal of the second LED light source module 24 . A second terminal of the third voltage sampling unit 26 is grounded, and a voltage division terminal of the third voltage sampling unit 26 is coupled to a second input terminal of the third switch unit 30 . A first input terminal of the third switch unit 30 is coupled to an output terminal of the third LED light source module 28 , and an output terminal of the third switch unit 30 is grounded. Similar to the first-stage LED DC drive circuit, the third switch unit 30 receives, through the third LED light source module 28 , a third switch-on voltage, and receives, through the voltage division terminal of the third voltage sampling unit 26 , a third switch-off voltage. When either the first switch unit or the second switch unit is conducted, the third-stage LED DC drive circuit is short circuited, and thereby, the third LED light source module does not emit light. When the first switch unit and the second switch unit are both switched off, the third switch-on voltage gradually rises. When the third switch-on voltage rises to reach a third switch-on voltage threshold of the third switch unit 30 , the third switch unit 30 is conducted and the first to third LED light source modules 28 continuously emit light. When the received third switch-off voltage rises to reach a third switch-off voltage threshold of the third switch unit 30 , the third switch unit 30 is switched off such that all the LED light source modules 28 stop emitting light, thereby achieving the objective of protecting the LED module units.
In the second-stage LED DC drive circuit, the second voltage sampling unit is formed of two resistors, and the second switch unit is formed of two MOSFETs, three resistors, and two Zener diodes. Similarly, in the third-stage LED DC drive circuit, the third voltage sampling unit is formed of two resistors, and the third switch unit is formed of two MOSFETs, three resistors, and two Zener diodes. The specific configuration of the circuit of the second-stage LED DC drive circuit is similar to that of the third-stage LED DC drive circuit, which is not repeated herein.
In this embodiment, the AC dimming drive circuit may adjust the brightness, color temperature, or hue of the first to third LED light source modules. Specifically, internal parameters of each of the first to third voltage sampling units, for example, resistances of two voltage division resistors in each voltage sampling unit are set, such that each stage of switch unit may have a different switch-off time. In this way, a conduction time of the LED light source module for a specific color temperature or hue is controlled, and thus changes of the color temperature or hue of the entire lighting device are adjusted.
Optionally, the AC dimming drive circuit may further include an input protection unit 10 to protect the entire circuit.
In the above embodiment, the AC dimming drive circuit for an LED includes one stage of LED DC dimming drive circuit or three stages of LED DC dimming drive circuits. Based on the principles of the above embodiments, it may be understood by those skilled in the art that the present disclosure may be applicable to two stages or more than three stages of LED DC dimming drive circuits.
In N stages of LED DC dimming drive circuits (N is a natural number greater than 1), the configuration of the circuit of the first-stage LED DC dimming drive circuit is described as the above, and in addition, an i th stage is coupled to an i−1 th stage of LED DC dimming drive circuit in a same manner the second stage is coupled to the first stage of LED DC dimming drive circuit, where, i is an integer, and i=2, 3, 4, . . . , N. The i th -stage LED DC drive circuit includes an i th voltage sampling unit, an i th LED light source module, and an i th switch unit. The specific configuration of the i th LED DC drive circuit is the same as the configuration of the first LED DC dimming drive circuit as described in the above embodiment. The i th switch unit receives, through the i th LED light source module, an i th switch-on voltage, and receives, through the voltage division terminal of the i th voltage sampling unit, an i th switch-off voltage. When the i th switch-on voltage rises to reach an i th switch-on voltage threshold of the i th switch unit, the i th switch unit is conducted and all of the first i LED light source modules continuously emit light. Then, after the i th switch unit is conducted, an input terminal and an output terminal of the next stage, i.e. of the (i+1) th -stage LED DC drive circuit, are short circuited. Thereby, the (i+1) th LED light source module does not emit light. When the received i th switch-off voltage rises to an i th switch-off voltage threshold of the i th switch unit, the i th switch unit is switched off. If i<N, after the i th switch unit is switched off, an (i+1) th switch-on voltage of the (i+1) th switch unit in the (i+1) th -stage LED DC drive circuit gradually rises to reach an (i+1) th switch-on voltage threshold. Then, the (i+1) th switch unit is conducted, and all of the first i+1 LED light source modules emit light. Otherwise, if i=N, after the i th switch unit is switched off, all of the LED light source modules stop emitting light.
Similarly, an internal parameter of the i th voltage sampling unit, for example, resistances of two voltage division resistors in each voltage sampling unit, are set such that each stage of switch unit has a different switch-off time. In this way, a conduction time of the LED light source module for a specific color temperature or hue is controlled, and thus changes of the color temperature or hue of the i th LED light source module in the entire lighting device are adjusted.
Accordingly, in the above embodiments of the present disclosure, the voltage sampling unit is capable of monitoring an input voltage, and also achieves the function of protecting the LED light source module. When the AC voltage is subjected to a great fluctuation, the switch unit in each stage may be timely switched off, thereby protecting the LED light source module in this stage from being damaged due to a large current.
In addition, the AC dimming drive circuit for an LED according to the present disclosure may further include a silicon-controlled dimmer (not illustrated in the drawings). Under such circumstances, the input terminal of the input protection unit may be coupled to an AC voltage via the silicon-controlled dimmer. The silicon-controlled dimmer may cut the phase of the input AC voltage. Therefore, the voltage input to the rectification unit does not have a complete sinusoidal waveform. A voltage switch-off point is set for each stage of switch unit in the voltage sampling unit in each stage of LED DC drive circuit, such that light source modules having different color temperatures or hues independently or collaboratively emit light, thereby adjusting the color temperature or hue of the LED light source module. In the present disclosure, the silicon-controlled dimmer may be directly coupled in series to a loop of the entire circuit, and the luminance, color temperature, or hue may be adjusted with no need of separately deploying a control loop.
In the present disclosure, the dimming drive circuit directly driving the LED module using an AC voltage is compatible with a traditional silicon-controlled dimmer, and the luminance, color temperature, or hue may be adjusted with no need of separately deploying wires. The circuit according to the present disclosure is simple in structure, small in size, light in weight, and low in cost. Use of the input protection unit improves reliability and safety of the device, enhances electromagnetic interference resistant capabilities, and reduces electromagnetic interference caused by the electric grid. A suitable switch-off voltage is set for the voltage sampling resistor network controlling conduction or switch-off of the switch unit, and therefore the LED light source module is directly driven by the AC voltage. In addition, the LED light source module does not flicker when the AC voltage is subjected to fluctuation. Moreover, when a transient voltage of the AC power is over-high, the switch unit is switched off, and the LED light source module does not emit light, thereby improving efficiency of the power and reducing power loss. In the mean time, this also prevents the LED light source module from being damaged due to a large current, and thus prolongs service life of the device.
Described above are preferred embodiments of the present disclosure. It should be noted that those skilled in the art may derive other alterations or modifications without departing from the principles of the present disclosure. Such alterations and modifications shall be deemed as falling within the protection scope of the present disclosure. | Disclosed is an alternating current dimming drive circuit for an LED, comprising a rectification unit and N stages of LED direct current drive circuits. In the i th stage of LED direct current drive circuit, a first end of the i th voltage sampling unit and an input end of the i th LED light source module directly or indirectly receive the output voltage of the rectification unit; a voltage division end of the i th voltage sampling unit is connected to a second input end of the i th switch unit; and a first input end of the i th switch unit is connected to an output end of the i th LED light source module, and an output end of the i th switch unit, a second end of the i th voltage sampling unit and a second output end of the rectification unit are grounded. When the i th switch unit is switched on, the first to the i th LED light source modules emit light. When the i th switch unit is switched off, if i is less than N, the first to the (i+1) th LED light source modules emit light, and if i is equal to N, the first to the N th LED light source modules stop emitting light. The present invention realizes an alternating current directly-driven LED light source module and will not flicker in the case of alternating current voltage fluctuation. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of co-pending U.S. patent application Ser. No. 11/556,031 filed Nov. 2, 2006, which is hereby incorporated herein in its entirety by reference.
FIELD OF THE INVENTION
The present invention generally relates to an analysis system, a income portfolio trade report, and a computer-readable medium for analyzing a stock portfolio, and more particularly the system, report, and medium using optimal covered call trades, optimal hedge trades, and a key rating in conjunction therewith for analyzing a stock portfolio and increasing equity gains.
BACKGROUND OF THE INVENTION
Corporations and other legal entities offer stocks to raise capital through the issuance and distribution of shares. Investors purchase shares through a stock market in which stocks and other securities are traded. These stock markets include, as well-known examples, the National Association of Securities Dealers Automated Quotations (NASDAQ) and the New York Stock Exchange (NYSE). Shares are purchased, held, and sold by third-party facilitators and grouped in portfolios of stocks and other securities. Most stock markets are managed and operated by a corporation or a mutual fund organization called a stock exchange, which often serves as a trading agent. These exchanges also create indexes such as the S&P 500 that groups 500 well-known companies listed in the NASDAQ or the NYSE. These stock exchanges assign a unique stock symbol to each corporation trading shares. For example, Microsoft Corporation is assigned the symbol MSFT, International Business Machine the symbol IBM, and The 3M Company the symbol MMM. Most stock exchanges or index providers rate stocks to guide investors in evaluating the worth of the stock at a precise moment in time based on contemplated future performance of the stock and/or the associated corporation. These service providers also provide financial analysis of the listed corporations and offer tools for the management of investment portfolio. For instance, S&P uses a STAR rating system, indicating the probability that a stock may be sold and depreciate in the future. The S&P STAR rating ranges from one star (strong sales contemplated) to five stars (weak sales contemplated).
Stock trades generally revolve around the purchase of a specific stock at a Purchase Price (PP) and the resale of the stock at a different sale price (SP) after market fluctuations have occurred, raising or lowering the current price (CP). Traders generally profit (P) if the resale price is higher than the purchase price shown by the equation P=SP−PP. A trader incurs a loss if the stock is sold at a price lower than the purchase price. Another way to quantify a profit from the sale of a stock in the present is P=CP−PP. A primary objective is to benefit from a transaction by selling stock at higher prices than the purchase price. Indexes are potential indicators of average and median values of CP for the entire market.
Over the years, secondary trading instruments have been developed by stock markets analysts to regulate and protect portfolios of stocks from excessive market fluctuations. One of these instruments is known as a “call option,” or more simply, a “call.” Another instrument is called a “put option,” or more simply, a “put.” The call and the put are options that may be traded alongside stocks and may be become part of a portfolio of assets even if they do not represent actual shares in stock. A call is a financial contract between the owner of a stock and a potential purchaser stating that the potential purchaser has a right, but not an obligation based on jurisdictions, to buy a stock from the owner at an agreed price. The call is reasonably associated with an expiration date called a strike date (SD), a date at which the contact expires. Generally, the agreed price of a call is called the bid price (BP) and corresponds to a value at which the parties agree to sell the stock on or before the strike date. A BP is normally higher than the CP of the stock on the stock market. The price paid for the call is a “premium” and is fixed between the parties. For example, a buyer holding $30 in cash can buy a share of stock with a CP of $30 and hope to profit if the CP increases. If a SP of $35 is obtained after as SD of 10 days, the buyer will have made a profit of $5. Once the buyer is in possession of the stock, he or she must wait patiently for fluctuations in the market to change the CP of his purchased stock. A second solution is to purchase a call from a third party in possession of a stock. Market conditions can dictate that the stock with a CP of $30 has a premium of $1 associated with a BP of $33 at an SD ten days later. In essence, the buyer pays $1 for the right to purchase the stock at the BP on the SD. Profit in that second option is only made if the CP at the SD is higher than the BP plus the premium. The profit from the trade of a call (Pc) is given by the following equations:
Pc {SD}=[CP{SD}−BP]−Premium
$1 =Pc {SD}=[$35−$33]−$1
The trade of a put option contract works in a similar way. The put has an analogous premium, for example $1 relating to a SD also in the future. At the SD, a trader is given the right to sell at a BP, for example at $27, a value that will hopefully be lower than the CP, which may have lowered to $25, by way of example. The profit (Ps) in that case would then be given by the following equations:
Ps {SD}=[BP−CP{SD}]−premium
$1 =Ps {SD}=[$27−$25]−$1
What is substantially different between a Pc and a Ps is the necessity to invest only BP instead of PP in order to obtain a profit. In the above examples, a PP of $30 would return a P of $5 or a profit of 17% while a BP of $1 would return a Pc or Ps of $1 or a 100% return on investment. Trading in call and put contracts is regarded as a risky investment because of the leverage effect between PP and Premium, and also because the CP may not reach the BP on the SD, which results in the premium being lost. Gain is achieved only if the CP reaches a value above the BP for a call and under the SP for a put above premium.
Other instruments exist to mitigate the risks associated with call and put contracts. A “covered call” (CC) is the concurrent use of a stock trade in a company and a put option contract relating to the stock in the portfolio. The covered call corresponds to securing the ownership in a stock and selling to a second party at a premium the profits associated with the situation where the stock reaches a high value above a BP. For example, the owner of 100 shares in International Business Machine (IBM) with a CP or PP of $70 per share may sell an option to a second party, fixing the BP at $80 per share for a premium of $2 per share at a SD. This CC corresponds to foregoing any potential benefits if the CP of IBM is higher than the BP at the SD in exchange for an immediate return of $2 per share. On an annualized basis, if the owner repeats this operation several times (N), in way of example 3 times in a year corresponding to a SD of four months, and the CP of the stock changes to $73 at the end of the year, an annualized return (AR) for the CC can be computed as follows:
AR=100 *[P +{Premium* N }]/PP=[{CP−PP}+{Premium* N }]/PP
12.9%=100*[{73−70}+{2*3}]/70=100*9/70
Whereas the benefit from the trade of the stock corresponds to 4.3% of the AR, the benefit from the three successive put contracts during the trade period is 8.6%. The benefit from the put contract associated with the underlying stock trade can be quantified alternatively as a downward protection (DP), a profit from the put contract that may be used to compensate for a light drop in the CP of the stock when compared to the initial PP. In the above example, the DP is 8.6%, and indicating that if the CP falls as low as $64, then the put contract protects the stock owner and places his overall investment at zero.
The downside to the covered call is the obligation to sell the stock if it performs at or above the expectations fixed in the option contract. In the above example, if the stock price reaches $80 per share at any time during the three put contract SDs, or any moment during the trade, the stock owner is forced to sell the stock to the contract holder at $10 above the CP. While this situation corresponds to a positive benefit from the trade, the stock owner generally wishes to maintain the position and is forced to purchase the stock at the CP and not the BP at a loss. What is needed is a tool designed to help stock traders to determine optimal CC trades that increase the AR while minimizing losses associated with a repositioning after an undesirable sale.
In yet another trade scenario, a trader may not wish to pay the PP of a stock in order to undertake a CC. In that case, a substantial risk is linked with the rapid increase of the CP and the need to sell a stock at a price that is not in the portfolio of an investor. The investor would have to purchase the stock at CP and sell it at the SP, suffering a loss. One possible solution is a hedge trade (HT) where a trader initiated a put option contract on a stock that is not owned in a portfolio but instead acquired a call contract with a longer SDc to cover any put option exercised against the portfolio. A HT is defined as the concurrent ownership of a short-lived put option contract on a stock and the ownership of a longer-lived buy option contract designed to be exercised prematurely if the put option contract is also exercised at or before the SDc. HT profits (Pht) are calculated by adding the different Premiums of the successive contracts minus the prices paid as premium on the call contract if no forced trades are initiated correlated to the price recovered when the call contract is exercised or replaced by a second call contract with a new SDc. By way of example, hedge trading with the above put contract of IBM at a premium of $2 for four months for a BPs of $80, and the purchase of an associated call contract designed to remain active during the period at the lowest value possible may correspond to buying at a premium of $40 a call with a BPc of $28. The advantage of taking on such a low position is to ensure that the call, on a stock with a CP of $70 is not likely to be exercised, and can be exercised with the best value at any time. The high BPc of the call is offset by the actual redemption value of the contract when the put is exercised. In the above example, the Pht if the CP remains within BPc and BPs, and where a position drops from $70 to $67 while remaining between $80 and $30, and not forcing a sale corresponds to a profit of:
Pht=(premium* N )−premium call+(CP−BP c )
$5=Pht=$2*3−$28+($67−$40)
The hedge trader receives $6 from the three put contracts and pays $28 to be able to exercise a call contract at $40 that is worth $67 on the market for a total benefit of $5. In the situation where the put contract is exercised by the buyer (where the CP rises above the BP at SDc), then the buy option must be exercised, in this example during the second period of Put contract (N=2), and the profit is as follows:
Pht=(premium* N )−premium call+(BP s −BP c )
$16=Pht=($2*2)−$28+($80−$40)
Where the stock CP is $85 above the BPc of $80 for a stock that initially went from a $70 position to a $85 position. What is needed is a device, method, and/or report that allows an optimal covered call to be determined based on the optimal covered call contract available within these and other parameters. What is also needed is a report, medium, and/or system able to determine the optimal combination of call contracts and put contracts for a selected stock and for a list of stocks in a portfolio. What is also needed is a rating system that allows covered call traders and hedge traders to quickly analyze, within a unique report, what trades are likely to improve the stock portfolio returns and performances.
While a series of specific examples and terms are given illustratively to help with the comprehension and the definition of the different terms, it is understood by one of ordinary skill in the art that flexibility in the terminology and method of application of these concepts may be contemplated based on the rapid change in the technology and the nature of stock and option trading.
BRIEF DESCRIPTION OF THE DRAWINGS
The features of the present disclosure are believed to be novel and are set forth with particularity in the appended claims. The disclosure may be best understood by reference to the following description taken in conjunction with the accompanying drawings. Figures that employ like reference numerals identify like elements.
FIG. 1 illustrates the general elements of the stock portfolio analysis system according to one possible embodiment of the present invention.
FIG. 2 illustrates in greater details and according to another possible embodiment the trading platform, the stock market, and the portfolio analysis system shown in FIG. 1 for a covered call trade.
FIG. 3 illustrates in greater details and according to another possible embodiment the trading platform, the stock market and the portfolio analysis system shown in FIG. 1 for a hedge trade.
FIG. 4 illustrates in greater details and according to another possible embodiment the key rating determination shown in FIG. 1 for a covered call and a hedge trade.
FIG. 5 illustrates in greater details and according to another possible embodiment the optimal report shown in FIG. 1 for a covered call trade.
FIG. 6 illustrates in greater details and according to another possible embodiment the optimal report shown in FIG. 1 for a hedge trade.
SUMMARY
In one general embodiment of the present invention, the present invention is directed to a stock portfolio analysis system able to determine an optimal covered call trade for each of a plurality of stocks within a stock investor's portfolio, determine an improved key rating factor associated with each optimal covered call trade, and produce a trade report that displays the optimal trades along with the key rating. In another embodiment of the present invention, the stock portfolio analysis system is able to determine an optimal hedge trade for each of a plurality of stocks within a stock investor's portfolio and provide the information along with a key rating determination in the form of a trade report. In yet another embodiment of the present invention, an income portfolio trade report is produced listing a covered call summary table, or alternatively, a hedge trade summary table, a table explanation section, and a financial summary where each covered call is associated with a key rating. In a further embodiment, the above-described embodiments of the present invention are implemented in a computer-readable medium where the report, information, analysis system are executed by a processor.
DETAILED DESCRIPTION
FIG. 1 illustrates the general elements of the stock portfolio analysis system 150 according to one possible embodiment of the present invention. The stock portfolio analysis system 150 includes a display 6 , a calculator 200 for the determination of an optimal covered call trade 11 for each of a plurality of stocks within a stock investor's portfolio, the calculator 200 being operatively coupled to the display 108 , a device for generating a trade report 201 on the display 6 the report including at least a data table 14 having a plurality of entries 51 as shown in FIG. 5 corresponding to a plurality of stocks selected from a user stock portfolio 9 , the device operatively coupled 108 to the display 6 , wherein each entry includes the single optimal covered call trade 202 shown in FIG. 5 selected from a list of available covered call trades for the stock 22 shown in FIG. 2 on a stock market 1 , and a key rating calculated using a key rating determination 4 shown in FIG. 4 . In an alternate embodiment, the stock portfolio analysis system 150 further includes a trading platform 2 for storing in a memory (not shown) the stock investor's portfolio 9 , the trading platform being coupled to the device for generating the trade report 5 . In yet another embodiment, the stock portfolio analysis system 150 includes a calculator 3 , the key rating determination 4 , and the device for generating the trade report 5 are software programs residing in a processing unit 200 . In another embodiment, the calculator 3 comprises a preliminary filter 23 shown in FIG. 2 and a secondary filter 24 shown also in FIG. 2 . The determination of the single optimal covered call trade 11 in a preferred embodiment, is based on a high value of annualized return 25 of the list of available covered call trades 22 for the stocks 21 having passed the preliminary filter 23 and the secondary filter 24 . In another preferred embodiment, the key rating determination 4 comprises a series of key rating factors 41 shown in FIG. 4 the key rating factors 41 in yet another embodiment include the Standard & Poors Star Rating.
FIG. 1 is a possible illustration of a stock portfolio analysis system 150 . Currently, stock markets 1 , including but not limited to the NASDAQ and the NYSE, are physically located in a central location and offer digital and electronic stock market services such as the trading of stocks and the purchase and sale of stock options. Clients generally referred to as “shareholders” purchase stocks via trading platforms 2 or through other service providers connected electronically 102 with the stock market 1 . Trading platforms in some instances manage a portfolio of stocks, bonds, cash, and other investments 9 allocated to a certain shareholder. The shareholder is connected either directly with the trading platform 2 or directly with the stock market 1 via an interface located on the shareholder's workstation 201 or remotely in another workstation. FIG. 1 shows a situation where a single shareholder workstation 6 is connected via lines (shown as elements 7 and 8 ) to trade stocks 7 or place new hedge and covered call trades 8 . While one possible system between a shareholder workstation 201 , a trading platform 2 , and a stock market 1 is shown as three distinct boxes on FIG. 1 , it is understood by one of ordinary skill in the art that trading and purchase of stocks may be conducted by a shareholder or portfolio owner from any computer terminal of via an intermediary using a computer terminal. For example, a shareholder may place a telephone call to a brokerage firm, which in turn places a purchase order and modifies the shareholder's stock portfolio. FIG. 1 is provided by way of illustration, and the relationship of the different entities (a shareholder, a trader, and a market trading platform) may vary without falling outside of the scope of the present disclosure. FIG. 1 further discloses communication interfaces 103 and 101 between the stock market 1 and the trading platform 2 . These interfaces are shown as a dashed line to represent the variety of possible configuration contemplated and to illustrate that while two distinct interfaces are shown based on the present disclosure, the use of a single stock market 1 with trading capacity 2 results in a single interface 101 between the stock portfolio 9 of a shareholder and a processing unit 200 .
FIG. 1 then illustrates one possible configuration where a processing unit 200 further comprises three distinct modules: software or hardware to perform a portfolio review 3 , a key rating determination 4 , and a trade report producing element 5 . Two parallel data processing lines are shown for the treatment of hedge trade-related information and covered call-related information. The hedge trade-related information is shown above the covered call-related information. These diagrams represent schematically the use of successive modules that allows for the processing of the information collected from the trading platform 2 and or the stock market 1 . In successive steps, the information from the portfolio is reviewed 3 in order to determine a covered call trade 11 for each stock in the portfolio or a hedge trade 10 with an optimal buy and put option for each stock. A key rating determination 4 is then performed based on the optimal trades determined in the first step for the hedge trade 12 and for the covered call trade 13 . Finally, the information is used and placed within a report shown by module 5 . The report includes but is not limited to table-type output 14 , 15 . It is understood by one of ordinary skill in the art that while different functions and diagrams are shown as a preferred embodiment, what is contemplated is the use of the disclosed information in any number of reasonable arrangements in association with the relevant technology in order to produce similar means in substantially the same ways, using substantially the same functions.
FIG. 2 illustrates in greater details and according to another possible embodiment the trading platform 2 , the stock market 1 , and the portfolio review 11 shown in FIG. 1 for a covered call trade where additional details are provided relating to a potential embodiment of the portfolio review module 11 . FIG. 3 illustrates in greater details and according to another possible embodiment the trading platform 2 , the stock market 1 , and the portfolio review 10 shown in FIG. 1 for a hedge trade where additional details are provided relating to a potential embodiment of the hedge trade portfolio review 10 . FIG. 4 illustrates in greater detail and according to another possible embodiment the key rating determination as shown in FIG. 1 for a covered call and a hedge trade 4 . FIG. 5 illustrates in greater detail and according to another possible embodiment the optimal report as shown in FIG. 1 for a covered call trade 14 . Finally, FIG. 6 illustrates in greater detail and according to another possible embodiment the optimal report as shown in FIG. 1 for a hedge trade 15 .
While a display 6 is shown in FIG. 1 as the screen of a personal computer 201 , what is contemplated is any display, including but not limited to paper printers or other displays where information can be provided to a shareholder. FIG. 1 also shows a single portfolio with stocks and options, but it is understood by one of normal skill in the art that any conglomeration of assets associated with stocks or other shares that may be traded on a stock market or any other platform where equity investments are found is contemplated. What is described as an investor does not necessarily relate to a single individual but includes any potential person, association, conglomerate, corporate entity, or other equivalent group able to invest in stocks and options and able to own a portfolio. By way of nonlimiting example, the ownership of a portfolio of stocks and options by a mutual fund and managed by a mutual fund operator is contemplated and falls within the definition of the investor described herein. What is contemplated as a trade report is not limited to a digital stream of information that can be displayed on a computer display. The report may also be stored and managed in digital format for use over an internet, intranet, or extranet, or the report may be printed as a hard copy on paper or other physical media. The report may also be sent to a wireless device, stored in a personal digital assistant (PDA), or any other communication device able to store and display such a report.
By way of additional disclosure, FIG. 2 illustrate a potential combination of different elements, features, and sub features used in conjunction with the embodiment disclosed in FIG. 1 to practice the invention. The stock market 1 is shown as having different stocks and options. The stock market, in addition to offering trading tools available for trading, provides and manages information relating to the stocks and options. For instance, a series of features of the stocks and options is shown, but it is understood that many other features and elements relating to stocks and options are contemplated. For example, the stock market 1 may include information relating to previous trading sessions, stock split history, and the like. While these and numerous other elements are not shown, what is contemplated is the full and complete range of elements relating to stocks and options. FIG. 2 shows as a possible implementation of the stock market 1 where a stock having a symbol, a company name, a beta (β), the current price (CP) of the stock, the dividend rate, and the presence of option (Y/N) is given. The information relating to options, calls, or puts include but is not limited to a symbol, a name or other denomination, a strike date (SD), a bid price (BP), a premium, and numerous other secondary categories of information such as the types of contract sold, the minimum quantities of options sold per contract, etc. What is contemplated is all of the information found and normally available on the stock market relating to stocks and options. Initially, the portfolio review module (shown as 11 in FIGS. 2 and 10 in FIG. 3 ) imports the user's portfolio information from the trading platform or any location where this information may be found. FIGS. 2-3 show a typical list of data associated with the numerous stocks numbered 1, 2, 3, . . . n from the user's portfolio. This information includes but is not limited to a symbol, a purchase price, the number of contracts or stocks held, the out of money indicator (OOMI), the status of the stock, the star rating indicator (STAR) of the stock or any other rating of the stock, the availability of the stock for a report as selected by a user or determined by any other third party, and a target price indicator (TP). The portfolio review is designed to find an optimal covered call for a stock 25 shown in FIG. 2 or from an hedge trade 37 shown in FIG. 3 . In a first step, the module reviews if the stock has options 21 , 31 . If the stock has no options 21 , 31 , then no optimal information can be obtained and the stock is stored 113 , 117 along with this information indicating that neither an optimal covered call 26 nor an optimal hedge trade 32 is available at this time. In one possible embodiment of the invention, the report lists each stock in the portfolio, including those stocks that do not have any options. In a preferred embodiment, only the stocks with optical covered calls or optimal hedge trades are displayed. While two possible displays are suggested, what is contemplated is any combination or user display of the relevant information associated with the review of a portfolio.
While the methodology of calculation of the optimal covered call trade and the optimal hedge trade varies as shown in FIGS. 2-3 , both use a calculator to determine a series of factors to be inserted in a preliminary filter 23 , 33 in order to reject a first series of options associated with each stock. In a secondary step, the secondary filter 24 , 35 provides the optimal hedge trade module 37 and the optimal covered call module 25 with possible trades. Finally, the optimal hedge trade module 37 and the optimal covered call module 25 use a last determination in order to find, when possible, a single optimal trade for either the hedge trade shown in FIG. 3 , and the covered call shown in FIG. 2 .
FIG. 2 shows one possible embodiment of the portfolio review 11 designed to obtain the optimal covered call 25 from stocks found in the user's portfolio 2 based on option information found in the stock market 1 . As described above, once the portfolio information is obtained from the trading platform 2 or any other alternative source, a first module 21 reviews the stock market for the presence of options 21 . Not all stocks have option trading. If there is no option found for the stock, then the information is stored 113 where no optimal covered call 26 can be found. In a second step 22 , a calculator module reviews each successive option for the stocks in the portfolio 2 . Several factors are called in turn from the stock market as associated with the investor's portfolio: the brown variation, the brown variation percentage, the covered call price (CCP), the downside protection in percentage (DP) resulting from successive trades, the percentage in the money (IM), the return in dollars if assigned (RA), the return in percentage if assigned (RIA), the number of days of the option (D), and the annualized return in percentage (AR). The brown variation is defined as a fixed factor between the premium and the asked price. In one preferred embodiment, a brown factor of 5¢ per trade is taken. Since both the CP of a stock and the premium are subject to market fluctuation between the time the report is created and when the investor decides to place the trade, the fudge factor allows for the use and calculation using an asked price, not the premium. The different values calculated may be defined in a preferred embodiment as the following:
CCP=CP−premium
brown variation=last price−premium
downside protection=premium/CP
IM =(CP−BP)/CP
RA =BP−CCP
RIA=RA /CCP
D =SD−report day (in days)
AR=( RIA/D )*365
A series of values and calculated variables are provided by way of example to illustrate one possible embodiment of the present disclosure, but what is contemplated is the use of any combination of variables or value associated with a stock. What is also contemplated in the present disclosure is the use of other variables and values taken directly from the stock market or the user's portfolio that provide the same resulting information. The AR is a value that guides investors by showing potential annual return if an option is exercised at the current premium price and bid price for one full year. Downward protection provides information relative to this return when compared with the stock price. What is contemplated is the search for options that provide the best downward protection, provide the highest annualized return, have a positive out-of-money indicator, have a low premium, and have a strike date set at a distance in the future adequate to protect the trader. By way of nonlimiting example, very short trades may present the inherent problem of being subject to greater daily market fluctuations, whereas long trades are vulnerable to external factors associated with the management of the corporation.
In one preferred embodiment, these calculated values are then used 109 by a preliminary filter 23 in order to make a first level of selection from the often numerous available options available for a covered call of a stock. In one preferred embodiment, that is subject to market variation, inflation, and changes based on observed results, shown as 114 . Stocks option trades are rejected if the SD is less than 60 days or greater than 370 days away. The OOMI is currently defined as a series of plusses or no plus. If the OOMI is not a plus, then the bid price must be below the current stock price, if the OOMI is at least one plus, then the BP must be above the CP but not by more than 5% for each plus sign associated with the OOMI. Another possible preliminary filter factor is the need for the premium to be equal to or greater than 800, and the RIA must be at least 2% of the RA or assigned to be at least $2. While a series of values are given by way of example and illustrate a preferred embodiment, what is known in the art is the capacity to modulate and change these filtering parameters based on a plurality of conditions. Options trades that do not meet the requirements of the preliminary filter 23 are removed 114 from the list of possible optimal covered calls.
A second filter 24 is then used to select from the remaining options for each stock a single optimal covered call. The secondary filter consists of defining the closest possible strike month (CPSM), the farthest out expiration month (FOEM), the lowest possible strike price (LPSP), and the highest possible strike price (HPSP) for each remaining options. The determination of CPSM and FOEM have already been validated by the preliminary filter to be within 60 to 370 days from the date. The CPSM and FOEM are calculated based on a value table that fixes end dates to a trading calendar. For example, a March 2007 expiration date may be associated with Mar. 17, 2007, based on table calculations. The LPSP is calculated as the lowest BP possible based on the OOMI is the CP plus 3% for each plus in the OOMI. If OOMI has no plus signs, then the current stock price is calculated minus 3% and minus 500. Finally, the HPSP is calculated as the highest BP possible based on the OOMI and is the CP plus 6% if the stock has an OOMI plus sign. If the stock does not have an OOMI plus sign, then a value of CP plus 1% is calculated. The secondary filter 24 compares the SD and the BP of each option with these new values to determine if the option can qualify as the potential optimal trade 111 . Finally, the optimal covered call is obtained from the remaining options having the highest AR. These filtering tools correspond only to a preferred embodiment and should not be intended as limiting the scope of the above disclosure.
The methodology for finding the optimal hedge trade is similar to the methodology for finding the covered call described above. FIG. 3 shows the steps associated with the calculator 34 and the filters 33 , 35 to be used during the determination. A hedge trade is defined as the conjunction of two contract options working in tandem to project a put position on a first short contract. The hedge trade is determined by first identifying an optimal put contract as defined here above. This contract must be at a SD located between the CPSM and the FOEM, generally 60 to 370 days out. What is then required is the determination of a second purchase option contract that covers the entire duration of the trade or that is located at a sufficient distance in time to prevent repositioning. The purchase option in a preferred embodiment must be at least 6 months away, possibly in January of the next available year. For example, a put position in September 2006 with a strike date of 12 months would expire in September 2007. The purchase position associated must be at least 6 months after the SD and must occur in January, so it cannot be January 2007. Rather, it must be January 2008. These values reflect an illustration of a preferred embodiment and do not in any way limit the scope of the disclosure. Other possible dates and time intervals are contemplated. These dates correspond to a preliminary filter shown as 33 in FIG. 3 . Each potential purchase position is analyzed in the way described above in order to determine all relevant parameters including but not limited to the bid price, the asked price, the premium, the brown variation, the brown variation percentage, the covered call price (CCP), the downside protection in percentage (DP) resulting from successive trades, the percentage in the money (IM), the return in dollars if assigned (RA), the return in percentage if assigned (RIA), the number of days of the option (D), and the annualized return in percentage (AR). In one preferred embodiment, the secondary filter 35 include a strike date of at least 180 days away but not more than 550 days away, the profit on the trade if assigned must be at least 700, and the return rate if assigned must be at least 2%. Finally, the annualized return rate, if assigned must be at least 8%. The numerical values given are again only illustrative of a potential preferred embodiment. What is contemplated is any reasonable variation of these figures that leads to the same end result. Once again, of the purchase positions associated with the stock having the highest annualized return rate are taken as the optimal hedge trade 37 .
In one embodiment of the present disclosure, both the optimal covered call and the optimal hedge trade are associated with a key rating factor defined to guide users toward more profitable trades. In one possible embodiment, a five-level key rating system is provided as a preferred embodiment. This rating indicates the relative risk of losing the stock if the stock price rises higher than the bid price before the strike date. One key equates to a highest relative risk, two keys to a considerable relative risk, three keys to a moderate relative risk, four keys to a low relative risk, and five keys to the lowest relative risk. While one potential rating factor is disclosed, what is contemplated is any factor used to provide the portfolio manager and investor with a relative indication of which stock is likely to hit the bid price. Either the stock is sold under the option contract or a stock needs to be purchased to cover a second put option.
The key rating for the optimal covered call 25 for each stock in the investor's portfolio 2 is calculated from key rating factors such as the star rating (STAR), the CP, the calculated 12-month target price, the SD, the Bid price, and the β. From these values, a pro rata range is calculated for each of six factors: the STAR rating for 35% of the value, the IM for 15% of the value, the downward protection for 12.5% of the value, the days to expiration for 15% of the value, the price relative to target for 12.5% of the value, and the β for the remaining 15% of the value. The values are prorated based on possible values ranging from 5 to 1 for the Star rating with 5 being the best, an IM ranging from −20% to +10% with −20% being the best, a downside protection ranging from 10% to 0% with 10% being the best, the days to expiration ranging from 365 days to 30 days with 365 days being the best if no OOMI plus is found, the days to expiration ranging from 1 to 365 days with 365 days being the worst if an OOMI plus is found, the price relative to target ranging from 80% to 110% with 80% being the best, and finally the β ranging from 0.5 to 2 with 0.5 being the best. These values are then normalized on a scale of 1 to 5, averaged, and rounded to obtain the key rating factor. For example, if the best of each factor is found, then every normalized value is a 5 and the rounded value is 5 keys. If the worst of each factor is found in the option to be reviewed, then every normalized value is a 1 and the rounded value is 1 key. These values are shown as element 42 in FIG. 4 but only represent one preferred embodiment. What is contemplated is the use of a plurality of factors in order to provide a rating scale. What is also contemplated is the modification and change of these parameters according to evolving market conditions. For example, in a volatile market, the days to expiration may be given less weight, and other factors, such as the downside protection, may be given greater weight. While one possible embodiment is shown, one of ordinary skill in the art understands the potential of the disclosure in relationship with market conditions.
FIG. 4 shows how the key rating is found for an hedge trade 12 . The covered call key rating is first determined as describe above 13 and is then corrected based on the STAR rating of each trade bought. The overall hedge trade for a trade is a combination of the first key rating corrected for the star rating of the option contract bought to cover the put option contract. In a preferred embodiment, if the option contract bought is rated at 5 STARS, then the key rating value determined is lowered by 0.5 after being normalized and is rounded to the closest integer. If the STAR rating is 4, then the key value is lowered by 0.75. If the rating is 3, it is lowered by 1.2. If the STAR rating is 2, the key value is lowered by 1.5. And finally, if the STAR rating is only 1, then the key factor is lowered by 2 to a resulting value never to be lower than 1.
In an nonlimiting example, if a key rating for a covered call of 3.8 rounded to 4 is found based on the put option contract, and a optimal hedge trade of only 2 STARS is determined to be the best available option for the hedge trade, then the new calculated key rating is 3, or 3.8 minus 1.2 (2.6 rounded to 3). While one possible method for determining a key rating value is shown, what is contemplated is any combination of parameters and correction factors.
In a preferred embodiment, the report includes a customized section showing the date when the report was prepared, the advisor's name, the advisor's contact phone number, the total stock value of the portfolio, the potential income for now, the return in percentage, the average risk in rating keys, the potential annual income in dollars, the minimum and maximum period in days, and the annualized return in percentage. The report includes seven more sections: a summary, a description how the report was prepared, a description how to use the report, the outlook for the general market of the Standard & Poor, the strategy for selling covered calls on portfolio stocks, the time considerations for this strategy, and the primary risk for the strategy. In addition, the potential income generating trade table is given as described above. This table is made of successive lines for each stock in a first area where the basic information about the underlying stock is given, including but not limited to the stock symbol, the S&P STAR rating, the target date in days, the target price in dollars, the basis of acquisition in dollars, the number of shares owned and the option symbol, and the current stock price. In a second line, the option-specific information relating to the optimal covered call uncovered by the disclosure is listed. This information includes the option strike price (BP), the number of contract sold, the expiration date (SD), the premium (also called the bid price per share), the downward protection in dollars, the percentage of downward protection, the strike percentage from the stock price, the return in dollars, the return as a percentage of the basis, the annualized return rate, the key rating, the potential call sales per year, and the annualized amount in dollars. Table explanations for each of these factors is provided to the user. Finally, the report includes potential outcomes of the covered call income strategy as described in a number of possible cases, important assumptions, and warnings, risks, and other considerations.
In another possible preferred embodiment, a stock hedge strategy report is created and includes a summary table for the covered call trade for each stock. The summary table contains a trade date, a stock symbol, the put option, the sell amount in dollars for the premium, the net debit or break even, the percentage in downside protection, the assigned return date, the percentage in the money, and the expiration date along with the key rating. In the second part of the report, a hedge trade summary table is provided. The table includes columns with the trade date, the stock symbol, the buy option, the put option, the net debit, the break even, the percentage in the money, the number of contracts, the total debit, the target return, the return date, and the near-term expiration date along with the key rating. The tables and key rating are explained in the report. Finally, a section on the essential information on these types of trades is listed.
FIGS. 5-6 illustrate a potential type of report according to a preferred embodiment of the present disclosure. FIG. 5 shows a table 51 where stock line information 52 and option line information 210 are provided. FIG. 6 shows a table 61 where each line is dedicated to a different stock. The stock line information 62 includes several categories of information. While one preferred embodiment is provided, it is understood by one of ordinary skill in this art that any of a number of different structures and arrangements of different categories of information can be provided. What is also contemplated is a dynamically created report that provides only a portion of the information on the initial page and requires an action from the report reader to access the remaining information. By way of a nonlimiting example, a dynamic HTML page can be created where the specific information is arranged and accessible by following a plurality of dynamic links. What is also contemplated is the use of a fragmented report or the creation of a website where the information is replaced continuously and updated at regular intervals. What is also contemplated is the creation of a series of orders prepared for a portfolio owner in anticipation of the placement of orders with the stock market 1 via a trading platform 2 or placed directly with a stock market 1 quipped with trading capacity.
In yet another embodiment, the stock portfolio analysis system 150 includes a display 6 , a calculator 200 for the determination of an optimal hedge trade for each of a plurality of stocks within a stock investor's portfolio 10 , the calculator 3 being operatively coupled to the display 108 , a device for generating a trade report 201 on the display 6 comprising at least a data table 15 having a plurality of entries corresponding to the optimal hedge trade for each of the plurality of stocks within the stock portfolio 9 , and an associated optimal covered call trade corresponding to each of the optimal hedge trades, the device operatively coupled 108 to the display 6 , wherein each entry further comprises a key rating determination 12 for optimal hedge trade and the associated optimal covered call trade. The stock portfolio analysis system 150 further includes a trading platform 2 for storing in a memory unit (not shown) the stock investor's portfolio 9 , the trading platform being coupled to the device for generating the trade report 5 . The stock portfolio analysis system 150 also includes a calculator comprising a preliminary filter 33 and a secondary filter 35 for the determination of the optimal hedge trade based on the highest AR value from among the list of available hedge trades for the stocks having passed the preliminary filter 33 and the secondary filter 35 .
In another embodiment, the income portfolio trade report 5 includes a covered call summary table 14 with a plurality of entries corresponding to a plurality of stocks selected from a user's stock portfolio 9 , a table explanation section with descriptions of a series of parameters corresponding to each of the plurality of entries, and a financial summary section with a summary of the user's stock portfolio, where each of the plurality of entries includes an optimal covered call trade selected from a list of available covered calls and a key rating. The trade report 5 also includes descriptions of the series of parameters in the table explanation section corresponding to a series of parameters assigned to each of the plurality of entries in the covered call summary table.
In yet another embodiment, the income portfolio trade report 5 includes a hedge trade summary table 15 with a plurality of entries corresponding to a plurality of stocks selected from a user's stock portfolio 9 , a table explanation section with descriptions of a series of parameters corresponding to each of the plurality of entries, and a financial summary section comprising a summary of the user's stock portfolio, where each of the plurality of entries includes an optimal covered call trade selected from a list of available covered calls, a stock position, and a key rating. The trade report 5 also includes descriptions of the series of parameters in the table explanation section corresponding to a series of parameters assigned to each of the plurality of entries in the hedge trade summary table. In yet another embodiment, the trade report 5 includes a stock position for a stock in the user's stock portfolio where the position is a buy call option of the hedge trade.
In another embodiment of the present disclosure, what is contemplated is a computer-readable medium having stored thereon instructions that, when executed by a processor, cause the processor to compute an optimal covered call trade for each of a plurality of stocks within a stock portfolio of an investor 9 , compute a key rating for each of the optimal covered calls 13 , produce an income portfolio trade report 14 comprising a covered call trade summary table further comprising a plurality of entries corresponding to the plurality of stocks selected from the investor's stock portfolio where each of the plurality of entries further comprises the optimal covered call trade and the key rating. The computer-readable medium also has instructions that, when executed by a processor, cause the processor to compute an optimal covered call 10 trade for each of a plurality of stocks within an investor's stock portfolio 9 , compute an associated optimal hedge trade 10 for each of the plurality of stocks within the investor's stock portfolio, compute a key rating for each of the optimal covered calls 13 and the associated optimal hedge trade 12 , and produce an income portfolio trade report comprising a hedge trade summary table 15 with a plurality of entries corresponding to the plurality of stocks selected from the investor's stock portfolio, wherein each of the plurality of entries further comprises the optimal covered call trade, the optimal hedge trade, and the key rating.
The invention is not limited to the particular details of the apparatus or method depicted, and other modifications and applications may be contemplated. Further changes may be made in the above-described method and device without departing from the true spirit of the scope of the invention herein involved. It is intended, therefore, that the subject matter in the above depiction should be interpreted as illustrative, not in a limiting sense. | The present invention generally relates to a method for automatically generating a series of natural language news-based stories to be presented via a digital interface or printed publication to a portfolio user, and more specifically to a filter or selection of a handful of relevant and desired financial instruments, or events created in a large group of events such as sports results, travel information, auction related data, online shopping tools, social media, retail store promotion generation, search engine daily report, etc. for a specific use. These financial instruments, based on different selections from a portfolio manager via a management tool, are then used to either produce a strategies page where a list of useful covered call trade and hedged trade are displayed in the form of a table, or natural language news-based stories relating to a selected list of financial instruments found in a portfolio. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is based on and claims priority from Korean Patent Application No. 10-2006-65745, filed on Jul. 13, 2006 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a rain hat attached to an exhaust tube of an engine.
[0004] 2. Description of the Background Art
[0005] Heavy construction equipment is equipped with an exhaust tube which exhausts gas. Exhaust gas is exhausted via an exhaust tube. Here, the exhaust tube is engaged at an upper swing structure of the equipment. Since an upper swing structure of heavy construction equipment swings in the course of work, the exhaust tube is generally engaged at an upper swing structure so that any interference does not occur with wheels, etc.
[0006] Since the exhaust tube is engaged at the upper swing structure and is vertically installed, the exhaust tube needs a cover on an upper end of the vertically installed exhaust tube. Otherwise, rain may fall into the exhaust tube. Some heavy construction equipment are equipped with an improved exhaust tube of which upper end is horizontally bent so that rain does not fall into the exhaust tube. In case of large size heavy construction equipment, a rain hat is generally provided for preventing rain from falling into the exhaust tube.
[0007] In case of conventional heavy construction equipment which is provided with a rain hat, rattling noises may occur from the rain hat. When the revolution of an engine is low, the discharge force of exhaust gas is weak, so that the rain hat should be installed at a relatively lower side. In case that an engine works, since exhaust gas is discharged whenever one cycle of the engine finishes, the gas discharge pressure of the exhaust tube is not constant.
[0008] In case of a rain hat which is installed at a conventional heavy construction equipment, since the rain hat, which receives a discharge pressure of exhaust gas, is designed to operate with the help of a hinge operation of a pin, the rain hat should freely move with a certain gap from a pin hole. In the conventional art, since a discharge pressure of exhaust gas is not constant, rattling noises occur owing to a gap between the pin and the pin hole when the rain hat works.
[0009] So, an operator or other persons may feel uneasy when the above rattling noises occur for thereby causing a lot of problems in the course of work.
SUMMARY OF THE INVENTION
[0010] Accordingly, it is an object of the present invention to provide a rain hat attached to an exhaust tube of an engine which is able to prevent rattling noises occurring owing to a conventional rain hat, so that an operator or other persons can feel comfortable in the course of work.
[0011] To achieve the above object, in a rain hat which is mounted on an exhaust tube of heavy construction equipment, there is provided a rain hat for heavy construction equipment which comprises a plate which corresponds to a shape of an outlet of the exhaust tube; a connection part which is formed at one end of the plate and is extended in a downward direction; and an elastic plate of which one end is connected with the connection part, and the other end is engaged with the exhaust tube, the elastic plate having a certain length, whereby the outlet of the exhaust tube, which is closed by means of the plate, opens as a discharge pressure overcomes an elastic force of the elastic plate when exhaust gas is discharged from the exhaust tube.
[0012] For an easier engagement, the rain hat of the heavy construction equipment is formed larger than the outlet depending on the shape of the outlet of the exhaust tube. Since too larger size rain hat does not look nice, the plate slightly larger than the size of the outlet of the exhaust is preferably used. A rectangular protrusion is formed at an end of the rain hat plate. The protrusion allows the connection part to be formed at a lower surface of the plate and to be connected with the elastic plate. So, the whole shape of the rain hat is a spoon shape.
[0013] The connection part is welded at a lower surface of the protrusion of the rain hat plate. The welded connection part is engaged with one end of the elastic plate in the longitudinal direction using an engaging member by forming a bolt hole or a rivet hole for an engagement using an engaging member such as a bolt, etc. A bolt hole or a rivet hole is formed at the portion connected with the connection part of the elastic plate like the connection part.
[0014] Here, the elastic plate has a certain length. When it is too short, since the elastic coefficient of the elastic member is not large, greater pressure is needed for moving the rain hat. So, the length of the elastic plate is preferably determined depending on the discharge pressure of the exhaust tube. The other end of the elastic plate is connected with the exhaust tube. Namely, it is connected with a fixing terminal, which is formed at an outer side of the exhaust tube, by using an engaging member such as a bolt, etc. The fixing terminal may be directly connected with the exhaust tube based on a welding method, etc.
[0015] According to the operation principle of the present invention which uses the elastic plate, when the discharge pressure of exhaust gas is applied to the rain hat, a force for pushing the rain hat is generated. Moment is generated at the lower side of the elastic plate fixed at the exhaust tube depending on the force which pushes the rain hat upward. The elastic plate has a rotational force owing to the moment, so that the rain hat opens. In case that the pressure decreases, it returns to its original state owing to the elastic force of the plate.
[0016] To achieve the above object, in a rain hat which is mounted on an exhaust tube of heavy construction equipment, there is provided a rain hat for heavy construction equipment which comprises a plate which corresponds to a shape of an outlet of the exhaust tube; a connection part which is formed at one end of the plate and is extended in a downward direction; a pair of coil springs of which ends are connected with both lower sides of the connection part; and a bracket which is mounted on the exhaust tube in which the other end of each coil spring is horizontally connected, whereby the outlet of the exhaust tube, which is closed by means of the plate, opens as a discharge pressure overcomes an elastic force of the coil spring when exhaust gas is discharged from the exhaust tube.
[0017] Like the above construction, a rain hat plate shaped depending on the shape of an outlet of the exhaust tube, and a rectangular protrusion integrally formed at one end of the plate are provided, which form a spoon shaped rain hat plate. A connection part is welded at a lower surface of the protrusion of the plate. Two holes are formed at both lower ends of the connection part for connecting the coil spring. A spring having a ring shaped end is engaged at the holes. The ring shaped other end of the spring is fixed at the bracket mounted on both sides of the exhaust tube. Two ends are vertically protruded from both sides of the channel shaped bracket. A fixing hole is formed at an upper side of the vertically formed plate.
[0018] According to the operation principle, when the discharge pressure of exhaust gas is applied to the rain hat, the rain hat is forced to lift up. When the rain hat is lifted up, rotational force is applied to the coil spring. The present invention does not use a pin as compared to the conventional art, even when pressure is continuously applied thereto, rattling noises do not occur. When pressure decreases, the rotational force of the spring allows the rain hat to be pushed and closed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The present invention will become better understood with reference to the accompanying drawings which are given only by way of illustration and thus are not limitative of the present invention, wherein;
[0020] FIG. 1 is a view illustrating an excavator of a conventional art;
[0021] FIG. 2 is a cross sectional view illustrating an engine and an exhaust device of a conventional art;
[0022] FIG. 3 is a side and plane view illustrating a conventional rain hat;
[0023] FIG. 4 is a plane, side and rear view illustrating a rain hat according to an embodiment of the present invention;
[0024] FIG. 5 is a view for describing an operation of a rain hat according to an embodiment of the present invention;
[0025] FIG. 6 is a view for describing an operation force of a rain hat according to an embodiment of the present invention; 5 FIG. 7 is an operation graph of a rain hat according to the present invention; and
[0026] FIG. 8 is a plane, side and rear view illustrating a rain hat according to another embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] The preferred embodiments of the present invention will be described with reference to the accompanying drawings.
[0028] FIG. 1 is a view illustrating an excavator. The above excavator comprises an upper swing structure 101 , a lower driving structure 102 and a work unit 103 . The upper swing structure 101 is equipped with various instruments such as an engine room 104 for driving the work unit 103 and a driver's seat 105 .
[0029] FIG. 2 is a view illustrating an engine and an exhaust apparatus mounted. As shown therein, there are provided an engine 1 , an exhaust manifold 2 for exhausting gas from the engine, a supercharger 3 which compresses air with the help of exhaust gas, an exhaust tube path 4 which is connected from the supercharger to a muffler, a muffler 5 , and a rain hat 7 .
[0030] FIG. 3 is a view for describing a conventional rain hat. Here, the rain hat is designed to prevent rain from falling into the exhaust tube. When the engine stops, the rain hat closes the outlet of the exhaust tube for thereby preventing rain from falling to the exhaust tube. When the engine works, the rain hat is forced to open by means of the pressure of exhaust gas for thereby forming a discharge path of exhaust gas. In the drawing, reference numeral 7 represents a body of a rain hat, and 8 is a bracket fixed at the exhaust The rain hat 7 is connected with the bracket 8 by means of a pin 9 and is freely rotatable about the pin. Since the above connection portion directly contacts with exhaust gas, carbon is attached. So, an enough space is obtained during the engagement of the pin 9 so that the rain hat 7 can freely rotate. In the conventional, rattling noises occur in the conventional rain hat structure.
[0031] FIG. 4 is a plane, side and rear view illustrating a rain hat according to an embodiment of the present invention. The rain hat according to the present invention comprises a spoon shaped rain hat plate 11 , a connection part 12 mounted on a lower surface of a protrusion of the rain hat plate, an elastic plate 14 of which one longitudinal end is connected with the connection part with an engaging member 13 such as a bolt, etc., and the other end is connected with an exhaust tube 6 with an engaging member such as a bolt, etc., and a fixing terminal 16 which is engaged at the exhaust tube with a welding method.
[0032] FIG. 5 is a view of an operation of FIG. 4 . The rain hat 11 is supported by means of a plate spring 14 which is formed of an elastic plate. When the engine stops, the rain hat 11 covers the upper end of the exhaust tube 6 for thereby preventing rain from falling into the exhaust tube. When the engine 1 operates and discharges exhaust gas, the rain hat 11 is forced to open by means of the exhaust gas. Here, since the rain hat 11 is supported by means of the plate spring 14 , the rain hat 11 is forced to open as the plate spring 14 is elastically transformed. The exhaust gas allows the rain hat 11 to open and is discharged. When the engine 1 stops and does not discharge exhaust gas, the rain hat 14 returns its original position by means of the elastic force of the plate spring 14 . So, when the engine does not work, the rain hat covers the upper end of the exhaust tube 6 for thereby preventing rain from falling into the exhaust tube 6 . When the discharge force of the exhaust gas is weak, the rain hat keeps opening with a slight open.
[0033] In the present invention, since the pin is not used, it is possible to prevent the occurrence of rattling noises which may cause uneasy to an operator or other persons.
[0034] The elastic plate 14 of the rain hat 11 may be formed of a certain elastic material which has elastic force. Since the elastic plate 14 contacts with high temperature, it should be preferably made of a heat resistance material.
[0035] FIG. 6 is a view illustrating force and moment with respect to an operation principle that the elastic plate moves according to the present invention. As shown in the left side of FIG. 6 , a discharge pressure of exhaust gas is applied to the rain hat 11 . Since discharge pressure is applied to the rain hat, the force may be expressed as F y . The rain hat 11 is forced to open by means of the force F y . Since the elastic plate 14 is attached to the rain hat 11 , the rain hat 11 does not open limitlessly. Moment M occurs by means of the arm length R and the force F y instead.
[0000] M=R•F y
[0036] The above moment value may be neglected since the weight of the rain hat is not heavy. So, it is possible to simplify like the right side of FIG. 6 . The force F x is applied to the elastic plate 14 . In this case, since the moment M has the same value,
[0000] R•F y =L•F x
[0000] ∴F x =F y •R/L
[0037] Therefore, when discharge pressure is applied to the rain hat 11 , the elastic plate 14 opens. Since the force larger than the unit elastic coefficient of the elastic plate is needed so that the elastic plate moves, the elastic plate 14 opens slightly at first. When the pressure exceeds a certain level, it can easily open. FIG. 7 shoes the above-described operation. FIG. 7 shows a state that the rain hat 11 smoothly moves by means of the elastic plate 14 mounted on the rain hat 11 .
[0038] FIG. 8 is a view illustrating another structure of the present invention. As shown therein, a rain hat plate 21 is provided. A first connection part 22 is formed at a lower protruded portion of the rain hat 21 . A ring formed at one end of each coil spring 24 a , 24 b is engaged at a corresponding hole 23 a , 23 b formed at both lower sides of the first connection part. A bracket 26 is vertically formed at both ends of a channel shaped bracket 26 . The ring of other end of the coil spring is horizontally connected with the fixing terminal 25 a , 25 b . The fixing terminal 25 a , 25 b of the coil spring 24 a , 24 b is connected with the bracket 26 fixed at the exhaust tube 6 . When exhaust gas tries to allow the rain hat 21 to open, the coil spring 24 a , 24 b is curved, so that the rain hat 21 opens for allowing the exhaust gas to discharge.
[0039] As shown in FIG. 8 , when discharge pressure of the exhaust gas is applied to the rain hat 21 , the rain hat 21 is lifted up. Here, since a pin is not used for lifting up the rain hat 21 as compared to the conventional art, rattling noises do not occur. When pressure becomes weaker, the rain hat 21 moves down. When no pressure is applied, the rain hat 21 is closed for thereby preventing rain from falling into the exhaust tube.
[0040] As described above, in the present invention, it is possible to prevent rattling noises which occur owing to the movement of a support pin of a rain hat. So, an operator or other persons do not feel uneasy.
[0041] In addition, an operator's convenience facility is improved. The work efficiency increases by preventing uneasy noises.
[0042] As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described examples are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims. | A rain hat for heavy construction equipment is disclosed, which comprises a plate which corresponds to a shape of an outlet of the exhaust tube; a connection part which is formed at one end of the plate and is extended in a downward direction; and an elastic plate of which one end is connected with the connection part, and the other end is engaged with the exhaust tube, said elastic plate having a certain length, whereby the outlet of the exhaust tube, which is closed by means of the plate, opens as a discharge pressure overcomes an elastic force of the elastic plate when exhaust gas is discharged from the exhaust tube. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to a stencil printing method suitable for obtaining prints on which the ink is smoothly and thickly applied and to an apparatus used for carrying out the method.
Stencil printing is utilized in various fields because of its easy preparation of master stencil sheets. However, according to the stencil printing, a printing ink is applied onto the outer surface of the master stencil sheet superposed on a material to be printed (hereinafter referred to as "printing material") and the printing ink is forced out through perforations of the stencil sheet by an ink supply means such as a pressing plate or a roller to transfer the ink onto the printing material, and thereafter the stencil sheet and the printing material are separated. Therefore, the amount of the printing ink transferred is great, and it is especially difficult to transfer the printing ink at a uniform thickness without causing uneven transfer.
Particularly, uneven transfer of the printing ink is conspicuous in the solid print portion, whereby appearance of printed images is apt to be damaged. This uneven transfer can be improved by using printing materials high in permeability to the printing ink. However, when coated papers, plastics and glass sheets, which are low in permeability to the printing ink and high in smoothness, are used, such improvement cannot be expected. Moreover, if an ink high in fluidity is used, printing high in smoothness is possible thanks to self-leveling of the ink, but it becomes difficult to retain the ink in stencil sheets or to obtain prints onto which the ink is thickly applied.
Causes for such uneven transfer as mentioned above are considered to be as follows. That is, since the ink per se has viscosity, when the stencil sheet and the printing material are separated, an internal stress is generated between the ink on the side of the stencil sheet and the ink transferred to the printing material, and these inks string with each other to cause the ink to finally be cut in pieces irregularly.
For reducing the uneven transfer, Japanese Patent Laid-open (Kokai) No. 61-14978 proposes to make constant a time in which a master stencil sheet is pressed to a printing material to transfer an ink to the material. However, according to this method, unevenness in the amount of the transferred printing ink, which is caused by a difference in the pressing time, can be diminished, but the unevenness on a surface of the transferred printing ink, which is caused by stringiness of the printing ink at the time of separation of the master stencil sheet, cannot be diminished.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a stencil printing method suitable for obtaining prints on which ink is smoothly and thickly applied and to a stencil printing apparatus therefor.
According to the present invention, the above object has been attained by a stencil printing method comprising
a step of pressing together an ink supply means and a printing material to be printed while a master stencil sheet and an ink-passing porous member are interposed between said ink supply means and said printing material, whereby an ink is transferred from said ink supply means to said printing material in accordance with an image of said master stencil sheet,
a step of separating said ink supply means from said porous member while said porous member is left on said printing material, and
a step of separating said porous member from said printing material.
That is, the present invention relates to a stencil printing method in which when a master stencil sheet and a printing material are superposed one upon another and an ink supply means is pressed to an outer surface of the master stencil sheet to allow a printing ink to reach the printing material from the ink supply means through perforations of the master stencil sheet, an ink-passing porous member is provided in a route through which the printing ink reaches the printing material from the ink supply means so that the printing ink is transferred to the printing material through the porous member, and, furthermore, after the printing ink is transferred to the printing material in this way, the ink supply means is removed from the porous member while the porous member is kept on the side of the printing material and thereafter the porous member is separated from the printing material.
In the present invention, after the printing ink is transferred to the printing material, the ink supply means is first removed from the porous member. Therefore, at this point of time, the printing ink which is impregnated in the porous member and transferred to the printing material is kept under atmospheric pressure, and the transferred ink is adjusted to a uniform thickness in accordance with a thickness of the porous member. Thereafter, when the porous member is separated from the printing material, the printing ink is not exposed to an abrupt change of pressure so as not to generate an internal stress in the ink and in this state the ink retained in the porous member is transferred to the printing material. Thus, unevenness of the surface of the printing ink hardly occurs and uneven transfer can be reduced to the minimum. When the porous member is separated from the printing material, the transfer of the ink to the printing material may be aided by application of wind pressure to an extent that does not affect the image.
DESCRIPTION OF THE INVENTION
In the present invention, as the porous member, there may be used, for example, a gauze made of fibers such as of polyester, nylon, rayon, stainless steel, silk, cotton and metal, and, besides, Japanese paper, woven fabric, nonwoven fabric, sponge and open-cell foamed sheet. Preferred are those which do not diffuse the printing ink. Conveniently, a sheet-like porous member can be obtained by subjecting a known stencil sheet comprising a thermoplastic film laminated on an ink-passing porous support to overall solid perforation in which the thermoplastic film is entirely perforated so as to expose substantially all the surfaces of the porous support. It is desired that the material, size and structure of the porous member are optionally selected considering thickness of the printing ink to be printed on the printing material, passing property of ink and wettability of ink.
As mentioned above, in the present invention, the porous member may be provided at any position in the route through which the printing ink is transferred to the printing material from the ink supply means at the time of printing. Specifically, it can be provided between the ink supply means and the master stencil sheet or between the master stencil sheet and the printing material. Furthermore the master stencil sheet and the porous member may be integrated into one sheet which can be made porous at portions through which an ink is to be passed to print an image on a printing material.
In the present invention, the master stencil sheet can be produced by perforating a known stencil sheet by heat sensitive perforation method or by perforating an ink-impermeable sheet by photosensitive perforation method, drawing method or cutting method. The master stencil sheet may be separate from the porous member or may be integratedly laminated on one of the surfaces of the porous member. In the latter case, a master stencil sheet laminated on the porous member can readily be obtained by perforating a known stencil sheet comprising a thermoplastic film laminated on an ink-permeable porous support in conformity with a desired image.
In the present invention, any ink supply means can be used as far as they can be inked and used for pressing out the printing ink to the printing material through perforations of the master stencil sheet and the porous member to transfer the ink to the printing material. For example, mention may be made of a pad, sponge and roller impregnated or coated with a printing ink. Conveniently, the ink supply means can be constructed by subjecting to overall solid perforation a known stencil sheet comprising a thermoplastic film laminated on an ink-passing porous support, and then supporting it on a pressing plate with a printing ink between the stencil sheet and the pressing plate. Furthermore, in the case of the stencil sheet being perforated in accordance with the desired print image, the perforated stencil sheet may be inked to act as, as a whole, not only the ink supply means but also the master stencil sheet.
The printing ink usable in the present invention has no special limitation, and oil ink, water ink, emulsion ink and the like can be used. However, in case wettability of the ink to the porous member is higher than that of the ink to the printing material, transfer of the printing ink to the printing material from the porous member sometimes becomes non-uniform, and hence it is preferred to use an ink which is higher in wettability to the printing material than that to the porous member.
The stencil printing method of the present invention can be performed not only by a pressing type portable stencil printing apparatus commercially available under a product name of PRINT GOCCO (registered trademark: manufactured by RISO KAGAKU CORPORATION), but also by rotary stencil printing apparatuses.
The stencil printing method of the present invention can be performed by, for example, a stencil printing apparatus comprising a first member supporting a printing material, a second member arranged opposing the first member so as to be able to press the printing material and holding an ink supply means and a master stencil sheet laminated in succession on the surface opposing the printing material, and a third member holding a porous member between the first member and the second member.
The stencil printing method of the present invention can also be performed by a stencil printing apparatus comprising a first member supporting a printing material, a second member arranged opposing the first member so as to be able to press the printing material and holding an ink supply means on the surface opposing the printing material, and a third member holding a master stencil sheet and a porous member laminated in succession between the first member and the second member.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1(a)-(d) are sectional views which show one example of the stencil printing method of the present invention.
FIGS. 2(a)-(c) are sectional views which show a modification example of FIG. 1.
FIG. 3 is an oblique view which shows one example of the stencil printing apparatus of the present invention.
FIGS. 4(a)-(d) is a partly enlarged sectional view of the stencil printing apparatus shown in FIG. 3, taken along line A--A of FIG. 3.
FIG. 5 is a side view which shows an operation of the printing apparatus of FIG. 3.
FIG. 6 is a side view which shows an operation of the printing apparatus of FIG. 3.
FIG. 7 is a side view which shows an operation of the printing apparatus of FIG. 3
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
An example of the present invention will be explained in more detail referring to the above drawings.
In FIG. 1, the reference numeral 1 indicates a printing material, i.e., a material to be printed, 2 indicates an ink supply means, 3 indicates a master stencil sheet, and 4 indicates a porous member.
The ink supply means 2 is constructed by stretching an ink-passing gauze 22 on a frame 21 and placing a printing ink 23 on one surface of the gauze 22. This ink supply means 2 can be obtained, for example, from a known stencil sheet unit comprising a frame of cardboard or plastics on which is extended a stencil sheet composed of a thermoplastic resin film laminated on an ink-passing porous support by subjecting it to overall solid perforation so as to totally remove the thermoplastic resin film. Such a stencil sheet unit may have substantially the same structure as disclosed in Japanese Utility Model Laid-open (Kokai) No.51-132007 and regarding the detail thereof, the publication should be referred to. The stencil sheet unit may have an ink cover sheet (not shown) which is fixed at an end to the stencil sheet unit on a side on which the ink is placed, in such a manner that it can be opened and closed.
The porous member 4 comprises an ink-passing gauze 42 stretched on a frame 41. The example of FIG. 1 shows an embodiment where the master stencil sheet 3 is provided between the printing material 1 and the porous member 4. Furthermore, in the example of FIG. 1, the master stencil sheet 3 is bonded to the porous member 4. Such a bonded assembly consisting of the master stencil sheet 3 and the porous member 4 can be produced by perforating a stencil sheet of the above-mentioned stencil sheet unit by a usual perforating method using a flash lamp or a thermal head to obtain perforations in conformity with a desired image.
For carrying out a printing by the stencil printing method of the present invention, first the master stencil sheet 3 and the porous member 4 are provided above the printing material 1 and besides the ink supply means 2 is provided above the porous member 4 with the ink-placed side facing upward as shown in FIG. 1(a). Then, as shown in FIG. 1(b), the printing material 1, the master stencil sheet 3, the porous member 4 and the ink supply means 2 are brought into close contact with each other, and a pressing force is applied in the direction shown by the arrow in the FIG. 1(b) to press out the printing ink 23, whereby the printing ink 23 is passed through the gauze 22 and the gauze 42 and through the perforations of the master stencil sheet 3 and transferred onto the printing material 1. Thereafter, as shown in FIG. 1(c), with the printing material 1, the master stencil sheet 3 and the porous member 4 being maintained in layers, only the ink supply means 2 is separated from the porous member 4. In this instance, the printing ink 23 transferred to the printing material through the gauze 42 is kept at a uniform thickness and the surface thereof is again under atmospheric pressure. Therefore, when the porous member 4 together with the master stencil sheet 3 are separated from the printing material 1 as shown in FIG. 1(d), the surface of the printing ink 23 is not subjected to abrupt change of pressure, and, as a result, formation of irregularity on the surface caused by viscosity or stringiness of the ink is inhibited and the ink held in the porous member is transferred to the printing material to form a print surface high in smoothness. The ink is supplied also to non-image portions of the porous member, and thus in the case of printing of many copies, care should be taken so that the ink is inhibited from being supplied excessively to the porous member and overflowing therefrom, for example, by adjusting the ink supplied from the ink supply means to an amount that compensates for the transferred ink. When ink is supplied so that thickness of the ink is greater than that of the porous member, there may be generated an internal stress between the ink on the porous member and the ink in the porous member, which sometimes causes uneven transfer when the porous substrate is removed. Therefore, it is preferred to supply the ink so as to be equal to or smaller than the thickness of the porous member.
The present invention is not limited to only the embodiment of FIG. 1(c) in which the master stencil sheet 3 is provided between the printing material 1 and the porous member 4 as far as the ink supply means 2 can be separated while the porous member 4 is left on the side of the printing material 1 after the printing ink 23 has been transferred to the printing material 1. That is, the master stencil sheet 3 may be provided between the porous member 4 and the ink supply means 2 as shown in FIGS. 2(a) and 2(b). In the arrangement of FIG. 2(a), the master stencil sheet 3 is bonded to the porous member 4 as a unit. In the arrangement of FIG. 2(b), the master stencil sheet 3 is bonded to the gauze 22 of the ink supply means 2 as a unit. Such units comprising the master stencil sheet 3 and the porous member 4 or the ink supply means 2 can be easily produced by perforating a stencil sheet of the abovementioned stencil sheet unit with a usual perforation method using a flash lamp or a thermal head to obtain perforations in conformity with the desired images. Moreover, as shown in FIG. 2(c), the master stencil sheet 3 may be arranged coplanar with the porous member, and, in other words, may be composed of a porous member impregnated with a photosensitive resin, which can yield a stencil by exposing the resin to a light through a mask of a positive film. However, in the embodiments of FIGS. 2(a) and 2(b), owing to spread of the ink in the porous member, the images printed on the printing material 1 are apt to blur, and, on the other hand, the embodiment of FIG. 2(c) requires much labor in perforation. Therefore, it is preferred to carry out the present invention according to the embodiment illustrated in FIG. 1.
Hereinafter, an example of the stencil printing apparatus of the present invention will be explained referring to FIG. 3 to FIG. 7.
FIG. 3 is an oblique view which illustrates the whole of an example of the printing apparatus according to the present invention. This printing apparatus has a base stand 10 as a first member supporting a printing material 1 and a pressing plate 20 fitted, rotatably at one end, to a shaft 12 provided at one edge side of the base stand 10. The pressing plate 20 acts as a second member supporting an ink supply means. The base stand 10 has a paper stacking stand 11 on the upper surface. The paper stacking stand 11 has a cushioning member, on which several sheets of printing paper can be stacked as the printing material 1. At the time of printing, a pressing force is applied to the printing papers on the paper stacking stand 11 by the pressing plate 20, and the cushioning member is elastically compressed by the pressing force.
In FIG. 3, the pressing plate 20 is apart from the base stand 10, and the pressing plate 20 and the base stand 10 are parted from each other at an angle of about 90° in respect to the revolving shaft 12. A fitting part 25 is provided on the lower surface of the pressing plate 20 and a frame of a known stencil sheet unit mentioned above can be removably fitted and held thereby. This example is such that can carry out printing according to the arrangement of FIG. 2(b).
Therefore, to the fitting part 25 is fitted a known stencil sheet unit perforated in conformity with a desired image. The stencil sheet unit can comprise a nearly rectangular frame 21 on one side of which is stretched a stencil sheet comprising a thermoplastic resin film laminated with a gauze 22 and to another side of which is fitted an ink-impermeable cover sheet (not shown) which can be opened or closed with respect to the frame 21. After the stencil sheet is perforated in conformity with the desired image, the ink-impermeable sheet is opened, then a printing ink 23 is charged inside the frame 21, and the ink-impermeable sheet is again closed to enclose the printing ink 23 in the frame 21. The stencil sheet unit containing the printing ink is fitted to the fitting part 25 of the pressing pate 20 and the printing is carried out.
In FIG. 3, a porous member 4 is disposed between the base stand 10 and the pressing plate 20. The porous member 4 comprises a frame 41 as a third member of the present invention and a gauze 42 stretched on the frame 41 and held thereby. The frame 41 is removably fitted to the revolving shaft 12 of the pressing plate 20. The frame 41 comprises a material of high rigidity, such as a cardboard, a metal or a plastic. When the gauze 42 is held thereby under application of tension, separation from the printing material can be uniformly performed at the time of printing and this is preferred. Moreover, the gauze 42 may be removably held by the frame 41 so that exchanging or cleaning of the gauze can be easily performed.
As shown in FIG. 4(a), the frame 41 is fitted so as to keep a given angle with the pressing plate 20 and can turn together with the pressing plate 20 with maintaining the above angle when it is not in contact with the printing material (printing paper) 1. A spring 15 is provided as a biasing means between the frame 41 and the pressing plate 20. The spring 15 is fitted to the revolving shaft 12 and gives a biasing force to the frame 41 in the direction toward the base stand 10 when the frame 41 comes close to the pressing plate 20 and the angle therebetween becomes smaller than the above angle.
As shown in FIGS. 4(a) and (b), a projection 45 is provided on the surface of the frame 41 on the side of the pressing plate 20 at the position near the revolving shaft 12. The spring 15 contacts with the frame 41 at the projection 45. As compared with a case where the spring 15 is supposed to directly contact with the surface of the frame 41 on the side of pressing plate 20, when the spring 15 is deformed by pressing the pressing plate 20 onto the side of the base stand 10, deformation of the spring 15 increases in correspondence to the projection 45. Thus, the springing force of the spring 15 increases accordingly, and separability between the frame 41 and the pressing plate 20 at the time of opening the pressing plate 20 after completion of printing is improved. In this way, when the springing force of the spring 15 is increased, the pressing plate 20 can be easily separated from the porous member 4 with the porous member 4 being left onto the printing material 1.
Next, operation of the printing apparatus of the present invention will be explained. Several sheets of printing papers are stacked on the paper stacking stand 11 of the base stand 10. A perforated stencil sheet unit containing an ink is fitted to the fitting part 25 of the pressing plate 20. The porous member 4 is fitted to the printing apparatus. The pressing plate 20 is turned toward the base stand 10. As shown in FIG. 5, when the pressing plate 20 is apart from the base stand 10 at a maximum, the pressing plate 20 forms an angle of about 90° with the base stand 10. In this state, the porous member 4 is positioned at an angle of about 60° with the base stand 10. With turning of the pressing plate 20, the porous member 4 turns with keeping an angle of about 30° with the pressing plate 20. As shown in FIG. 6, after the porous member 4 contacts with the uppermost printing paper put on the base stand 10, the spring 15 deforms and only the pressing plate 20 turns. Furthermore, as shown in FIG. 7, the pressing plate 20 is pressed to the base stand 10, thereby pressing the stencil sheet unit onto the printing paper to carry out printing.
After completion of the printing, the pressing plate 20 is turned up. As shown in FIG. 6, the porous member 4 is held on the printing paper by the pressing force of the spring 15 until the angle between the pressing plate 20 and the base stand 10 reaches about 30°, and, therefore, the porous member 4 is separated from the stencil sheet unit which is an integral article of the master stencil and the ink supply means. When the pressing plate 20 is further turned upward and forms an angle of greater than about 30°, the porous member 4 begins to turn upward together with the pressing plate 20 and is separated from the printing paper. At this time, the surface of the printing ink impregnated in the porous member 4 has already been released from the pressing force of the pressing plate 20 and subjected to atmospheric pressure, and hence irregularities are hardly formed on the surface of the printing ink transferred to the printing paper. As a result, a print high in smoothness is obtained.
In the above example, an apparatus suitable for carrying out the embodiment of FIG. 2(b) has been explained, but it is a matter of course that if the frame 41 has a function to hold the stencil sheet unit, the printing apparatuses for carrying out the embodiments of FIG. 1 and FIGS. 2(a) and 2(b) can be constructed.
According to the present invention, the printing ink is temporarily retained in the porous member and controlled to a uniform thickness under atmospheric pressure in the porous member after having been transferred to a printing material, and then the porous member is separated from the printing material. Therefore, no abrupt change of pressure is applied to the surface of the printing ink transferred to the printing material. Accordingly, even if a printing ink of high viscosity is used, it can be transferred to the printing material at a uniform thickness, and a print less in irregularity on the surface of the ink and high in gloss of the ink can be obtained. Thus, printing of solid portions or printing on a paper low in ink permeability or on a smooth surface of plastics can be performed with giving high quality, and the present invention is especially suitable for printing on coated paper, CD-ROMs, name plates, glass sheets and others. | The disclosed stencil printing method can produce prints having high glossiness by inhibiting the uneven transfer of ink caused by operation of separation of stencil. A stencil printing apparatus is disclosed. The stencil printing method includes superposing one upon another a master stencil sheet (3) and a printing material (1) (a material to be printed) and pressing an ink supply element (2) to the master stencil sheet from the side opposite to the printing material, in the direction toward the printing material, thereby passing a printing ink through the master stencil sheet to transfer the ink to the printing material, wherein ink-passing porous member (4) is disposed between the ink supply element and the printing material to transfer the printing ink to the printing material through the porous member. The ink supply element is separated from the porous member while the porous member is left on the printing material, and then the porous member is separated from the printing material. The porous member may be disposed between the ink supply element and the master stencil sheet or between the master stencil sheet and the printing material. The master stencil sheet and the porous member or the ink supply element may be bonded to each other. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to a water-cooled high voltage device having: a plurality of electrical units three-dimensionally stacked in a plurality of levels, each electrical unit having a stackable frame and a plurality of electrical modules disposed at the frame; pumping means for delivering cooling water; and a pipeline network for supplying the cooling water to the electrical modules.
The water-cooled high voltage device of this type has been widely used. A water-cooled thyristor conversion device described later in an embodiment is a typical example. Along with a recent increase in power consumption, a high-voltage and large-current device is used for a power generating system, a power transforming system, an AC/DC conversion system and so on. A compact water-cooled high voltage device is desirable for easy installation. It is also desirable that the structure of the device be suitable for mass production, easy assembly, easy maintenance and repair. In response to the above needs, a method for manufacturing a high voltage device is proposed in which the device is divided into at least one type of standard electrical module for mass-production. Desired number of each type of modules are mounted on a frame to form a basic unit, that is, an electrical unit. A predetermined number of electrical units are integrally assembled and high voltage connections are performed to complete a single high voltage device.
In the high voltage device of the above arrangement, a compact device can be manufactured by appropriately designing the electrical module and the electrical unit. The installation space is thus decreased. However, the high voltage device as a whole is heated at a high temperature due to heat generated by each unit, resulting in degradation of performance of the device. Finally, the device may be broken. In order to eliminate this drawback, various cooling means are proposed. However, it is difficult to cool parts of the large-scaled high voltage device uniformly and efficiently. Temperatures of the units vary greatly as will be described below.
FIG. 1 shows a conventional water-cooled high voltage device 116 formed by stacking electrical units in two levels. In the water-cooled high voltage device 116, oblong members are electrical modules 110 of at least one type according to a standard design. Two sets of electrical modules 110 are aligned horizontally and eight electrical modules 110 are aligned vertically in each set, as shown in FIG. 1. These electrical modules 110 are mounted in a proper container. The container and thin wires are omitted so as to clearly show the arrangements of the electrical modules 110 and the pipeline network of the cooling water. This applies to the following drawings unless otherwise specified. Three conductors P, M, and N are connected to the water-cooled high voltage device 116. Eight electrical modules arranged between the conductors P and M are assembled integrally to form an upper level electrical unit 112, and eight electrical modules arranged between the conductors M and N are assembled integrally to form a lower level electrical unit 114. Although the three conductors P, M and N are illustrated in FIG. 1, the number of conductors may be arbitrarily selected in accordance with the type of device. An AC or DC voltage may be applied across the device and an AC or DC current may also flow therethrough.
Since the electrical modules 110 dissipate heat during operation, cooling water is supplied thereto. Water is usually delivered from a pump 118 which is installed underground or on the ground. The water is then cooled in a cooler 120. The cooling water rises in pipes 122a and 122b formed by an electrical insulator and is subsequently supplied from the lowest electrical modules 110 among the eight right electrical modules and the eight left electrical modules. The cooling water used for cooling the electrical modules 110 returns to the suction side of the pump 118 through pipes 122c and 122d made of an electrical insulator. The pump 118 is driven again to supply the cooling water to the electrical modules 110 which are then cooled. Since the electrical modules 110 have the same structure, the cooling water is supplied to the lower electrical modules 110 at a high pressure and in a great amount, while it is supplied to the upper electrical modules 110 at a relatively low pressure according to the above cooling system. As a result, temperature of the electrical modules at high level are higher than that of the electrical modules at low level.
FIG. 2 shows a cooling water pipeline network of the water-cooled high voltage device 116 shown in FIG. 1. The flow path of the water pipeline network in FIG. 2 correspond to that in FIG. 1. A zigzag symbol denotes a flow resistance in a corresponding portion. Reference numeral 124 denotes a flow resistance acting on the cooling water flowing through the electrical module 110. Reference numeral 126 denotes a flow resistance of the pipe 122c connecting the vertically adjacent electrical modules 110. Arrows in FIGS. 1 and 2 denote the flow of the cooling water.
In an example shown in FIGS. 1 and 2, the number of vertically arranged electrical modules 110 is small. These electrical modules are distributed and arranged in electrical units 112 and 114. The device is formed by two-level electrical units 112 and 114. Therefore, the level difference between the upper and lower electrical modules 110 is relatively small. However, in a large-scaled high voltage device, the electrical units 112 and 114 are preferably stacked at three or four levels. A thyristor conversion device which has a rated DC voltage of 125 kV and a DC current of 1,200 A (measured in a three-phase bridge circuit) is mounted in the three-phase bridge circuit, the level difference becomes 3 to 6 m. Further, when the two three-phase bridge circuits are cascade-connected, the level difference becomes 10 to 12 m. It is very difficult to uniformly cool the electrical modules 110 in different levels.
According to a graph in FIG. 3, the level of the electrical modules 110 is plotted along the axis of abscissa, while the flow rate of the cooling water flowing through the electrical module 110 as a function of the level of the electrical modules is plotted along the axis of ordinate. At point P, the flow rate of the cooling water flowing through the fourth electrical module 110 from the bottom is 0.4 times that of the cooling water flowing through the lowest electrical module. As is apparent from the graph, the upper electrical modules 110 are not sufficiently cooled. In order to solve the above problem, the diameters of the pipes 122a, 122b, 122c and 122d are enlarged to reduce the flow resistances in the pipes 122a to 122d. However, a piping work becomes cumbersome. Even if this operation is performed, the device as a whole becomes large in size. Theoretically, a flow resistance 124 within the electrical modules 110A need only be designed to be larger than a flow resistance 126 within the vertically aligned pipes 122a to 122d. However, a high output pump must be used and the cooling water pressure is increased. Therefore, highly rigid pipes and joints must be used, resulting in inconvenience.
The hydrokinetic problems in the cooling water pipeline network have been considered so far. Larger diameter pipes also result in inconvenience from the electrical point of view. The electrical modules for a high voltage are disposed at high level, while the electrical modules for a low voltage are disposed at low level. The pipes 122a to 122d vertically extend between the electrical modules at high and low levels. Therefore, parts at high and low voltages are shortcircuited by the cooling water flowing through the pipes 122a to 122d. A leakage current flows through the cooling water. The conductors on the sides of the high and low voltages are electrically corroded. This electrical corrosion frequently occurs when large diameter pipes are used and a large amount of cooling water exists between the members of the high and low voltages. Especially, this phenomenon occurs in a recently developed thyristor conversion device in which resistors, reactors and so on used in cooperation with thyristor elements are directly cooled by the cooling water. Therefore, small diameter pipes are preferably used to increase the leak resistance between the members of high and low voltages. Although a highly pure cooling water may be used to extremely decrease electrical conductivity theoretically, special equipment for maintaining an extremely low electrical conductivity is required, resulting in economic disadvantages.
It is thus strongly desired to develop a water-cooled high voltage device, which requires a small installation space, which rarely causes electrical corrosion even if water obtained from the conventional ion exchanger is used, and which substantially uniformly cool each electrical module.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a water-cooled high voltage device which requires a small installation space, which substantially eliminates flow of a leakage current, and which is substantially uniformly cooled.
In order to achieve the above object of the present invention, the pipeline network of the water-cooled high voltage device discribed at the beginning of this specification has a plurality of pipes each supplying cooling water delivered by the pumping means directly to each of the electrical units, respectively.
According to a water-cooled high voltage device using the pipeline network for circulating the cooling water according to the device described above, the cooling water supplied from the pump is not branched but supplied directly to a plurality of electrical modules included in a predetermined electrical unit. Therefore, the cooling water is supplied to the electrical modules in the upper electrical unit independently of the electrical modules in the lower electrical unit. All the electrical modules are thus substantially uniformly cooled.
The pipes which are vertically disposed from the pump to the electrical units need only flow the required amount of cooling water. As compared with the conventional cooling water supply system in which the cooling water is sequentially supplied first to the nearest pipes and then the farthest pipes, small diameter pipes can be used in the water-cooled high voltage device according to the present invention. Electrical corrosion due to the cooling water in the pipes is decreased and the service life of the device is prolonged.
In summary, since the electrical units having a plurality of electrical modules are stacked three-dimensionally, a necessary installation space is decreased. Further, since the cooling water from the pump is independently supplied to each electrical unit through separate pipes, all the electrical modules are substantially uniformly cooled. Further, since the diameter of the pipes is determined to be enough to supply the cooling water to the electrical modules belonging to each electrical unit, the leakage current which may flow between the electrical units is decreased and electrical corrosion is thus decreased.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view illustrating the one-phase arrangement of a conventional water-cooled high voltage device;
FIG. 2 is a view illustrating a cooling water pipeline network included in the arrangement shown in FIG. 1;
FIG. 3 is a graph for explaining various flow rates of the cooling water flowing through electrical modules included in the electrical units;
FIG. 4 is a view illustrating the one-phase arrangement of a water-cooled thyristor conversion device to which the present invention is applied;
FIG. 5 is a block diagram of an example for explaining internal connections of the thyristor modules arranged in the device shown in FIG. 4;
FIG. 6 is a view illustrating a cooling water pipeline network included in the arrangement shown in FIG. 4;
FIG. 7 is a block diagram of a three-phase bridge circuit used in the device according to the present invention;
FIG. 8 is a view illustrating a one-phase thyristor valve formed by stacking a high voltage thyristor unit and a low voltage thyristor unit;
FIG. 9 is a block diagram illustrating connections of a large capacity thyristor conversion device formed by cascade-connecting two three-phase bridge circuits shown in FIG. 7;
FIG. 10 is a view illustrating a four-stage thyristor valve formed by stacking the four thyristor units of the same phase of FIG. 9;
FIG. 11 is a view illustrating a one-phase thyristor valve of a water-cooled high voltage device according to another embodiment of the present invention;
FIG. 12 is a view illustrating a cooling water pipeline network used in the water-cooled high voltage device shown in FIG. 11; and
FIGS. 13 and 14 are views for explaining a water-cooled high voltage device according to still another embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Water-cooled high voltage devices according to embodiments of the present invention will be described with reference to the accompanying drawings. In order to describe the present invention in detail, water-cooled thyristor conversion devices are exemplified in the following description.
FIG. 4 shows an arrangement of 16 electrical modules, that is, thyristor modules 10 (to be referred to as a module hereinafter for brevity) included in one phase of a water-cooled thyristor conversion device. The 16 modules 10 are arranged in the same manner as in the conventional device shown in FIG. 1. An electrical unit 12 (to be referred to as a unit hereinafter for brevity) of a high voltage side which includes eight modules 10 is mounted on a frame 12a. An electrical unit 14 (to be referred to as a unit hereinafter for brevity) of a low voltage side which includes eight modules 10 is mounted on a frame 14a. These units 12 and 14 are separately assembled and stacked. The units 12 and 14 are connected in series between a conductor P at the high voltage output side and a conductor N at the low voltage output side. A conductor M is connected to one phase of a three-phase a.c. power source and a connecting portion of the units 12 and 14. The units 12 and 14 are integrally stacked in two stages to form a thyristor valve 16 corresponding to one phase. FIG. 5 shows the main part of the electrical circuit of the module 10 shown in FIG. 4. The module 10 is connected to an external circuit through terminals 10a and 10b. A plurality of main electrical circuits 11 are connected in series with each terminal through each anode reactor 10c. Each main electrical circuit 11 comprises three circuits which are parallel-connected. A first circuit 13 comprises a thyristor element 13a. A second circuit 15 has a snubber circuit 15a. A third circuit 17 includes a voltage divider series circuit 17a and an amplifier 17b for gate firing. The mode of operation of the main electrical circuit 11 is known, and a detailed description thereof will be omitted. Two more thyristor valves same as the thyristor valve 16 are assembled. These thyristor valves are connected in the manner as shown in FIG. 7 to assemble a three-phase thyristor conversion device.
A case 31 shown in FIG. 4 houses a one-phase thyristor valve 16. Water delivered from a pump 18 and cooled by a cooler 20 is supplied to the case 31. The cooling water is then supplied to a cooling path 32 in each module through a cooling water pipeline network 30 (FIG. 6).
The pipeline network 30 shown in FIG. 4 is different from the pipelines in the conventional device shown in FIGS. 1 and 2. The water delivered from the pump 18 and cooled in the cooler 20 is immediately branched into three cooling water supply pipes. Among these pipes, pipes 34a and 34b supply the cooling water to one and the other modules, respectively, each consisting of four modules 10 arranged in the unit 14. A third pipe 36 which is independently of the pipes 34a and 34b supplies the cooling water to the unit 12. The pipe 36 which has reached the unit 12 is branched into two pipes 38a and 38b. The pipes 38a and 38b supply the cooling water to one and the other modules, respectively, each consisting of four modules arranged in the unit 12. The cooling water supplied to the unit 12 is not supplied to the unit 14. The cooling water supplied to the unit 14 is not supplied to the unit 12. Thus, the cooling water is directly supplied to each unit uniformly. The uniform supply of the cooling water is indicated by two lines L 1 and L 2 in FIG. 3.
FIG. 6 shows a circuit diagram of the cooling water pipeline network 30 shown in FIG. 4. The water used to cool the modules 10 returns to the suction side of the pump 18 through pipes 34c, 34d, 38c and 38d. The zigzag symbol indicated in each pipe denotes a flow resistance of the pipe.
The cooling water delivered from the pump 18 and drawn thereto is branched through the pipes 34a, 34b, 36, 34c, 34d, 38a, 38b, 38c and 38d shown in FIGS. 4 and 6. Therefore, the diameter of these pipes may be smaller than that of the pipes 122a, 122b, 122c and 122d shown in FIGS. 1 and 2. The electric resistance against the leakage current flowing through the conductors P, M and N in the device shown in FIGS. 4 and 6 is higher than that in the conventional device shown in FIGS. 1 and 2. Therefore, the leakage current is very small.
If three sets of thyristor valves shown in FIG. 4 are assembled to form a three-phase bridge circuit and if the three-phase bridge circuit is connected to a three-phase AC power source, a DC output is obtained from the output terminals of the thyristor conversion device.
FIG. 7 shows a block diagram of a two-stage water-cooled thyristor conversion device using units 12A, 12B and 12C of the high voltage side and units 14A, 14B and 14C of the low voltage side. Reference symbols P and N denote a high voltage terminal and a low voltage terminal, respectively. Reference numeral 40 denotes a three-phase power source. The units 12A and 14A, 12B and 14B, and 12C and 14C are vertically stacked to form first phase, second phase and third phase thyristor valves, respectively. FIG. 8 shows a first columnar-shaped and two-stage thyristor valve having the unit 12A of the high voltage side and the unit 14A of the low voltage side as shown in FIG. 4.
FIG. 9 is a block diagram of a four-stage water-cooled thyristor conversion device in which a high voltage three-phase bridge circuit 60 having units 50A, 50B, 50C, 52A, 52B and 52C is cascade-connected to a low voltage three-phase bridge circuit 62 having units 54A, 54B, 54C, 56A, 56B and 56C. The units 50A, 52A, 54A and 56A are vertically stacked to form a first phase four-stage thyristor valve. Similarly, the units 50B, 52B, 54B and 56A are stacked to form a second phase four-stage thyristor valve and the units 50C, 52C, 54C and 56C are stacked to form a third phase four-stage thyristor valve. Reference symbols P and N denote the conductors at the output sides. Reference numerals 40A and 40B denote a three-phase power source. FIG. 10 shows the outer appearance of the first phase four-stage thyristor valve comprising the units 50A, 52A, 54A and 56A shown in FIG. 8.
FIG. 11 shows a two-stage water-cooled thyristor conversion device having modules 10 arranged in the same manner as shown in FIG. 4, except that a cooling water pipeline network 31 is provided. In this case, the cooling water supplied from the cooler 20 is raised to a level between the unit 12 of the high voltage side and the unit 14 of the low voltage side through a pipe 64. From this level, the cooling water is branched into the high and low voltage sides and supplied to the units 12 and 14. After uniformly cooling all the modules 10, the cooling water returns to the suction side of the pump 18 as shown in the figure. The cooling water is not branched from the beginning. The cooling water is first raised to high level and supplied to the units 12 and 14. Therefore, the cooling water is substantially uniformly supplied to the units 12 and 14. The diameter of pipes 66, 68, 70 and 72 extending near the conductor P of the high voltage side can be small. The leakage current flowing through the conductors P, M and N is smaller than that in the conventional device shown in FIG. 1. FIG. 12 shows a flow path of the pipeline network shown in FIG. 11. The mode of operation of the circuit diagram in FIG. 12 is substantially the same as that of the circuit diagram in FIG. 5, and a detailed description thereof will be omitted.
In the device shown in FIGS. 11 and 12, a great amount of cooling water is supplied to the modules 10 near a cooling water supply point Q. The amount of cooling water supplied to the modules 10 apart from the cooling water supply point Q is decreased. However, the cooling water is not abruptly decreased as indicated by the lines L 3 and L 4 in FIG. 3 unlike the conventional case. In the device shown in FIG. 11, large diameter pipes need not be disposed between the terminals P and N, thus decreasing the leakage current between the terminals and the electrical corrosion.
FIG. 13 shows a two-stage water-cooled thyristor conversion device, in which a cooling water pipeline network 80 for the unit 12 of the high voltage side and a cooling water pipeline network 81 of the unit 14 of the low voltage side are separately disposed. A high pressure output pump 18a is connected to the unit 12 located at a high level position, while a low pressure output pump 18b is connected to the unit 14 located at a low level position.
The reason of using a high pressure output pump 18a for the unit 12 of the high voltage side is such that the flow speed of the cooling water through the pipe 36 extending between the conductor P of the high voltage side and the conductor N of the low voltage side can be made high even when the diameter of the pipe is small causing to maintain sufficient cooling effect of the modules 10 in the unit 12 of the high voltage side and to obtain large electric resistance of and low leak electric current through the cooling water in the pipe 36.
FIG. 14 shows a embodiment of this invention in which units 50A, 52A, 54A and 56A are stacked to form a four stage thyristor valve shown in FIG. 10, and the cooling water pipe line network is formed according to the feature of FIG. 11. In this embodiment, the cooling water is supplied to upper units 50A and 52A from the high pressure output pump 18a through the pipe 36, while the cooling water is supplied to lower units 54A and 56A from the low pressure output pump 18b through a pipe 136. | In a water-cooled high voltage device, a plurality of electrical modules are divided into a plurality of electrical units. The electrical modules are cooled by cooling water supplied from a pump through pipes which are disposed in the electrical units, respectively. The size of the pipe diameter is determined to be enough to allow cooling water to flow at a relatively low pressure and to properly cool the electrical modules. | 5 |
This application is a continuation-in-part of 09/122,610, filed Jul. 24, 1998 now in 6,209,665.
BACKGROUND OF THE INVENTION
The present invention is related to earth drilling equipment, and particularly to down hole, pneumatic, percussive hammer drilling systems. As noted in my related co-pending applications, Ser. No. 08/674,123, filed Jul. 1, 1996, and Ser. No. 09/122,616, filed Jul. 24, 1998, to which the present application is a continuation-in-part, underreamers are used for the formation of radially enlarged areas extending about a pilot bit for insertion of a casing.
Eccentrically mounted underreamers are known which include an arm which travels in an orbit for underreaming operation, and which are retractable toward the hole axis for tool removal purposes. However, eccentrically mounted underreamers can be diverted off-axis if the underreamer encounters rock fragments, buried metal objects, etc. Any diversion of a large drill bit is unacceptable in most drilling operations, and particularly where a series of closely spaced holes are being formed.
The installation of casing in a drilled ground hole is also greatly hindered by any such diversion.
Other known underreaming equipment utilizes three bit mounted plates which are outwardly displaceable, but which incorporate a total working surface which is substantially less than the perimeter of the bore. Such undersized plates are subject to excessive wear and result in slow drilling operation.
Underreaming can also be achieved by use of a crown or ring bit, but components of those bits must be left in the underreamed area when drilling is complete, which is costly and otherwise unacceptable in some drilling operations.
Each of these problems is addressed by my co-pending U.S. application Ser. No. 08/674,123, and by the additional related underreamer embodiments disclosed and claimed below.
In addition to the foregoing problems associated with known underreamers, quick and efficient removal of drilling debris from the hole and drilling bits remains a problem. In my U.S. Pat. No. 5,511,628, which is hereby expressly incorporated by reference into this application, I disclosed a pneumatic down-hole drill with a central evacuation outlet. The apparatus of U.S. '628 permits continuous evacuation of large debris fragments through a central axial bore formed in the bit and through a central evacuation tube attached thereto. Compressed air is directed downwardly through peripheral channels, under the drill bit, and into a central evacuation tube. The flow of compressed air through the central evacuation tube provides continuous and efficient removal of earthen fragments from the bore, including rapid removal of fragments that would be too large for removal through peripheral pathways along the casing.
However, a need remains for a reverse circulation pneumatic drill which provides for underreaming of the bore, continuous evacuation of drilling debris fragments from the drilling face in the bore, and for ready removal of the drill bit through the casing during or after completion of the drilling operation.
SUMMARY OF THE INVENTION
The present invention is embodied in a reverse circulation system that addresses the shortcomings of the prior art.
It is therefore an object of the invention to provide an underreamer that includes a pilot bit on which are mounted underreamer arms which can be extended and retracted by relative rotation between the pilot bit and the underreamer arms. Each underreamer arm includes a strengthening boss. The strengthening boss includes axial bearing surfaces that engage corresponding axial surfaces of the pilot bit. The bearing surfaces of the arm bosses and the bits include surfaces shaped to extend the arms as the pilot bit is rotated relative to the pilot bit. Surfaces are also provided for locking the arm in its extended underreaming position. As the bit is rotated in the opposite direction, the locking surfaces disengage and the arm can be retracted without vertical movement of the driver.
In another aspect of the invention, provision is made to continually flush the bit with compressed air which is exhausted from the down hole hammer. The flow of exhaust air is routed through porting in the bit assembly into the central evacuation tube. A second flow of compressed air may also be provided to continually flush the perimeter region of the bit. In one embodiment, the perimeter flushing air is received from compressed air introduced at the well-head to pressurize the casing.
These and other aspects of the invention will be described in further detail with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial cross-sectional view of a drilling assembly according to the present invention.
FIG. 2 is an expanded partial cross-sectional view of the assembly shown in FIG. 1, showing the power head assembly, compressed air inlet collar, and the upper terminus of the dual wall pipe assembly.
FIG. 3 is an expanded cross-sectional view of the assembly shown in FIG. 1, showing the casing driver in greater detail.
FIG. 4 is an expanded cross-sectional view of assembly shown in FIG. 1, showing the dual wall pipe assembly and the box and back head assembly connecting the lower terminus of the dual wall pipe assembly to the down-hole pneumatic hammer.
FIG. 5 is a cross-sectional view of the down-hole pneumatic hammer assembly, including the bit assembly.
FIG. 5A is a perspective view of an alternative design for the hammer barrel of the down-hole pneumatic hammer assembly.
FIG. 6A is an exploded perspective view of a first embodiment of a bit assembly according to the present invention.
FIG. 7A is a perspective view of the pilot bit on the embodiment of FIG. 6 A.
FIG. 7B is a bottom view of the pilot bit shown in FIG. 7 A.
FIG. 8 is a perspective view of an underreamer arm used in the embodiment shown in FIG. 6 A.
FIG. 9A is an end view of the underreamer arm shown in FIG. 8 .
FIG. 9B is an outer side view of the underreamer arm shown in FIG. 8 .
FIG. 10 is a bottom view of the bit driver of the embodiment shown in FIG. 6A, showing the axial surfaces which define the recesses which receive the underreamer arms, and the axial surfaces which bear against the underreamer arms for extension and retraction.
FIG. 11 is a bottom view of the bit driver in a second embodiment of the invention.
FIG. 12 is a bottom view of an underreamer arm of the embodiment referred to in FIG. 11 .
FIG. 13 is a bottom view of the arms depicted in FIG. 12 mounted in their retracted position on the bit driver shown in FIG. 11 .
FIG. 14 is a top view of a pilot bit for use with the bit driver and underreamer arms depicted in FIG. 13 .
FIG. 15 is a bottom view of the pilot bit depicted in FIG. 14 .
FIG. 16 is the bit driver and underreamer arms shown in FIG. 13 with the underreamer arms in their extended positions.
FIG. 17 is an enlarged partial view of the bit driver and underreamer arm shown in FIG. 13 .
FIG. 18 is a partial cutaway bottom view of the bit assembly depicted in FIGS. 11-17 showing the compressed air flow path.
DETAILED DESCRIPTION
Referring now to FIG. 1, a reverse circulation drilling system, shown generally at 10 , includes a head assembly 11 , a dual wall pipe assembly 12 , and a down hole pneumatic hammer 13 within a bore casing 14 . Turning to FIGS. 2 and 3, head assembly 11 includes a casing driver 15 for driving the bore casing 14 downwardly as the bit advances, and a power head assembly 16 of standard design for rotating the bore casing 14 it is driven downwardly. Casing driver 15 includes an annular hammer 17 which reciprocates vertically as compressed air is alternatively admitted to chambers above and below hammer 17 . Hammer 17 impacts on anvil 18 , which in turn impacts on casing cap 19 . Casing cap 19 is sealed against the inner surface of bore casing 14 to permit pressurization, through port 20 , of bore casing 14 between casing cap 19 and down hole hammer assembly 13 . Pressurization of the casing provides a downward flow of air between the casing and the down hole hammer, preventing upward migration of debris between the down hole hammer and casing, which can hinder the removal of the hammer.
In locations where there is a concern about the stability of the formation being drilled, use of a pressurizing fluid other than air is preferred. The alternative pressurizing fluid in such instances can be water, drilling mud, a polymeric liquid, or another substantially non-compressible fluid. When a non-compressible fluid is used to pressurize the casing, a portion of the fluid is discharged into the lower portion of the bore, and supports the surrounding formation, reducing the likelihood of the bore collapsing.
Power head assembly 16 is connected to anvil 18 through linkage assembly 21 to impart rotation to the dual pipe assembly and the down hole hammer. Power head assembly 16 is of a design generally known in the field, other than its central member 22 , that is threaded onto the upper end of dual wall pipe assembly 14 , includes a central bore in communication with the dual wall pipe assembly to extend the debris discharge path through the power head to the elbow 29 . The joint of central member 22 and the dual wall pipe 14 includes a port 23 for admitting air to the annulus 24 between the inner wall 25 and the outer wall 26 of the dual wall pipe assembly. Collar 27 is mounted around the joint, and includes air inlet 28 , through which compressed air is admitted into the dual wall pipe assembly for driving the down hole hammer as further described below. An elbow 29 is rotatably mounted and sealed to the upper end of central member 22 . Elbow 29 , central member 22 and the inner wall 25 of dual wall pipe assembly 14 together form a central drilling debris discharge tube for continuously discharging drilling debris from the down hole hammer as will also be described more fully below.
Turning also to FIG. 4, dual wall pipe assembly 12 is assembled from individual segments, each of which includes an inner pipe 31 and an outer pipe 33 . Each segment includes a threaded male connector 33 and a threaded female connector 35 at opposite ends. Male connector 14 and female connector 15 each includes air ports 36 and 37 respectively which are in communication with outer annulus 24 of dual wall pipe assembly 11 . At its upper end, dual wall pipe assembly is threaded in to central member 22 of power head 16 . At its lower end, dual wall pipe assembly 11 is connected to the box 38 , which in turn is threaded into back head 40 of down-hole hammer 13 . Ports 42 an 44 communicate with annulus 24 of the dual wall pipe assembly to route compressed air therefrom into the down hole hammer.
Turning now to FIG. 5, down-hole hammer 13 includes box 38 threaded onto back head 40 . A sleeve 41 and a hammer barrel 42 are threaded into back head 40 . A centrally located discharge tube 43 is pressed into sleeve 41 . A wear sleeve 44 is fitted around hammer barrel 40 , and press fitted over ring 45 and onto shoulder 46 of back head 40 . Sleeve 41 and barrel 42 define an annular upper air chamber 48 . Central evacuation tube 43 and barrel 42 define an annular lower air chamber 50 . The lower end of barrel 42 abuts bit driver 52 , and also includes a perimetrical lip 54 which engages wear sleeve 44 to center barrel 42 in the wear sleeve. Hammer 53 is slidingly fitted into barrel 42 for reciprocation. Bit driver 52 is slidably fitted into barrel 42 below hammer 53 , and over the lower end of central evacuation tube 43 . Bit driver 52 is retained in barrel 42 by a plurality of keys 56 , each of which is fitted into a keyway 58 and annular recess 60 of bit driver 52 . (See also applicant's U.S. Pat. No. 5,511,628, incorporated by reference above, for detail of an alternate barrel assembly incorporating a like key and keyway assembly for mounting the bit driver in the hammer barrel.) The key-keyway assembly permits the bit assembly to advance ahead of the dual wall pipe assembly during drilling.
A bit assembly according to the present invention is shown in FIG. 6 . Turning to FIG. 6, a bit assembly includes bit driver 52 , pilot bit 82 , and arms 88 a-c . Pilot bit 82 includes an upper shank 83 having a recessed chamfer 84 , camming surfaces 85 a and 85 b , and a lower portion 86 . Lower portion 86 includes three peripheral recesses 87 a-c . Hardened drilling buttons, preferably made of a carbide material, are mounted on the peripheral and bottom surfaces of the pilot bit (FIG. 7 ). Arms 88 a-c are nested atop pilot bit 82 , and slide thereon in an prescribed arcuate path as will be described. Each of the arms includes a raised boss 89 which is received into corresponding recess 90 of bit driver 52 (FIG. 10 ). Raised boss 89 serves several functions. First, impact forces from the hammer are transmitted downwardly to the pilot bit 82 through bit driver 52 , boss 89 , and arm 88 . Second, boss 89 is received and retained in recess 90 , where it rotates through a limited arc to extend and retract arm 88 . With arm 88 in its retracted position, surface 91 is adjacent camming surface 85 a . in this configuration, the overall diameter of the bit assembly is less than the inner diameter of the bore casing, permitting the bit assembly to be withdrawn from the bore. As arm 88 is rotated clockwise about pilot bit 82 by clockwise rotation of bit driver 52 , angled surfaces 85 a engage surface 92 and urge arm 88 outwardly. The rotation and extension of arm 88 continues until surface 92 a abuts surface 85 b and surface 92 b abuts surface 85 a , locking arm 88 in its extended position. To unlock and retract arm 88 , bit driver 52 is rotated in the opposite direction. In its fully retracted position, the overall diameter of the underreamer assembly is less than the inside diameter of the casing, permitting withdrawal of the entire underreamer bit assembly through the casing if necessary. This feature represents a significant advance over known underreamers, which cannot be retracted and withdrawn through the casing if necessary.
In operation, compressed air is delivered into annular chamber 59 through port 37 , radial ports 60 , annulus 62 and axial ports 64 . In FIG. 5, hammer 53 is shown during its downward stroke. Lip 66 is engaged with lip 68 , sealing off chamber 48 . Lip 72 is engaged with lip 74 , sealing off chamber 50 . Port 78 is closed. As piston 53 continues downwardly, port 76 is uncovered, exhausting chamber 48 . At about the same time, lip 74 disengages from lip 72 , admitting a fresh charge of compressed air into chamber 50 to raise piston 53 to its upper position after it has struck bit driver 52 . As piston 53 rises, port 78 is uncovered, exhausting chamber 50 . Lip 74 engages lip 72 , sealing chamber 50 . Port 76 is sealed by piston 53 , and lip 66 disengages from lip 68 , admitting a fresh charge of compressed air into chamber 48 . The fresh charge of compressed air in chamber 48 drives piston 53 downwardly to begin another stroke. The compressed air exhausted into ports 76 and 78 is collected in port 80 (FIG. 5 A), and discharged through the bit assembly into central evacuation tube 43 , carrying with it drilling debris and earthen fragments dislodged by the bit. As an added precaution against drilling debris becoming lodged between arms 88 a-c and the pilot bit, in the bit assembly embodiment shown in FIG. 6B, port 91 is provided through which compressed air can be discharged to clear debris. The flow of compressed air through the bit assembly is essentially continuous, and provides a continuous evacuation of drilling debris from the drilling face of the bore. Moreover, the essentially constant diameter of the evacuation tube and inner wall of the dual wall pipe assembly provides a constant air velocity, which further aids debris removal. The continuous removal of debris through the central evacuation tube promotes continuous drilling. It is seldom, if ever necessary to stop drilling and raise the bit to clear debris from the bore. Significant improvements in drilling rates directly result. In addition, since debris is quickly removed as it is dislodged, it is possible to obtain a relatively accurate “core” sample from the bore. This aspect of the invention is useful in both exploratory and environmental applications.
In another aspect of the invention, pilot bit 104 advances into the ground with the underreamer arms locked in a deployed position below and radially beyond the advancing end of the casing at C. Casing movement is facilitated by the relatively large underreamed area, and if required, by the casing driver 15 . In one embodiment shown in FIGS. 1 and 3, if the drill bit assembly advances more than a predetermined distance ahead of the casing, linkage 21 operates a valve to provide compressed air to the pneumatic hammer 17 and associated porting casing driver 15 .
An alternative embodiment of the invention will now be described with reference to FIGS. 11-19. In this embodiment, the bit assembly also includes a bit driver 100 , arms 102 a-c , and pilot bit 104 , which are fitted together as described in the previous embodiment shown in FIG. 6 . In this embodiment, however, compressed exhaust air from port 80 is routed through internal ports in the bit driver, arms and pilot bit. Referring to FIG. 1, hammer exhaust air from port 80 flows into and through bit driver 100 via ports 106 a-c . The hammer exhaust air then flows through ports 108 a-c formed in arms 102 a-c respectively (FIG. 12 ). In FIG. 13, the arms are shown mounted on the bit driver in their closed and retracted positions. Exhaust air from ports 108 a-c flows into ports 110 a-c in pilot bit 104 (FIGS. 14, 15 ), through channels 112 a-c , ports 114 a-c , and into central evacuation tube 43 (FIG. 5 ). Ports 106 a-c , 108 a-c and 110 a-c respectively are located so that they are all aligned when arms 102 a-c are extended; i.e., holes 106 a , 108 a and 110 a are aligned, holes 106 b , 108 b and 110 b are aligned, and holes 106 c , 108 c and 110 c are aligned. Referring to FIGS. 16 and 17, when driver 100 is rotated relative to pilot bit 104 to position arms 102 a-c in their closed, retracted positions, ports 108 a-c (through arms 102 a-c respectively) are partially offset from ports 106 a-c respectively; ports 110 a-c (through the pilot bit) are offset from ports 108 a-c (through the pilot bit) are entirely offset. To provide for a continuous flow of air through ports 106 a-c , 108 a-c and 110 a-c when the arms are retracted, channels 112 a-c are provided in the underside of arms 102 a-c . Turning again to FIG. 15, pilot bit 104 also includes axial recesses 114 a-c , and transverse channels 116 a-c . Recesses 114 a-c and channels 116 a-c provide a path for the discharge of compressed air from outside the bore casing to also be discharged through central evacuation tube 43 .
The foregoing description of the invention is intended to be illustrative rather than exhaustive. Those skilled in the art will appreciate that numerous changes in detail are possible without departing from the scope of the following claims. | A underreamer drill bit assembly including a pilot bit and extendable underreaming arms operatively connected to the pilot bit. The underreaming arms have an extended position for underreaming, and a retracted position in which the overall diameter of the underreamer drill bit assembly is less than the inside diameter of the well casing, permitting the entire bit assembly to be withdrawn through the well casing. In another aspect of the invention, the bit assembly is operatively connected to a dual wall pipe assembly. A supply of compressed air is conducted through the annulus of the dual wall pipe assembly to a down hole pneumatic hammer. Exhaust air from the down hole hammer is directed to the bit assembly for continuous removal of drilling debris through a central evacuation tube of the dual wall pipe assembly. In another aspect of the invention, a pressurized, incompressible fluid is injected into the annulus between the well casing and the downhole pneumatic hammer. | 4 |
FIELD OF THE INVENTION
[0001] This invention relates to novel compositions of botulinum toxin that can be applied topically for various therapeutic, aesthetic and/or cosmetic purposes and that have an improved safety profile compared to existing botulinum -containing compositions that are injected subcutaneously.
BACKGROUND OF THE INVENTION
[0002] Skin protects the body's organs from external environmental threats and acts as a thermostat to maintain body temperature. It consists of several different layers, each with specialized functions. The major layers include the epidermis, the dermis and the hypodermis. The epidermis is a stratifying layer of epithelial cells that overlies the dermis, which consists of connective tissue. Both the epidermis and the dermis are further supported by the hypodermis, an internal layer of adipose tissue.
[0003] The epidermis, the topmost layer of skin, is only 0.1 to 1.5 millimeters thick (Inlander, Skin, New York, N.Y.: People's Medical Society, 1-7 (1998)). It consists of keratinocytes and is divided into several layers based on their state of differentiation. The epidermis can be further classified into the stratum corneum and the viable epidermis, which consists of the granular melphigian and basal cells. The stratum corneum is hygroscopic and requires at least 10% moisture by weight to maintain its flexibility and softness. The hygroscopicity is attributable in part to the water-holding capacity of keratin. When the horny layer loses its softness and flexibility it becomes rough and brittle, resulting in dry skin.
[0004] The dermis, which lies just beneath the epidermis, is 1.5 to 4 millimeters thick. It is the thickest of the three layers of the skin. In addition, the dermis is also home to most of the skin's structures, including sweat and oil glands (which secrete substances through openings in the skin called pores, or comedos), hair follicles, nerve endings, and blood and lymph vessels (Inlander, Skin, New York, N.Y.: People's Medical Society, 1-7 (1998)). However, the main components of the dermis are collagen and elastin.
[0005] The hypodermis is the deepest layer of the skin. It acts both as an insulator for body heat conservation and as a shock absorber for organ protection (Inlander, Skin, New York, N.Y.: People's Medical Society, 1-7 (1998)). In addition, the hypodermis also stores fat for energy reserves. The pH of skin is normally between 5 and 6. This acidity is due to the presence of amphoteric amino acids, lactic acid, and fatty acids from the secretions of the sebaceous glands. The term “acid mantle” refers to the presence of the water-soluble substances on most regions of the skin. The buffering capacity of the skin is due in part to these secretions stored in the skin's horny layer.
[0006] Wrinkles, one of the telltale signs of aging, can be caused by biochemical, histological, and physiologic changes that accumulate from environmental damage to the skin. (Benedetto, International Journal of Dermatology, 38:641-655 (1999)). In addition, there are other secondary factors that can cause characteristic folds, furrows, and creases of facial wrinkles (Stegman et al., The Skin of the Aging Face Cosmetic Dermatological Surgery, 2 nd ed., St. Louis, Mo.: Mosby Year Book: 5-15 (1990)). These secondary factors include the constant pull of gravity, frequent and constant positional pressure on the skin (e.g., during sleep), and repeated facial movements caused by the contraction of facial muscles (Stegman et al., The Skin of the Aging Face Cosmetic Dermatological Surgery, 2 nd ed., St. Louis, Mo.: Mosby Year Book: 5-15 (1990)).
[0007] Different techniques have been utilized in order to potentially mollify some of the signs of aging. These techniques range from facial moisturizers containing alpha hydroxy acids and retinol to surgical procedures and injections of neurotoxins. For example, in 1986, Jean and Alastair Carruthers, a husband and wife team consisting of an ocuplastic surgeon and a dermatologist, developed a method of using the type A form of botulinum toxin for treatment of movement-associated wrinkles in the glabella area (Schantz and Scott, In Lewis GE (Ed) Biomedical Aspects of Botulinum, New York: Academic Press, 143-150 (1981)). The Carruthers' use of the type A form of botulinum toxin for the treatment of wrinkles led to the seminal publication of this approach in 1992 (Schantz and Scott, In Lewis GE (Ed) Biomedical Aspects of Botulinum, New York: Academic Press, 143-150 (1981)). By 1994, the same team reported experiences with other movement-associated wrinkles on the face (Scott, Ophthalmol, 87:1044-1049 (1980)). This in turn led to the birth of the era of cosmetic treatment using the type A form of botulinum toxin.
[0008] Interestingly, the type A form of botulinum toxin is said to be the most lethal natural biological agent known to man. Spores of C. botulinum are found in soil and can grow in improperly sterilized and sealed food containers. Ingestion of the bacteria can cause botulism, which can be fatal. Botulinum toxin acts to produce paralysis of muscles by preventing synaptic transmission or release of acetylcholine across the neuromuscular junction, and is thought to act in other ways as well. Its action essentially blocks signals that normally would cause muscle spasms or contractions, resulting in paralysis. However, the muscle-paralyzing effects of botulinum toxin have been used for therapeutic effects. Controlled administration of botulinum toxin has been used to provide muscle paralysis to treat conditions, for example, neuromuscular disorders characterized by hyperactive skeletal muscles. Conditions that have been treated with botulinum toxin include hemifacial spasm, adult onset spasmodic torticollis, anal fissure, blepharospasm, cerebral palsy, cervical dystonia, migraine headaches, strabismus, temporomandibular joint disorder, and various types of muscle cramping and spasms. More recently the muscle-paralyzing effects of botulinum toxin have been taken advantage of in therapeutic and cosmetic facial applications such as treatment of wrinkles, frown lines, and other results of spasms or contractions of facial muscles.
[0009] In addition to the type A form of botulinum toxin, there are seven other serologically distinct forms of botulinum toxin that are also produced by the gram-positive bacteria Clostridium botulinum. Of these eight serologically distinct types of botulinum toxin, the seven that can cause paralysis have been designated botulinum toxin serotypes A, B, C (also known as C, D, E, F and G. Each of these is distinguished by neutralization with type-specific antibodies. The molecular weight of the botulinum toxin protein molecule, for all seven of these active botulinum toxin serotypes, is about 150 kD. The different serotypes of botulinum toxin vary in the animal species that they affect and in the severity and duration of the paralysis they evoke. For example, it has been determined that botulinum toxin type A is 500 times more potent than botulinum toxin type B, as measured by the rate of paralysis produced in rats. Additionally, botulinum toxin type B has been determined to be non-toxic in primates at a dose of 480 U/kg, about 12 times the primate LD50 for type A. Due to the molecule size and molecular structure of botulinum toxin, it cannot cross stratum corneum and the multiple layers of the underlying skin architecture.
[0010] As released by Clostridium botulinum bacteria, botulinum toxin is a component of a toxin complex containing the approximately 150 kD botulinum toxin protein molecule along with associated non-toxin proteins. These endogenous non-toxin proteins are believed to include a family of hemagglutinin proteins, as well as non-hemagglutinin protein. The non-toxin proteins are believed to stabilize the botulinum toxin molecule in the toxin complex and protect it against denaturation, for example, by digestive acids when toxin complex is ingested. Thus, the non-toxin proteins of the toxin complex protect the activity of the botulinum toxin and enhance systemic penetration, particularly when the toxin complex is administered via the gastrointestinal tract. More specifically, it is believed that some of the non-toxin proteins specifically enhance penetration across the gastrointestinal epithelium while other non-toxin proteins stabilize the botulinum toxin molecule in blood. Additionally, the presence of non-toxin proteins in the toxin complexes typically causes the toxin complexes to have molecular weights that are greater than that of the bare botulinum toxin molecule, which is about 150 kD, as previously noted. For example, Clostridium botulinum bacteria can produce botulinum type A toxin complexes that have molecular weights of about 900 kD, 500 kD or 300 kD. Interestingly, botulinum toxin types B and C are apparently produced as only a 700 kD or a 500 kD complex. Botulinum toxin type D is produced as both 300 kD and 500 kD complexes. Botulinum toxin types E and F are produced as only approximately 300 kD complexes.
[0011] To provide additional stability to botulinum toxin, the toxin complexes are often stabilized by combining them with exogenous stabilizers, (e.g., gelatin, polysaccharides, or most commonly additional albumin) during manufacturing. The stabilizers serve to bind and to stabilize toxin complexes in disparate environments, including those associated with manufacturing, transportation, storage, and administration.
[0012] Typically, the botulinum toxin is administered to patients by carefully controlled injections of compositions containing the botulinum toxin complex and albumin, but there are several problems associated with this approach. Not only are the injections painful, but they often must deliver enough toxin to create large subdermal wells of toxin locally around the injection sites, in order to achieve the desired therapeutic or cosmetic effect. Even worse, many injections may be required when the area to be treated is large. Moreover, because the injected toxin complexes contain non-toxin proteins and albumin that stabilize the botulinum toxin and increase the molecular weight of the toxin complex, the toxin complexes have a long half-life in the body, are slow to diffuse through tissue, and may cause an undesirable antigenic response in the patient. Also, since the non-toxin proteins and albumin stabilize the botulinum toxin in blood, the injections must be carefully placed so that they do not release a large amount of toxin into the bloodstream of the patient, which could lead to fatal systemic poisoning. Thus, injections typically must be performed precisely by highly trained medical professionals with a deep understanding of human anatomy.
[0013] In view of all of the problems discussed in the foregoing, it would be highly desirable to have a method of administering botulinum toxin that would be painless and require less toxin than conventional injection-based methods. Additionally, it would be highly desirable if such a method were to reduce the antigenicity and blood stability of the botulinum toxin, while increasing the diffusion rate of botulinum toxin complexes within the body, thereby making it safer to use botulinum toxin for various therapeutic, aesthetic and/or cosmetic purposes. It also would be desirable to have a method of administration that does not critically depend on precise injection of the botulinum toxin by a medical professional in order to achieve safe administration of the toxin.
SUMMARY OF THE INVENTION
[0014] This invention provides a solution to the aforementioned problems by providing a therapeutic botulinum toxin composition that can be topically applied to the skin epithelium painlessly and easily. The botulinum toxin complexes in the topical compositions of this invention have reduced antigenicity, lower blood stability, a better safety profile, and higher diffusion rates through the skin epithelium compared to conventional commercial botulinum toxin complexes that are bound to exogenous albumin (e.g., BOTOX® or MYOBLOC®). Additionally, by using the compositions and associated methods of this invention, less botulinum toxin is required to achieve the same clinical result compared to conventional injection-based methods of administration.
[0015] One aspect of this invention is the recognition that the endogenous non-toxin proteins in a botulinum toxin complex obtained from Clostridium botulinum bacteria (viz., the non-toxic hemagglutinin and non-hemagglutinin proteins) undesirably increase the stability and toxicity of the toxin complex, while undesirably decreasing the ability of the toxin to diffuse through the skin epithelium. This invention further recognizes that these effects are exacerbated when an exogenous stabilizer, such as albumin, binds to botulinum toxin during conventional manufacturing processes. Thus, one aspect of this invention is to provide botulinum toxin complexes wherein the amounts of hemagglutinin, non-toxin non-hemagglutinin and/or exogenous albumin are selectively and independently reduced compared to conventional commercially available botulinum toxin (e.g., BOTOX® or MYOBLOC®).
[0016] Another aspect of this invention is the recognition that certain non-native molecules (i.e., molecules not found in botulinum toxin complexes obtained from Clostridium botulinum bacteria) can be added to botulinum toxin complexes, and in particular reduced botulinum toxin complexes, to improve the ability of the botulinum toxin complex to diffuse through the skin epithelium. In a particularly preferred embodiment, the non-native molecules bind non-covalently to the botulinum toxin complexes and act as skin-tropic “adhesion molecules” that improve the ability of the toxin complexes to adhere to and to penetrate the skin epithelium, and furthermore reduces the stability of the botulinum complex in blood. By way of example, the adhesion molecules may be certain proteins, such as sialoproteins.
[0017] Accordingly, one object of this invention is to provide a composition comprising a botulinum toxin complex (or a reduced botulinum toxin complex) and skin-targeting non-native adhesion molecules that enhance transdermal penetration of the composition for cosmeceutical or therapeutic treatments. The composition optionally may contain added exogenous stabilizers, such as albumin.
[0018] The invention further relates to a method for producing a biologic effect by topically applying an effective amount of the compositions within this invention, preferably to the skin, of a subject or patient in need of such treatment. The biologic effect may include, for example, muscle paralysis, reduction of hypersecretion or sweating, treatment of neurologic pain or migraine headache, reduction of muscle spasms, prevention or reduction of acne, reduction or enhancement of an immune response, reduction of wrinkles, or prevention or treatment of various other disorders.
[0019] This invention also provides kits for preparing formulations containing a botulinum toxin complex (or a reduced botulinum toxin complex) and adhesion molecules, or a premix that may in turn be used to produce such a formulation. Also provided are kits that contain means for sequentially administering a botulinum toxin complex (or a reduced botulinum toxin complex) and adhesion molecules to a subject.
DETAILED DESCRIPTION OF THE INVENTION
[0020] This invention relates to novel compositions comprising a botulinum toxin, more specifically to such compositions that enable the transport or delivery of a botulinum toxin through the skin epithelium (also referred to as “transdermal delivery”) with improved skin adherence and penetration, reduced antigenicity and blood stability. The compositions of the invention may be used as topical applications for providing a botulinum toxin to a subject, for various therapeutic, aesthetic and/or cosmetic purposes, as described herein. The compositions of the invention also have an improved safety profile over other compositions and methods of delivery of botulinum toxin. In addition, these compositions can afford beneficial reductions in immune responses to the botulinum toxin.
[0021] The term “ botulinum toxin” as used herein refers to any of the known types of botulinum toxin (i.e., the approximately 150 kD botulinum toxin protein molecule), whether produced by the bacterium or by recombinant techniques, as well as any such types that may be subsequently discovered including newly discovered serotypes, and engineered variants or fusion proteins. As mentioned above, currently seven immunologically distinct botulinum neurotoxins have been characterized, namely botulinum neurotoxin serotypes A, B, C, D, E, F and G, each of which is distinguished by neutralization with type-specific antibodies. The botulinum toxin serotypes are commercially available, for example, from Sigma-Aldrich (St. Louis, Mo.) and from Metabiologics, Inc. (Madison, Wis.), as well as from other sources. The different serotypes of botulinum toxin vary in the animal species that they affect and in the severity and duration of the paralysis they evoke. At least two types of botulinum toxin, types A and B, are available commercially in formulations for treatment of certain conditions. Type A, for example, is contained in preparations of Allergan having the trademark BOTOX® and of Ipsen having the trademark DYSPORT®, and type B is contained in preparations of Elan having the trademark MYOBLOC®.
[0022] The term “ botulinum toxin” used in the compositions of this invention can alternatively refer to a botulinum toxin derivative, that is, a compound that has botulinum toxin activity but contains one or more chemical or functional alterations on any part or on any chain relative to naturally occurring or recombinant native botulinum toxins. For instance, the botulinum toxin may be a modified neurotoxin that is a neurotoxin which has at least one of its amino acids deleted, modified or replaced, as compared to a native, or the modified neurotoxin can be a recombinantly produced neurotoxin or a derivative or fragment thereof. For instance, the botulinum toxin may be one that has been modified in a way that, for instance, enhances its properties or decreases undesirable side effects, but that still retains the desired botulinum toxin activity. The botulinum toxin may be any of the botulinum toxin complexes produced by the bacterium, as described above. Alternatively the botulinum toxin used in this invention may be a toxin prepared using recombinant or synthetic chemical techniques, e.g. a recombinant peptide, a fusion protein, or a hybrid neurotoxin, for example prepared from subunits or domains of different botulinum toxin serotypes (see U.S. Pat. No. 6,444,209, for instance). The botulinum toxin may also be a portion of the overall molecule that has been shown to possess the necessary botulinum toxin activity, and in such case may be used per se or as part of a combination or conjugate molecule, for instance a fusion protein. Alternatively, the botulinum toxin may be in the form of a botulinum toxin precursor, which may itself be non-toxic, for instance a non-toxic zinc protease that becomes toxic on proteolytic cleavage.
[0023] The term “ botulinum toxin complex” or “toxin complex” as used herein refers to the approximately 150 kD botulinum toxin protein molecule (belonging to any one of botulinum toxin serotypes A-G), along with associated endogenous non-toxin proteins (i.e., hemagglutinin protein and non-toxin non-hemagglutinin protein produced by Clostridium botulinum bacteria). Note, however, that the botulinum toxin complex need not be derived from Clostridium botulinum bacteria as one unitary toxin complex. For example, botulinum toxin or modified botulinum toxin may be recombinantly prepared first and then subsequently combined with the non-toxin proteins. Recombinant botulinum toxin can also be purchased (e.g., from List Biological Laboratories, Campbell, Calif.) and then combined with non-toxin proteins.
[0024] This invention also contemplates “reduced botulinum toxin complexes”, in which the botulinum toxin complexes have reduced amounts of non-toxin protein compared to the amounts naturally found in botulinum toxin complexes produced by Clostridium botulinum bacteria. In one embodiment, reduced botulinum toxin complexes are prepared using any conventional protein separation method to extract a fraction of the hemagglutinin protein or non-toxin non-hemagglutinin protein from botulinum toxin complexes derived from Clostridium botulinum bacteria. For example, reduced botulinum toxin complexes may be produced by dissociating botulinum toxin complexes through exposure to red blood cells at a pH of 7.3 (e.g., see EP 1514556 A1, hereby incorporated by reference). HPLC, dialysis, columns, centrifugation, and other methods for extracting proteins from proteins can be used. Alternatively, when the reduced botulinum toxin complexes are to be produced by combining synthetically produced botulinum toxin with non-toxin proteins, one may simply add less hemagglutinin or non-toxin non-hemagglutinin protein to the mixture than what would be present for naturally occurring botulinum toxin complexes. Any of the non-toxin proteins (e.g., hemagglutinin protein or non-toxin non-hemagglutinin protein or both) in the reduced botulinum toxin complexes according to the invention may be reduced independently by any amount. In certain exemplary embodiments, one or more non-toxin proteins are reduced by at least about 0.5%, 1%, 3%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% compared to the amounts normally found in botulinum toxin complexes. Clostridium botulinum bacteria produce seven different serotypes of toxin and commercial preparations are manufactured with different relative amounts of non-toxin proteins (i.e. different amount of toxin complexes). For example, Myobloc has 5000 U of Botulinum toxin type B per ml with 0.05% human serum albumin, 0.01 M sodium succinate, and 0.1 M sodium chloride. Dysport has 500 U of botulinum toxin type A-haemaglutinin complex with 125 mcg albumin and 2.4 mg lactose. In one particularly interesting embodiment, substantially all of the non-toxin protein (e.g., >95% of the hemagglutinin protein and non-toxin non-hemagglutinin protein) that would normally be found in botulinum toxin complexes derived from Clostridium botulinum bacteria is removed from the botulinum toxin complex. Furthermore, although the amount endogenous non-toxin proteins may be reduced by the same amount in some cases, this invention also contemplates reducing each of the endogenous non-toxin proteins by different amounts, as well as reducing at least one of the endogenous non-toxin proteins, but not the others.
[0025] In addition to (or instead of) reducing the amount of endogenous non-toxin protein to destabilize the botulinum toxin complex, this invention also contemplates the reducing the amount of exogenous stabilizers that are normally added during manufacturing. An example of such an exogenous stabilizer is albumin, which is normally added during manufacturing to botulinum toxin complexes in amount equal to 1000 times the amount of albumin found in the endogenous non-toxin, non-hemagglutinin component of a naturally occurring botulinum toxin complex. According to this invention, the amount of added exogenous albumin can be any amount less than the conventional thousand-fold excess of exogenous albumin. In certain exemplary embodiments of the invention, only about 500×, 400×, 300×, 200×, 100×, 50×, 10×, 5×, 1×, 0.5×, 0.1×, or 0.01× the amount of the albumin in naturally occurring botulinum toxin complexes is added. In one embodiment, no exogenous albumin is added as a stabilizer to the compositions of the invention. In other embodiments, exogenous stabilizers in addition to (or instead of) albumin are added to the therapeutic topical compositions of the invention. For example, other stabilizers contemplated by the invention include lactose, gelatin and polysaccharides.
[0026] An “adhesion molecule” according to this invention may be a protein or other molecule that possesses at least the following properties: (1) it is not found in naturally occurring botulinum toxin complexes (i.e., “non-native”); (2) it serves to stabilize botulinum toxin complexes or reduced botulinum toxin complexes, especially those that have been combined with little or no excess exogenous albumin or other stabilizer; and (3) when mixed with botulinum toxin complexes or reduced botulinum toxin complexes, it promotes transdermal penetration of the botulinum toxin, enabling the toxin to be administered to muscles and/or other skin-associated structures in amounts that are sufficient to produce a desired therapeutic or cosmetic effect. Generally speaking, it is preferable if the transport may occur without covalent modification of the botulinum toxin. In certain preferred embodiments, the adhesion molecules are capable of binding to specific components of skin, non-limiting examples of which include keratinocytes, epidermal cells, and hair follicles. By way of example, the adhesion molecules according to the invention may be proteins capable of binding to keratinocyte growth factor, keratinocyte binding proteins, epidermal growth factor (EGF), EGF-like proteins, and neurotrophins such as nerve growth factor, brain-derived neurotrophic factor, neurotrophin-3, and neurotrophin-4/5. In some embodiments of the invention, the therapeutic topical composition includes more than one different type of non-native adhesion molecule.
[0027] In one particularly interesting embodiment, the non-native adhesion molecules are sialoproteins. Without wishing to be bound by any particular scientific theory, it is believed that sialoproteins promote skin adherence and transdermal penetration of the botulinum toxin, while enhancing stabilization of the botulinum toxin in skin and in vitro, and reducing blood and systemic activity for an improved safety profile. Non-limiting examples of sialoproteins contemplated by this invention include bone sialoprotein I (also known as BSPI, bone sialoprotein, osteopontin, OPN, secreted phosphoprotein 1, Spp 1, early T lymphocyte activation protein-1, ETA-1, urinary stone protein, nephropontin) and bone sialoprotein II (also known as BSPII, integrin-binding sialoprotein, cell binding sialoprotein, BNSP). Sialoproteins are commercially available, for example, from Chemicon International. Other adhesion molecules that bind and internalize in the epithelial cells especially skin and bladder epithelial cells can be used. Family of adhesion molecules such as cadherins, integrins, immunoglobulin superfamily, selectins and other transmembrane sialoprotein such as podocalyxin may be added.
[0028] Generally speaking, the concentration of adhesion molecules in the compositions according to the invention should be sufficient to allow the botulinum toxin to be delivered transdermally. Furthermore, without wishing to be bound by theory, it is believed that the transdermal transport rate follows receptor-mediated kinetics, such that transdermal transport increases with increasing amounts of adhesion molecules up to a saturation point, upon which the transport rate becomes constant. Thus, in a preferred embodiment, the amount of added adhesion molecules is equal to the amount that maximizes transdermal penetration rate right before saturation. A useful concentration range for the adhesion molecules in the topical compositions of this invention is about 0.1 ng to about 1.0 mg per unit of the botulinum toxin composition as described herein. More preferably, the adhesion molecules in the topical compositions of the invention are in the range of about 0.1 mg to 0.5 mg per unit of botulinum toxin. For example, in the case of bone sialoprotein I, which is an example of a sialoprotein contemplated by the invention, a useful range is between about 0.1 ng and about 1.0 mg, more preferably between about 0.1 mg and about 0.5 mg.
[0029] Compositions of this invention are preferably in the form of products to be applied to the skin or epithelium of subjects or patients, i.e. humans or other mammals in need of the particular treatment. The term “in need” is meant to include both pharmaceutical or health-related needs, for example, treating conditions involving undesirable facial muscle spasms, as well as cosmetic and subjective needs, for example, altering or improving the appearance of facial tissue. In general the compositions are prepared by mixing the botulinum toxin (either containing the associated non-toxin proteins or reduced associated non-toxin proteins) with the non-native adhesion molecules, and usually with one or more additional pharmaceutically acceptable carriers or excipients. In their simplest form they may contain a simple aqueous pharmaceutically acceptable carrier or diluent, such as buffered saline. However, the compositions may contain other ingredients typical in topical pharmaceutical or cosmeceutical compositions, that is, a dermatologically or pharmaceutically acceptable carrier, vehicle or medium, i.e. a carrier, vehicle or medium that is compatible with the tissues to which they will be applied. The term “dermatologically or pharmaceutically acceptable,” as used herein, means that the compositions or components thereof so described are suitable for use in contact with these tissues or for use in patients in general without undue toxicity, incompatibility, instability, allergic response, and the like. As appropriate, compositions of the invention may comprise any ingredient conventionally used in the fields under consideration, and particularly in cosmetics and dermatology.
[0030] In terms of their form, compositions of this invention may include solutions, emulsions (including microemulsions), suspensions, creams, lotions, gels, powders, or other typical solid or liquid compositions used for application to skin and other tissues where the compositions may be used. Such compositions may contain, in addition to the botulinum toxin and non-native adhesion molecules, other ingredients typically used in such products, such as antimicrobials, moisturizers and hydration agents, penetration agents, preservatives, emulsifiers, natural or synthetic oils, solvents, surfactants, detergents, gelling agents, emollients, antioxidants, fragrances, fillers, thickeners, waxes, odor absorbers, dyestuffs, coloring agents, powders, viscosity-controlling agents and water, and optionally including anesthetics, anti-itch actives, botanical extracts, conditioning agents, darkening or lightening agents, glitter, humectants, mica, minerals, polyphenols, silicones or derivatives thereof, sunblocks, vitamins, and phytomedicinals.
[0031] Compositions according to this invention may be in the form of controlled-release or sustained-release compositions, wherein the botulinum toxin and the non-native adhesion molecules are encapsulated or otherwise contained within a material such that they are released onto the skin in a controlled manner over time. The composition comprising the botulinum toxin and non-native adhesion molecules may be contained within matrixes, liposomes, vesicles, microcapsules, microspheres and the like, or within a solid particulate material, all of which is selected and/or constructed to provide release of the botulinum toxin over time. The botulinum toxin and the non-native adhesion molecules may be encapsulated together (e.g., in the same capsule) or separately (in separate capsules).
[0032] Botulinum toxin can be delivered to muscles underlying the skin, or to glandular structures within the skin, in an effective amount to produce paralysis, produce relaxation, alleviate contractions, prevent or alleviate spasms, reduce glandular output, or other desired effects. Local delivery of the botulinum toxin in this manner could afford dosage reductions, reduce toxicity and allow more precise dosage optimization for desired effects relative to injectable or implantable materials.
[0033] The compositions of the invention are applied so as to administer an effective amount of the botulinum toxin. The term “effective amount” as used herein means an amount of a botulinum toxin as defined above that is sufficient to produce the desired muscular paralysis or other biological or aesthetic effect, but that implicitly is a safe amount, i.e. one that is low enough to avoid serious side effects. Desired effects include the relaxation of certain muscles with the aim of, for instance, decreasing the appearance of fine lines and/or wrinkles, especially in the face, or adjusting facial appearance in other ways such as widening the eyes, lifting the corners of the mouth, or smoothing lines that fan out from the upper lip, or the general relief of muscular tension. The last-mentioned effect, general relief of muscular tension, can be effected in the face or elsewhere. The compositions of the invention may contain an appropriate effective amount of the botulinum toxin for application as a single-dose treatment, or may be more concentrated, either for dilution at the place of administration or for use in multiple applications. Through the use of the skin-targeting non-native adhesion molecules of this invention, a botulinum toxin can be administered transdermally to a subject for treating conditions such as undesirable facial muscle or other muscular spasms, hyperhidrosis, acne, or conditions elsewhere in the body in which relief of muscular ache or spasms is desired. The botulinum toxin is administered topically for transdermal delivery to muscles or to other skin-associated structures. The administration may be made, for example, to the legs, shoulders, back (including lower back), axilla, palms, feet, neck, groin, dorsa of the hands or feet, elbows, upper arms, knees, upper legs, buttocks, torso, pelvis, or any other parts of the body where administration of the botulinum toxin is desired.
[0034] Administration of botulinum toxin may also be carried out to treat other conditions, including but not limited to treating neurologic pain, prevention or reduction of migraine headache or other headache pain, prevention or reduction of acne, prevention or reduction of dystonia or dystonic contractions (whether subjective or clinical), prevention or reduction of symptoms associated with subjective or clinical hyperhidrosis, reducing hypersecretion or sweating, reducing or enhancing immune response, or treatment of other conditions for which administration of botulinum toxin by injection has been suggested or performed.
[0035] Most preferably, the compositions are administered by or under the direction of a physician or other health care professional. They may be administered in a single treatment or in a series of periodic treatments over time. For transdermal delivery of botulinum toxin for the purposes mentioned above, a composition as described above is applied topically to the skin at a location or locations where the effect is desired. Because of its nature, most preferably the amount of botulinum toxin applied should be applied with care, at an application rate and frequency of application that will produce the desired result without producing any adverse or undesired results. Accordingly, for instance, topical compositions of the invention should be applied at a rate of from about 1 U to about 20,000 U, preferably from about 1 U to about 10,000 U botulinum toxin per cm 2 of skin surface. Higher dosages within these ranges could preferably be employed in conjunction with controlled release materials, for instance, or allowed a shorter dwell time on the skin prior to removal.
[0036] This invention also includes transdermal delivery devices for transmitting botulinum toxin-containing compositions described herein across skin. Such devices may be as simple in construction as a skin patch, or may be a more complicated device that includes means for dispensing and monitoring the dispensing of the composition, and optionally means for monitoring the condition of the subject in one or more aspects, including monitoring the reaction of the subject to the substances being dispensed.
[0037] The compositions, both in general, and in such devices, can be pre-formulated or pre-installed in the device as such, or can be prepared later, for example using a kit that contains the two ingredients ( botulinum toxin and non-native adhesion molecules) for combining at or prior to the time of application. The amount of non-native adhesion molecule or the ratio of it to the botulinum toxin will depend on which carrier is chosen for use in the composition in question. The appropriate amount or ratio of carrier molecule in a given case can readily be determined, for example, by conducting one or more experiments such as those described below.
[0038] In general, the invention also contemplates a method for administering botulinum toxin (preferably as reduced botulinum toxin complexes) to a subject or patient in need thereof, in which an effective amount of botulinum toxin is topically administered in conjunction with adhesion molecules, as described herein. By “in conjunction with” it is meant that the two components ( botulinum toxin and adhesion molecules) are administered in a combination procedure, which may involve either combining them prior to topical administration to a subject, or separately administering them, but in a manner such that they act together to provide the requisite delivery of an effective amount of the therapeutic protein. For example, a composition containing the adhesion molecules may first be applied to the skin of the subject, followed by applying a skin patch or other device containing the botulinum toxin The botulinum toxin may be incorporated in dry form in a skin patch or other dispensing device and the adhesion molecules may be applied to the skin surface before application of the patch so that the two act together, resulting in the desired transdermal delivery. In that sense, thus, the two substances (adhesion molecule and botulinum toxin) act in combination or perhaps interact to form a composition or combination in situ. Accordingly, the invention also includes a kit with a device for dispensing botulinum toxin via the skin and a liquid, gel, cream or the like that contains the adhesion molecules, and that is suitable for applying to the skin or epithelium of a subject. Kits for administering the compositions of the inventions, either under direction of a health care professional or by the patient or subject, may also include a custom applicator suitable for that purpose.
[0039] The compositions of this invention are suitable for use in physiologic environments with pH ranging from about 4.5 to about 6.3, and may thus have such a pH. The compositions according to this invention may be stored either at room temperature or under refrigerated conditions.
[0040] It is understood that the following examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.
EXAMPLE 1
Transport of a Botulinum Toxin in vivo Using Sialoproteins
[0041] This experiment demonstrates the use of sialoproteins to transport a large complex containing an intact labeled protein botulinum toxin across intact skin after a single time administration.
[0042] Botox® brand of botulinum toxin type A (Allergan, Irvine, Calif.) is selected for this experiment. The botulinum toxin is reconstituted according to the manufacturer's instructions. An aliquot of the protein is biotinylated with a calculated 12-fold molar excess of sulfo-NHS-LC biotin (Pierce Chemical, Rockford, Ill.). 2.0 units of botulinum toxin per aliquot (i.e., 20 U total) and sialoprotein at a calculated MW ratio of 4:1 are mixed to homogeneity and diluted to 200 microliters with phosphate buffered saline. The resulting composition is mixed to homogeneity with 1.8 ml of Cetaphil® lotion and aliquoted in 200 microliter portions.
[0000] Animal Experiment to Determine Transdermal Delivery Efficiencies After Single Time Treatment with Botulinum Toxin Composition Containing Sialoproteins:
[0043] Animals are anesthetized via inhalation of isoflurane during application of treatments. After being anesthetized, C57BLK/6 mice (n=10) undergo topical application of metered 200 microliter dose of the appropriate treatment applied to the cranial portion of dorsal back skin (selected because the mouse cannot reach this region with mouth or limbs). Animals do not undergo depilation. At 30 minutes after the initial treatment, mice are euthanized via inhalation of CO 2 , and treated skin segments are harvested at full thickness by blinded observers. Treated segments are divided into three equal portions; the cranial portion was fixed in 10% neutral buffered formalin for 12-16 hours then stored in 70% ethanol until paraffin embedding. The central portion is snap-frozen and employed directly for biotin visualization by blinded observers as summarized below. The treated caudal segment is snap-frozen for solubilization studies.
[0044] Biotin visualization is conducted as follows. Briefly, each section is immersed for 1 hour in NeutrAvidin® (Pierce Biotechnology, Rockford, Ill.) buffer solution at room temperature. To visualize alkaline phosphatase activity, cross sections are washed in saline four times then immersed in NBT BCIP (Pierce Biotechnology) for approximately 1 hour. Sections are then rinsed in saline and photographed in entirety on a Nikon E600 microscope with plan-apochromat lenses. Total positive staining is determined by blinded observer via batch image analysis using Image Pro Plus software (Media Cybernetics, Silver Spring, Md.) and is normalized to total cross-sectional area to determine percent positive staining for each. Mean and standard error are subsequently determined for each group with analysis of significance at 95% confidence in one way ANOVA repeated measures using Statview software (Abacus, Berkeley, Calif.). The results demonstrate that sialoproteins allow efficient transfer of botulinum toxin after topical administration in a murine model of intact skin.
EXAMPLE 2
Botulinum Toxin Administered Transdermally to Treat Facial Wrinkles
[0045] A female wishes to reduce the fine lines that fan out from the left side of her upper lip. A transdermal patch containing a composition containing 1 Unit botulinum toxin type A, 0.01 mg sialoprotein, and is essentially free of non-toxin proteins and albumin is applied to the area on her face containing the fine lines. The patch is applied only at night when the subject is asleep. Within 1-7 days the appearance of the fine lines is greatly reduced. This beneficial effect persists with continued application of the patch. The reduced antigenicity as a result of the lack of animal-derived albumin or gelatin allows for repeated use of the botulinum toxin composition. | This invention relates to novel compositions of botulinum toxin that can be applied topically for various therapeutic, aesthetic and/or cosmetic purposes. The compositions may include botulinum toxin complexes, wherein the amounts of hemagglutinin, non-toxin non-hemagglutinin and/or exogenous albumin are selectively and independently reduced compared to conventional commercially available botulinum toxin. The compositions may further contain molecules that are not native to botulinum toxin and that bind non-covalently to the botulinum toxin complexes, thereby acting as skin-tropic “adhesion molecules” to improve the ability of the toxin complexes to adhere to and to penetrate the skin epithelium. The compositions have an improved safety profile compared to existing botulinum -containing compositions that are injected subcutaneously. Methods for the use of such compositions are also contemplated by this invention. | 0 |
SUMMARY OF THE INVENTION
This invention relates to an apparatus for breaking a fluorescent lamp tube or other elongated frangible article into small fragments which are caught in a disposable container, such as a bag.
Many large buildings, such as office buildings, factories and schools, have such a large number of fluorescent lamp tubes that in any given week several such tubes will be replaced. If the burned-out tubes are stored for trash pickup there is a likelihood that some may be broken accidentally, sometimes with the possibility of injuring a person and always with the certainty that someone will have to sweep up the broken fragments.
The present invention is directed to a simple and safe apparatus for breaking burned-out fluorescent tubes into small fragments and storing the fragments in a disposable bag which is suitable for trash pickup.
A principal object of this invention is to provide a novel apparatus for breaking an elongated article, such as a fluorescent lamp tube, into small particles which are caught in a disposable container, such as a bag.
Another object of this invention is to provide such an apparatus which substantially prevents the escape of any broken fragments while the article is being broken up.
Another object of this invention is to provide such an apparatus which can be operated entirely by hand.
Further objects and advantages of this invention will be apparent from the following description of a presently-preferred embodiment which is illustrated schematically in the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation of the present apparatus;
FIG. 2 is a top plan view;
FIG. 3 is an end elevation taken from the right end of FIGS. 1 and 2;
FIG. 4 is a vertical cross-section taken along the line 4--4 in FIG. 1;
FIG. 5 is a vertical longitudinal section taken along the line 5--5 in FIG. 2;
FIG. 6 is a horizontal longitudinal section taken along the line 6--6 in FIG. 1; and
FIG. 7 is a view similar to FIG. 5 showing the frangible article being crushed.
Before explaining the disclosed embodiment of the present invention in detail, it is to be understood that the invention is not limited in its application to the details of the particular arrangement shown since the invention is capable of other embodiments. Also, the terminology used herein is for the purpose of description and not of limitation.
DETAILED DESCRIPTION
As shown in the drawings, the present apparatus has a support stand having four upwardly and inwardly inclined legs 11, 12, 13 and 14 (FIG. 2) which extend up from the ground or other horizontal support surface. The upper ends of these legs are connected through rigid sockets 15, 16, 17 and 18 (FIGS. 1 and 6) to the four sides of a rectangular generally horizontal frame in the stand. The side of this frame which extends between sockets 15 and 16 has two rigid tubes 19 and 20 connected end-to-end by a T-socket 21. The side which extends between sockets 16 and 17 consists of a single rigid tube 22 of shallow V shape from end to end. The side which extends between sockets 17 and 18 has two rigid tubes 23 and 24 connected end-to-end by a T-socket 25. The fourth side, which extends between sockets 15 and 18, consists of a single rigid tube 26.
The stand also has four rigid vertical tubes 27, 28, 29 and 30 (FIGS. 1, 4 and 5) which extend up from sockets 15, 16, 17 and 18, respectively. Sockets 31, 32, 33 and 34 on the upper ends of these vertical tubes connect them to two opposite horizontal sides of the top of the stand. One of these sides (FIGS. 1 and 2) consists of rigid tubes 35 and 36 connected end to end by a socket 37 and located vertically above the side 19, 20, 21 in the rectangular frame below. The opposite side at the top (FIGS. 2 and 5) consists of rigid tubes 38 and 39 connected end to end by a socket 40 and located vertically above the side 23, 24, 25 in the rectangular frame below.
As shown in FIG. 4, sockets 37 and 40 rotatably receive the opposite end segments 41a and 41b of a crankshaft which has an offset middle segment 42 rigidly connected to the end segments 41a and 41b by elbows and tubes 43, 44, 45, 46, 47 and 48. End segment 41a has its outer end connected to a handle 49 which is manually operable to revolve the offset middle segment 42 of the crankshaft about the conjoint axis of its end segments 41a and 41b.
A connecting rod 50 is rotatably mounted at its upper end on the crank arm 42. At its lower end this connecting rod is pivotally coupled at 51 to the upper end of a plunger 52 having a tapered tip 53 at its lower end. Plunger 52 is slidably received in a vertical guide tube 54 fastened to the inner end of rigid horizontal arms 55a and 55b (FIG. 6) whose respective outer ends are attached to sleeves 56a and 56b (FIGS. 1 and 5) which directly 30 overlie sockets 15 and 18 in the stand. The guide tube 54 presents a tapered, elliptical bottom edge 57, as shown in FIGS. 5 and 4, which is inclined downward to the right in FIGS. 1 and 5.
A stop bar 58 extends horizontally between the vertical tubes 28 and 29 on the left side of the frame in FIGS. 1 and 5. This stop bar is attached to sleeves 59 and 60 on its opposite ends (FIG. 4) which are welded to the vertical tubes 28 and 29, respectively. As best seen in FIG. 5, the stop bar 58 is inclined outward and downward, and on its outer face it carries a resilient pad 61 of rubber or rubber-like material.
As best seen in FIGS. 4 and 6, a rigid, horizontal, tubular rod 62 extends inward from the T-socket 21 and a similar rod 63 extends inward from the T-socket 25 in axial alignment with rod 62. Each of these rods is rotatably received in the corresponding socket. The inner ends of rods 62 and 63 are joined to a rigid tubular guide 64, which extends perpendicular to them across the top of the shallow V tube 22 at one side of the frame. The sockets 21, 25 and rods 62, 63 define a horizontal pivot for guide 64, enabling it to be raised from the horizontal position shown in full lines in FIG. 1 to the inclined position shown in phantom. As shown in FIGS. 1 and 2, guide 64 carries a bumper sleeve 65 which engages the bumper pad 61 on the frame to limit the upward movement of guide 64 to an angle of about 45° to the horizontal.
An inverted, funnel-shaped, annular housing 66 hangs down from the pivot rods 62 and 63 below the tubular guide 64. At its upper end, housing 66 presents upstanding ears 67 and 68 (FIG. 4) with circular openings which pass the pivot rods 62 and 63 loosely. These ears are located just outward from annular flanges 62a and 63a on the pivot rods. Immediately below its suspension ears 67 and 68 the housing 66 presents a vertical opening 69 of circular cross-section which leads down into a frusto-conical passageway 70 whose cross-sectional size increases downward. The lower end of the housing 66 presents a generally cylindrical segment 71 with a horizontal, annular outwardly projecting lip 72 at the bottom. A bag 73 of plastic or other suitable flexible material has its mouth releasably camped around the lower end segment 71 of annular housing 66 by an adjustable strap 74 of known design. Bag 73 hangs down inside the frame at the middle, as shown in FIG. 1.
As shown in FIG. 5, the annular housing 66 is cut away at the top inside its suspension ears 67 and 68, presenting an upwardly-facing, elliptical, tapered ears 75 whose upper end is on the left side of the pivot axis of guide 64 in FIG. 5 and whose lower end is on the right side of this axis.
The tubular guide 64 is closed at its right end in FIG. 5, presenting a circular end wall 76 there, and immediately to the left of this end wall it has an elliptical opening 77 in the bottom which registers with the elliptical edge 75 on the top of housing 66 when guide 64 is raised to the inclined position shown in FIG. 7 and in phantom in FIG. 1.
The pivoted tubular guide 64 is formed with an elliptical top opening 74 which registers with the elliptical tapered bottom edge of the plunger guide 54 when guide 64 is raised to the position shown in FIG. 7.
The outer end of guide 64 (the left end in FIG. 1) is externally screw-threaded for the attachment of an internally screw-threaded end cap 79. When this cap is removed and the guide 64 is horizontal, a frangible article, such as a fluorescent lamp 80, may be inserted into the guide 64. This is done when the crank handle 49 is in the position shown in FIG. 4, in which it holds the plunger 52 raised above the lower end of its guide tube 54. Then the guide 64 is tilted up to the phantom-line position in FIG. 1, causing the frangible article to slide down against the inner end wall 76 of guide 64. The handle 49 now is revolved from the position shown in FIG. 4, in which the plunger 52 is raised, to the lowered position shown in FIG. 7. As the handle is revolved, the plunger is forced down through the top opening 78 in guide 64 and smashes the underlying part of the frangible article and then continues down through the bottom opening 77 in guide 64. The particles of glass or other frangible material of article 80 drop down through the annular housing 66 into the bag 73 below.
When the handle 49 is revolved back around to the position shown in FIG. 4, the next section of the frangible article 80 will slide down against the inner end wall 76 of guide 64, so that it is positioned to be broken up in the next downward stroke of plunger 52.
The guide 64 preferably has a length greater than the longest frangible article 80 which it will receive, so that the end cap 79 can be put on guide 64 after the frangible article 80 has been inserted. In one practical embodiment, guide 64 is 8 feet long. However, frangible articles longer than the guide 64 can be accommodated by providing an adapter extension with an end cap.
It will be evident from FIG. 7, that the top opening 78 in guide 64 is sealed around almost its entire periphery by the tapered bottom edge 57 of the plunger guide 54 when guide 64 is raised. Also in this position of guide 64 its bottom opening 77 is sealed around its entire periphery by the tapered top edge 75 of annular housing 66. With this arrangement, the end of the frangible article which is being smashed is virtually totally enclosed and the only place its fragments can go is down into the bag 73.
It will be apparent that the present apparatus provides maximum safety for the person using it, so that he or she is not exposed to flying glass fragments. In addition, the apparatus is completely manually operated, making it inexpensive, simple and safe to use. The top and bottom openings in the guide 64 near its inner end are so located that the plunger 52 cannot be operated to break a frangible article in the guide unless the guide is raised to the position shown in FIG. 7, where broken glass fragments cannot escape. | For breaking up fluorescent lamp tubes and other frangible articles, a plunger is reciprocated vertically by a manually operated crankshaft on a stand. An elongated tubular guide extends out from the stand and may be raised to an inclined position to feed the lamp tube by gravity beneath the plunger. This guide has top and bottom openings which register respectively with the bottom of a guide sleeve for the vertically reciprocable plunger and the top of an inverted funnel-shaped housing for guiding the broken fragments into a bag suspended from this housing. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of co-pending U.S. application Ser. No. 14/691,983 filed on Apr. 21, 2015, which itself claims benefit of U.S. Provisional Application Ser. No. 62/119,653 filed on Feb. 23, 2015, each of which this application claims benefit from and the contents of which are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates generally to firearms, and more particularly to an automatic firearm apparatus and method of operation thereof.
BACKGROUND OF THE INVENTION
[0003] A firearm is a portable gun that fires a bullet which travels in a projectile motion. The firearm may be is used for security or defence purposes. There are many companies which manufacture firearms. One of the criterions for judging the quality of the firearm is endurance capacity of the firearm. The endurance capacity of the firearm relates to number of bullets the firearm is capable of continuously without encountering any problem. For determining the endurance capacity of a firearm an endurance test is usually performed in which a human operator shoots bullets from the firearm.
[0004] The manual endurance test for a firearm as is prevalent in the state of the art systems is has several limitations. One limitation is number of firearms may be tested using manual testing due to inherent capability of a human operator to work only for a limited number of times. A second limitation is cost of testing the firearms as the human operator needs to be paid for his or her services. A third limitation is that a human operator is limited in his or her capability to shoot only with a limited frequency which is below a satisfactory frequency level. A fourth limitation of manual testing of firearms is negative effect of the exhaust of the bullets on health of the human operator.
SUMMARY OF THE INVENTION
[0005] Therefore, there exists a need for an automatic firing apparatus that is safe, reliable, easy to use and maintain, stable, and portable. Further, the automatic firing apparatus should be configurable to fire and test different types of firearms which may have differing shapes and sizes.
[0006] As a first aspect of the invention, there is provided an automatic firing method comprising initiating a trigger actuator for automatically firing bullets contained in a magazine of a firearm; releasing the empty magazine using a magazine release actuator; and loading a new magazine inside to the firearm from a magazine bank adapted to store bullet magazines using a magazine loading actuator.
[0007] Preferably, the trigger actuator is any one of a hydraulic, electrical, pneumatic, or magnetic actuator.
[0008] Preferably, the magazine release actuator is any one of a hydraulic, electrical, pneumatic, or magnetic actuator.
[0009] Preferably, the magazine loading actuator is any one of a hydraulic, electrical, pneumatic, or magnetic actuator.
[0010] Preferably, the method further comprises automatically determining the number of bullets being fired, automatically initiating the magazine release actuator for releasing the empty magazine once all the bullets of the magazine are fired and automatically initiating the magazine loading actuator for loading the new magazine inside the firearm once the empty magazine is released and for reinitiating these actuator actions until exhaustion of all the magazines stored inside the magazine bank.
[0011] Preferably, the method further comprises automatically initiating a slider release actuator for releasing the fired bullets from the firearm and repeating the above steps until all the magazines inside the magazine bank are consumed.
[0012] Preferably, the slider release actuator is any one of a hydraulic, electrical, pneumatic, or magnetic actuator.
[0013] Preferably, the method further comprises automatically initiating a door actuator for opening a door to a discard box once the empty magazine is released, wherein the empty magazine is forced inside the discard box through the opened door using a magazine discard actuator after the door is opened.
[0014] Preferably, each one of the door actuator and the magazine discard actuator is any one of a hydraulic, electrical, pneumatic, or magnetic actuator.
[0015] Preferably, the method further comprises using a gripping actuator for automatically adjusting a gripping apparatus for securely gripping the firearm in place before initiating the triggering actuator.
[0016] Preferably, the method further comprises automatically releasing the gripping actuator after all the filled magazines stored in the magazine disk have been consumed.
[0000] Preferably, the slider release actuator is any one of a hydraulic, electrical, pneumatic, or magnetic actuator.
[0017] Preferably, the magazine disk is a rotatable magazine disk and wherein the loading action of a new magazine comprises rotating the magazine disk by a magazine disk actuator at a predefined angle, direction and time to make available the next filled magazine in position to be loaded inside the firearm.
[0018] Preferably, the torque required for rotating the magazine disk is preconfigured as a function of moment of inertia and angular acceleration of the magazine disk.
[0019] Preferably, the moment of inertia is a function of total weight of the magazine disk and radius of the magazine disk.
[0020] Preferably, the total weight of the magazine disk comprises a weight of the magazine disk and the weight of the plurality of filled magazines.
[0000] Preferably, the actions of the actuators are initiated and coordinated using an electronic circuit, a microcontroller or microprocessor.
[0021] Preferably, the method utilizes a power source comprising at least one of an AC plug-in power, fuel generated power, and a battery or any suitable other power source.
[0000] Preferably, the firing is conducted according to a firing frequency preconfigured using an electronic circuit, a microcontroller or a microprocessor.
[0022] Preferably, the method is for purpose of testing at least one of the firearm and the firearm bullets.
[0023] As a further aspect of the invention, there is provided an automatic firing apparatus comprising:
a trigger actuator for automatically firing bullets contained in a magazine of a firearm; a magazine release actuator for releasing an empty magazine from the firearm; a magazine bank for storing a bullet magazine inside the firearm; and a magazine loading actuator for loading a new magazine inside the firearm from the magazine bank.
[0028] Preferably, the apparatus further comprises a slider release actuator for releasing the fired bullets from the firearm.
[0029] Preferably, the apparatus further comprises a door actuator and a magazine discard actuator, the door actuator being adapted for opening a door to a discard box once the empty magazine is released, wherein the empty magazine is forced inside the discard box through the opened door using the magazine discard actuator after the door is opened.
[0030] Preferably, the apparatus further comprises a gripping apparatus for securely receiving the firearm and a gripping actuator for automatically adjusting the gripping apparatus for securely gripping the firearm in place before initiating the triggering actuator.
[0031] Preferably, the magazine bank is a rotatable magazine disk, the apparatus further comprising a magazine disk actuator for rotating the magazine disk in predetermined angle, direction and time to make available the next bullet magazine in position to be loaded inside the firearm once the empty magazine is released.
[0032] Preferably, the apparatus further comprises an electronic circuit, microcontroller or microprocessor adapted to be connected to the actuators for initiating the coordinating the actions of the actuators.
[0033] Preferably, the electronic circuit, microcontroller or microprocessor is adapted for automatically determining the number of bullets being fired, automatically initiating the magazine release actuator for releasing the empty magazine once all the bullets of the magazine are fired and automatically initiating the magazine loading actuator for loading the new magazine inside the firearm once the empty magazine is released and for reinitiating these actuator actions until exhaustion of all the magazines stored inside the magazine bank.
[0034] Preferably, each one of the actuators is any one of a hydraulic, electrical, pneumatic, or magnetic actuator.
[0035] Preferably, the apparatus further comprises a power supply for supplying power to the electrical/electronic components comprising the actuators and the electronic circuit/microcontroller/microprocessor.
[0036] Preferably, the apparatus is for purpose of testing at least one of the firearm and the firearm bullets.
[0037] As another aspect of the invention, there is provided a magazine bank apparatus for use with a firearm comprising:
a magazine bank base having a plurality of slots adapted to receive and store bullet magazines; a magazine load actuator adapted to be automatically triggered for loading a bullet magazine among the stored bullet magazines inside the firearm.
[0040] Preferably, the magazine bank base is a rotatable magazine disk.
[0041] Preferably, the magazine bank apparatus further comprises a magazine bank actuator adapted to rotate the magazine disk at a predefined angle, direction and time to make available the bullet magazines in position to be loaded inside the firearm one at a time.
[0042] Preferably, the magazine bank apparatus 33 further comprises a microcontroller adapted to be connected to the magazine bank actuator, the microcontroller being preconfigured with the predefined angle and direction.
[0043] Preferably, the microcontroller is further adapted to be connected to the magazine load actuator for initiating the loading action of the magazine inside the firearm once the bullet magazine has been put in position to be loaded by the magazine bank actuator.
[0044] Preferably, the microcontroller is further adapted to be connected to a trigger actuator and to a magazine release actuator for releasing an empty magazine from the firearm once the bullets are fired using the trigger actuator.
[0045] Preferably, the microcontroller is further adapted to rotate the magazine disk to make available a next bullet magazine in position to be loaded once the empty magazine is released from the firearm.
[0046] Preferably, the microcontroller is further adapted to iteratively initiate the trigger actuator for firing all the bullets inside a bullet magazine, determine once all the bullets inside the magazine are fired, initiate the magazine release actuator for releasing the empty magazine once all the bullets are fired, initiate the magazine disk to rotate to make available the next bullet magazine in position to be loaded inside the firearm once the empty magazine is released, initiate the magazine loading actuator to load the next bullet magazine inside the firearm once the next magazine is in position to be loaded and to repeat these steps until all the magazines stored inside the magazine bank are exhausted.
[0047] Preferably, the slots are positioned along the radial axis of the magazine disk.
[0048] As a further aspect of the invention, there is provided method of using a firearm comprising:
a. positioning a firearm using a gripping apparatus; b. positioning a slot having a charged magazine of a magazine bank in a first position to face a magazine receiving portion of the firearm by rotating the magazine bank along an axis of rotation in a predetermined direction by a predetermined angle using a magazine disk actuator; c. loading the charged magazine into the firearm using a magazine loading actuator; d. initiating a firing sequence of the firearm to fire all bullets in the charged magazine; e. releasing the empty magazine from the firearm using a magazine release actuator; f. moving the empty magazine into a container using a magazine discard actuator; and g. repeating steps b through e till all charged magazines of the magazine bank are emptied.
[0056] Preferably, the positioning action of the slot comprises rotating the magazine bank to the first position within a predetermined time interval.
[0057] Preferably, the predetermined time interval is determined based on a required firing frequency for the firearm.
[0058] Preferably, the magazine bank is rotated by a step motor of a predetermined power and rounds per minute (RPM).
[0059] Preferably, the firing sequence is initiated by a trigger actuator, wherein the trigger actuator is one of a pneumatic actuator, a hydraulic actuator, an electrical actuator and a mechanical actuator.
[0060] Preferably, the trigger actuator comprises a pneumatic piston.
[0061] Preferably, initiating the firing frequency comprises determining the required firing frequency for the firearm.
BRIEF DESCRIPTION OF THE DRAWINGS
[0062] The present automatic firing apparatus and methods of use thereof will be better understood by reading the Detailed Description of the embodiments with reference to the accompanying drawing FIGS. 1-6 , in which like reference numerals denote similar structure and refer to like elements throughout, and in which:
[0063] FIG. 1 illustrates block diagram of a control system for an automatic firing apparatus according to an exemplary embodiment of the present invention;
[0064] FIG. 2 illustrates an exemplary view of an automatic firing apparatus according to one embodiment of the present invention;
[0065] FIG. 3 illustrates an exemplary view of an automatic firing apparatus of FIG. 2 with a firearm positioned thereat according to one embodiment of the present invention;
[0066] FIG. 4 illustrates a magazine bank of the automatic firing apparatus according to one embodiment of the present invention;
[0067] FIG. 5 shows a flow diagram illustrating a method for automatic firing apparatus according to an embodiment of the present invention;
[0068] FIG. 6 shows a logical flow diagram illustrating a control sequence of the automatic firing apparatus.
[0069] It is to be noted that the drawings presented are intended solely for the purpose of illustration and that they are, therefore, neither desired nor intended to limit the disclosure to any or all of the exact details of construction shown, except insofar as they may be deemed essential to the claimed invention.
DETAILED DESCRIPTION OF THE INVENTION
[0070] The automatic firing apparatus comprises a microcontroller and one or more actuators. The microcontroller may be programmed to control the automatic firing apparatus. A gripping actuator activates a gripper which holds the firearm in a required position. The gripper exerts a required force to ensure the tightness of the firearm on the fixture. A triggering actuator controls the trigger of the firearm. The firearm may fire till all the bullets in the magazine are fired. A door actuator opens a door of a container. A magazine release actuator releases an empty magazine from the firearm. A magazine bank actuator commands a motor to rotate a magazine bank in a predetermined direction by a predetermined angle. The microcontroller determines if all the charged magazines of the magazine bank have been exhausted. A magazine loading actuator loads next available charged magazine from the magazine bank in the firearm.
[0071] In describing the exemplary embodiments of the present invention, as illustrated in FIGS. 1-6 specific terminology is employed for the sake of clarity. The present disclosure, however, is not intended to be limited to the specific terminology so selected, and it is to be understood that each specific element includes all technical equivalents that operate in a similar manner to accomplish similar functions. Embodiments of the claims may, however, be embodied in many different forms and should not be construed to be limited to the embodiments set forth herein. The examples set forth herein are non-limiting examples, and are merely examples among other possible examples.
[0072] Referring now to FIG. 1 , which shows a an automatic firing apparatus according to an exemplary embodiment of the present invention. The automatic firing apparatus is a power driven apparatus for automatic firing of a firearm comprising a gripping apparatus for securely gripping an arm, a gripping actuator 20 for adjusting the gripping apparatus to securely hold in place the firearm, a triggering actuator 30 for engaging a trigger of the firearm placed on the gripping apparatus, a slider release actuator 80 for engaging a release slider of the arm for releasing the bullets, a magazine release actuator 40 for releasing the empty magazine from the firearm when all the bullets of the magazine have been fired, a door actuator 50 for pushing the released magazine inside a container to store the empty magazines, a rotating magazine bank for storing filled magazines, a magazine bank actuator 60 for rotating the magazine bank according to predetermined angle, direction and time, a magazine loading actuator 70 for loading a filled magazine from the magazine bank inside the firearm, and a microcontroller 10 in connection with the gripping actuator 20 , the triggering actuator 30 , the slider release actuator 80 , the magazine release actuator 40 , the door actuator 50 , the magazine bank actuator 60 and the magazine loading actuator 70 for coordinating the actions of the actuators.
[0073] Referring now to FIG. 2 which illustrates an exemplary view of an automatic firing apparatus 200 according to one exemplary embodiment of the present invention. The automatic firing apparatus 200 has a base 202 to which one or more components may be coupled to or operatively connected to. In one embodiment, the base 202 is rectangular. However, a person of ordinary skill in the art would understand that the base 202 may be triangular, circular, poles or of any other appropriate shape. In one embodiment, the base 202 is made of stainless steel. However, a person of ordinary skill in the art would understand that the base 202 may be made of any other metal, alloy, plastic, wood, or any other appropriate material. In one embodiment, the base 202 is an upper portion of a table. The base 202 provides stability and support to other components attached thereto.
[0074] An arm module 208 is coupled to a first surface 204 of the base 202 . The arm portion may receive a firearm therein and grip it firmly in place. The arm module 208 may be operatively connected to the gripping actuator 20 , the triggering actuator 30 , the magazine release actuator 40 , the door actuator 50 , the magazine bank actuator 60 , the magazine loading actuator 70 , and the slider release actuator 80 for operating the automatic firing apparatus 200 .
[0075] Further, a magazine bank 210 is operatively connected to a second surface 206 of the base 202 . In one embodiment, the second surface 206 of the base 202 is substantially parallel to the first surface 204 of the base 202 . The magazine bank 210 may be positioned on a support 214 and operatively connected to the base 202 . The magazine bank 210 may be rotated about an axis of rotation in a predetermined direction by a predetermined angular distance. An angular speed and an angular acceleration of the rotation of the magazine bank 210 may also be controlled using the microcontroller 10 via the magazine bank actuator 60 .
[0076] In one embodiment of the present invention, the magazine bank actuator 60 may activate a motor that may rotate the magazine bank 210 based on one or more commands received from the microcontroller 10 . In one embodiment, the motor is a servo motor. The servo motor controls an angular position of the rotating magazine bank 210 . In one embodiment, the servo motor is a velocity controlled servo motor. In this embodiment, recalibration of the servo motor is performed by adding a potentiometer. The potentiometer readings are transferred into angles traveled by the servo motor. The potentiometer readings may be converted into required angular distance and the servo motor may rotate the magazine bank 210 to the required position.
[0077] In another embodiment, the magazine bank 210 may be rotated by any other rotational mechanism known in the art without departing from the scope of the present invention. The rotational mechanism used should be able to rotate the magazine bank 210 with a predetermined angular velocity and a predetermined angular acceleration. More details of the magazine bank 210 are illustrated with reference to FIG. 4 .
[0078] The automatic firing apparatus 200 may further include one or more power supplies 212 . The power supplies 212 may be positioned at the support 214 . The power supplies 212 provide power to one or more power operated components of the automatic firing apparatus 200 . In one embodiment of the present invention, the power supplies 212 supplies power to the gripping actuator 20 , the triggering actuator 30 , the magazine release actuator 40 , the door actuator 50 , the magazine bank actuator 60 , the magazine loading actuator 70 , and the slider release actuator 80 of the automatic firing apparatus 200 .
[0079] The automatic firing apparatus 200 may further include a control box (not shown) having therein the microcontroller 10 and one or more controllers for the gripping actuator 20 , the triggering actuator 30 , the magazine release actuator 40 , the door actuator 50 , the magazine bank actuator 60 , the magazine loading actuator 70 , and the slider release actuator 80 . In one embodiment of the present invention, one or more of the actuators 20 , 30 , 40 , 50 , 60 , 70 and 80 may include linear actuators. In one embodiment of the present invention, the one or more of the actuators 20 , 30 , 40 , 50 , 60 , 70 and 80 may be operated by a hydraulic, mechanical, electrical, pneumatic, or magnetic means. The microcontroller 10 may control one or more functions and timing of the one or more controllers associated with the actuators 20 , 30 , 40 , 50 , 60 , 70 and 80 .
[0080] The automatic firing apparatus 200 may further include a trigger means 216 . In one embodiment, the trigger means 216 is a pneumatic piston. The pneumatic piston may be controlled based on one or more commands from the microcontroller 10 . The pneumatic piston pulls and releases a trigger of a firearm at a predetermined frequency.
[0081] Referring now to FIG. 3 , which illustrates an exemplary view of the automatic firing apparatus 200 with a firearm 322 positioned thereat according to one embodiment of the present invention.
[0082] A base plate 302 is affixed to the base 202 . A holder 306 is affixed at the top of the base plate 302 . A fixture is supported on the holder 306 . The fixture includes a fixture base 308 , fixture plates 310 and 314 , and a fixture slider 312 . The fixture base 308 may be attached to the holder 306 with nuts and bolts, screws or any other preferred mechanism. The fixture plates 310 and 314 are arranged perpendicular to the fixture base 308 and substantially parallel to each other at a predetermined distance from each other so that a hollow receiving portion is formed between them. The distance between the fixture plates 310 and 314 may be varied for accommodating firearms of different sizes or shapes.
[0083] A firearm 322 is shown in a simplified manner for the sake of clarity. The firearm 322 is shown raised from its actual position for the sake of clarity and explanation. The firearm 322 has slide button 316 which is operated with the fixture slider 312 . The movement of the fixture slider 312 can operate to release and hold the slide button 316 of the firearm 322 .
[0084] The firearm 322 further includes a trigger 318 which is operatively connected to the pneumatic piston 216 via the triggering actuator 30 . The movement of the pneumatic piston along its axis pulls and releases the trigger 318 to achieve firing of bullets from the firearm 322 at a predetermined rate.
[0085] The firearm 322 further includes a magazine release button 320 which is operatively connected to the magazine release actuator 40 to release an empty magazine from the firearm 322 .
[0086] Also shown in FIG. 3 is a partial view of the magazine bank 210 . The magazine bank 210 has a plurality of slots 304 to hold one or more magazines. The complete operation of the automatic firing apparatus 200 is further explained with reference to FIGS. 5-6 .
[0087] Referring now to FIG. 4 , which illustrates in an exemplary embodiment, a top view of the magazine bank 210 of the automatic firing apparatus 200 . The magazine bank 210 has a base having a first surface, a second surface substantially parallel to the first surface. The magazine bank 210 may have an intermediate structure for coupling the first surface and the second surface at a predetermined distance from each other. The magazine bank 210 includes a plurality of slots 304 movable in a direction substantially perpendicular the first surface. The magazine bank 210 has an attached pushing mechanism which is configured to push a slot of the plurality of slots 304 in the movable direction. As described above with reference to FIG. 2 , the magazine bank 210 may be rotated about an axis of rotation 402 with a predetermined angular velocity. In one embodiment the axis 402 is substantially perpendicular to the base of the magazine bank 210 . In one embodiment, a servo motor rotates the magazine bank 210 on receiving a command from the microcontroller 10 via the magazine bank actuator 60 .
[0088] In one embodiment of the present invention, shape of the magazine bank 210 is one of a cuboid, a cube, a hollow disk and a solid disk. In one embodiment, the magazine bank 210 has the plurality of slots 304 arranged around the axis 402 among one or more plates. The one or more plates are positioned at different radial distances from the axis 402 . Although only a single plate comprising the plurality of slots 304 arranged along a periphery 404 of the circular disk is shown in FIG. 4 , it is contemplated that more than one plates of the plurality of slots 304 may be arranged on the magazine bank 210 with suitable modification. Therefore, arrangement of the plurality of slots 304 in various configurations is considered to be within the scope of the present invention. The number of the plurality of slots 304 may be varied as per the requirement.
[0089] Referring now to FIG. 5 , which shows a flow diagram illustrating a method 500 for automatic firing apparatus 200 according to an exemplary embodiment of the present invention. The method starts at step 502 .
[0090] At step 502 , the firearm 322 is positioned in a receiving portion of the arm module 208 of the automatic firing apparatus 200 . A gripping mechanism is activated by providing a command from the microcontroller 10 via the gripping actuator 20 . The gripping actuator 20 activates a gripper which holds the firearm 322 in a required position. In one embodiment of the present invention, the fixture plates 310 and 314 are moved to grip the firearm 322 . In another embodiment, additional grippers may be used to restrict the movement of the firearm 322 in a particular direction. The step 502 may further include putting one or more charged magazines in the magazine bank 210 . In one embodiment, the magazine bank 210 has N slots each is filled with a charged magazine, where N is a natural number. In one embodiment, one or more slots of the magazine bank 210 remain empty.
[0091] Once the firearm 322 is firmly gripped at the arm module 208 and the magazine bank 210 has been filled with one or more charged magazines, the method proceeds to step 504 .
[0092] At step 504 , a charged magazine from the magazine bank 210 is loaded into the firearm 322 . The loading may be performed by various loading means. In one embodiment, the magazine loading actuator 70 pushes the charged magazine from the slot of the magazine bank 210 upwards into the magazine receiving portion of the firearm 322 . In one embodiment, the magazine loading actuator 70 is a linear actuator. Simultaneously, the magazine release actuator 40 may operate on the magazine release button 320 of the firearm 322 to facilitate the loading of the charged magazine into the firearm 322 . Alternative mechanisms such as pneumatic, hydraulic, mechanical, electrical, or magnetic to load the charged magazine from the magazine bank 210 into the firearm 322 are considered within the scope of the present invention. The magazine release actuator 40 and the magazine loading actuator 70 may be controlled by the microcontroller 10 .
[0093] At step 506 , a firing sequence of the firearm 322 is initiated by activating the pneumatic piston 216 which controls the trigger 318 of the firearm 322 . The firing sequence is continued till all bullets in the charged magazine are fired. Subsequently, the empty magazine is released from the firearm 322 and moved to a container (not shown) which is operatively connected to the arm module 208 and collects the empty magazines. Moving an empty magazine from the firearm 322 to the container may be achieved with the help of magazine release actuator 40 and the door actuator 50 . The door actuator 50 opens a door of the container and the magazine release actuator 40 pushes the magazine release button 320 so the empty magazine drops into the container. Once the empty magazine has been moved from the firearm 322 into the container, the door of the container is closed by the door actuator 50 . At that moment in the method 500 , the magazine receiving portion of the firearm 322 faces an empty slot of magazine bank 210 . To load the next available charged magazine from the magazine bank 210 into the firearm 322 , the magazine bank 210 needs to be rotated which function is achieved in step 508 as explained below.
[0094] At step 508 a slot of the magazine bank 210 having a charged magazine is positioned in a first position to face a magazine receiving portion of the firearm 222 by rotating the magazine bank 210 along the axis of rotation 402 in a predetermined direction by a predetermined angle. In one embodiment, the magazine bank 210 is rotated by the magazine bank actuator 60 on receiving a command from the microcontroller 10 . In one embodiment of the present invention, the angle of rotation may be determined by number or slots available on the magazine bank 210 . For example, if the magazine bank 210 has N slots then the required angle of rotation may be obtained by dividing 360 by N. Once the angle of rotation is determined, the servo motor may receive a command from the microcontroller 10 to rotate the magazine bank 210 by the determined angle of rotation. The direction of the rotation of the magazine bank 210 may be either clockwise or anticlockwise. The rotation of the magazine bank 210 places the next available charged magazine in a position from which the charged magazine can be loaded into the firearm 322 as explained in step 504 .
[0095] At step 510 , the empty magazine is released from the firearm 322 and moved into the container as explained in step 506 .
[0096] At step 512 , it is determined whether there is at least one charged magazine in the magazine bank 210 . If it is determined at step 512 that there is at least one charged magazine present in the magazine bank 210 then the method 500 proceeds to step 504 . However, if it is determined at step 512 that there is no charged magazine present in the magazine bank 210 then the method is ended.
[0097] Referring now to FIG. 6 , which shows a logical flow diagram illustrating a control sequence 600 of the microcontroller 10 of the automatic firing apparatus 200 . The sequence 600 starts with step 602 . At step 602 the microcontroller 10 is reset. The microcontroller 10 may be programmed to loop the control sequence N times, where N is the number of slots available on the magazine bank 210 . At step 604 , control transfer to the gripping actuator 20 . The gripping actuator 20 activates a gripper which holds the firearm 322 in a required position. The gripper exerts required force to ensure the tightness of the firearm 322 on the fixture. In one embodiment of the present invention, a feedback sensor is installed within the gripping actuator 20 to ensure that a stroking length is positioned accurately as much as possible and the force exerted is consistently the required force to hold the firearm 322 firmly in position.
[0098] At step 606 , the control passes to the trigger means 216 via the triggering actuator 30 which controls the trigger 318 of the firearm 322 . The trigger means 216 may fire till all the bullets in the magazine are fired.
[0099] At step 608 , the control passes to the door actuator 50 which opens the door of the container. At step 610 , the control passes to the magazine release actuator 40 which releases an empty magazine from the firearm 322 . The control is passed again to the door actuator 50 to close the door of the container.
[0100] At step 612 , the control passes to the magazine bank actuator 60 and commands the servo motor to rotate the magazine bank 210 in a predetermined direction by a predetermined angle along the axis of rotation 402 of the magazine bank 210 . Then the control passes to the microcontroller 10 at step 614 which determines if all the charged magazines of the magazine bank 210 have been exhausted. In one embodiment, this is determined by comparing a loop variable ‘I’ to the number of slots ‘N’ in the magazine bank 210 . If ‘I’ equals ‘N−1’ at step 614 then all the charged magazines of the magazine bank 210 have been exhausted. Thereafter, the control passes to the gripping actuator 20 at step 516 which opens the gripper and the control sequence ends. However, If ‘I<N−1’, at step 614 , the control passes to the magazine loading actuator 70 which at step 618 loads next available charged magazine from the magazine bank 210 in to the firearm 322 . At step 620 , the control passes to the slider release actuator 80 and the triggering actuator 30 . As already noted above, the control sequence is repeated till all the charged magazines in the magazine bank 210 have been exhausted.
[0101] The foregoing specification describes the automatic firing apparatus 200 comprises the microcontroller 10 programmed to control the automatic firing apparatus 200 . The automatic firing apparatus 200 is safe, reliable, easy to use and maintain, stable, and portable. Further, the automatic firing apparatus 200 is configurable to fire and test different types of firearms which may have differing shapes and sizes.
[0102] The foregoing description and drawings comprise illustrative embodiments of the present invention. Having thus described exemplary embodiments, it should be noted by those ordinarily skilled in the art that the within disclosures are exemplary only, and that various other alternatives, adaptations, and modifications may be made within the scope of the present invention. Merely listing or numbering the steps of a method in a certain order does not constitute any limitation on the order of the steps of that method. Many modifications and other embodiments of the invention will come to mind to one ordinarily skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Although specific terms may be employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Moreover, the present invention has been described in detail; it should be understood that various changes, substitutions and alterations can be made thereto without departing from the spirit and scope of the invention as defined by the appended claims. Accordingly, the present invention is not limited to the specific embodiments illustrated herein, but is limited only by the following claims | There is provided an automatic firing apparatus, and a method for operating the automatic firing apparatus, the apparatus comprising a trigger actuator for automatically firing bullets contained in a magazine of a firearm; a magazine release actuator for releasing an empty magazine from the firearm; a magazine bank for storing a bullet magazine inside the firearm; and a magazine loading actuator for loading a new magazine inside the firearm from the magazine bank. There is further provided a magazine bank apparatus for use with a firearm comprising a magazine bank base having a plurality of slots adapted to receive and store bullet magazines; and a magazine load actuator adapted to be automatically triggered for loading a bullet magazine among the stored bullet magazines inside the firearm. | 5 |
FIELD OF THE INVENTION
[0001] The present invention generally relates to chemical or biological attack detection and mitigation systems, and more particularly to chemical or biological attack detection and mitigation systems for buildings.
BACKGROUND OF THE INVENTION
[0002] The recent demise of the cold war and decline in super-power tensions has been accompanied by an increase in concern over the viability of weapons of mass destruction such as chemical and biological (CB) weapons. CB weapons include chemical agents such as blood, blister and nerve agents, and biological agents such as anthrax or small pox. CB weapons may be delivered to occupants within a building by releasing the agents external to the building but close to an air intake of the building. The air intake may be located near the ground, near the roof, or somewhere in between, depending on the building architecture. Agents may also be released within a public area of a building, and be dispersed to other, private areas of the same building. Agents released in one area of a building may be further dispersed by the heating, ventilating, and air conditioning (HVAC) system of the building. Therefore, the HVAC system may effectively deliver an agent from one room to the entire building. While the agent is being delivered through the building, the location of the agent source may remain unknown, as well as the extent of the harm caused.
[0003] There are various agent delivery mechanisms. For example, agents may be delivered in vehicles giving some warnings as to the delivery, such as missiles. Agents may also be delivered in vehicles giving no warning, such as a pedestrian held putative asthma inhaler activated near an air intake in the building.
[0004] Certain buildings, such as key military sites, can be equipped or designed well in advance to deal with the use of CB weapons. Such buildings may include elaborate, built-in fixed chemical and biological sensors. Such fixed sensors, even when thorough, are generally limited to sensing one area of a building, and may be too expensive to place in all desired areas of a the building. Some buildings, however, such as hotels may be more susceptible to a CB weapons attack, lacking even fixed sensors. What would be desirable, therefore, are chemical and biological sensors that can be deployed at multiple locations in a building. What would also be advantageous are sensors that are able to search for and identify the location of harm agents. Devices able to assist building inhabitants during an attack would also be valuable.
SUMMARY OF THE INVENTION
[0005] The present invention includes systems for detecting agents harmful to human life in buildings. The systems can include a self-propelled harmful agent detector for traversing spaces anywhere in buildings. The self-propelled agent detectors can include a harmful agent sensor for sensing chemical and/or biological agents injurious to human health, with the harmful agent sensor having a data output. A transmitter can be coupled to the harmful agent sensor data output for transmitting data from the self-propelled harmful agent detector to a receiver. A power source can supply a motor having a moving output, with a traction device coupled to the motor moving output for moving the self-propelled harmful agent detector. One embodiment has a rotating shaft as the motor moving output, with the rotating shaft coupled to at least one wheel. Some embodiments use wheels as a traction device, other embodiments utilize tracks, and still other embodiments utilize capstans for moving the detector along suspended wires or strings. Some devices use take-up pulleys or winches to move the device up and down along strings or wires.
[0006] Some detectors have sensors that can measure levels of harmful agent concentration, wherein the sensor data contains data indicating harmful agent levels, and the transmitter can transmit the agent level data. Sample traps, such as vacuum vessels or adhesives, may be included in some devices to capture samples for later analysis. Some detectors can identify the type of the harmful agent and transmit that as well. Many detectors according to the present invention also broadcast the identity and absolute or relative location of the detector. Devices may have cameras and transmitters coupled to the cameras for transmitting images near the detectors to a receiver. Such mobile transmitting cameras may be used to transmit images including victim location.
[0007] Systems incorporating moving detectors according to the present invention are also provided. Systems can include receivers for receiving data transmitted by the moving detectors. The received information can include the mobile detector ID, the type of agent detected, the agent level detected, and the location of the detector. Some systems include machine intelligence for propelling the detector toward areas having higher harmful agent concentrations. Some mobile detectors have repeating capabilities, for receiving and re-transmitting signals received from other mobile detectors in order to extend the range of transmitters, which may be disposed in areas not conducive to RF transmissions, such as within air ducts. Some systems have mobile agent detector location systems, such as a triangulation system within a building, in order to locate the position of a transmission without requiring a mobile detector to have knowledge of its position.
[0008] Some embodiments of the invention, in addition to collecting and transmitting data, can assist building inhabitants. One class of devices according to the present invention can carry information, guidance, life support equipment, and even decontamination equipment to people located within a building. One such device is large enough to carry air bottles, air packs, face masks, breathing filters, protective garments, and communication gear within the device. Some devices transmit photographic views of the area surrounding the device to a central site. Other embodiments include speakers and/or changeable message signs which can be used to transmit instructions to building inhabitants. One use of such devices is to find a safe egress route from a building that is contaminated, and instruct building inhabitants as to the route and/or instruct the building inhabitants to “follow me.”
[0009] Methods according to the present invention include providing the mobile detectors and/or receiving systems described above. The mobile harmful agent detectors can be disposed within the building and allowed to move throughout the building, and transmit information related to any harmful agent present. Some methods include mobile detectors disposed and programmed to roam outside of a building. Mobile detectors can be disposed along building floors, within air ducts, disposed along suspended wires, strings, or shafts, and hung from hanging wires, strings, ribbons, or pendulums, both within open atriums and within vertical air shafts. Some systems move the self-propelled detectors by providing the motor on one end of a string or wire and the detector on the other end. The detector is then moved by advancing the motor to move the string or wire. Other systems provide a fixed string or wire, with the detector and motor moved together. Flying mobile detectors, for example, sensors mounted on micro air vehicles (MAVs), are also included within the invention.
[0010] Some methods include providing self-propelled detector sensors to measure levels of harmful agent concentration, wherein the transmitted sensor data contains data indicating harmful agent levels, which is received and stored. Other methods include directing self-propelled mobile detectors to areas of interest, where the direction is provided from a central controller, either machine or human. In some systems, a central computer creates maps of agent type and/or intensity using the data provided by the mobile detectors.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] [0011]FIG. 1 is a highly diagrammatic, perspective, cutaway view of a conventional building HVAC system shown delivering a harmful agent from a public area return air duct to private areas in the building interior;
[0012] [0012]FIG. 2 is a highly diagrammatic, side view of a mobile harmful agent detector device having a power source, controller, transmitter, motor, and wheels for traction;
[0013] [0013]FIG. 3 is a highly diagrammatic, side view of a mobile harmful agent detector device similar to that of FIG. 2, but having a track for traction;
[0014] [0014]FIG. 4 is a highly diagrammatic, side view of a mobile harmful agent detector device similar to that of FIG. 2, but having legs for traction;
[0015] [0015]FIG. 5 is a highly diagrammatic, side view of a mobile harmful agent detector device similar to that of FIG. 2, but having driven pulleys or capstans for traction along a wire or cable which may be substantially horizontal;
[0016] [0016]FIG. 6 is a highly diagrammatic, side view of a mobile harmful agent detector device similar to that of FIG. 5, but having driven pulleys or capstans for traction along a wire or cable which may be substantially vertical;
[0017] [0017]FIG. 7 is a highly diagrammatic, side view of a mobile harmful agent detector device similar to that of FIG. 6, but having motor driven traction pulleys or spools mounted on the mobile detector for taking up a wire or cable which may be substantially vertical;
[0018] [0018]FIG. 8 is a highly diagrammatic, side view of a mobile harmful agent detector device similar to that of FIG. 7, but having motor driven traction take up pulleys or spools mounted on the opposing end of a wire or cable which may be substantially vertical;
[0019] [0019]FIG. 9 is a highly diagrammatic, side view of a mobile harmful agent detector which can be used to transmit pictures to a remote site, transmit information to building inhabitants, and carry safety equipment to inhabits; and
[0020] [0020]FIG. 10 is a block diagram of a system for communication with and coordination of mobile harmful agent detectors.
DETAILED DESCRIPTION OF THE INVENTION
[0021] Various embodiments of the invention are described below in some illustrative examples of the invention. Such examples are intended to be illustrative rather than limiting. Identical reference numerals are used across the multiple figures to describe identical or similar elements, which are not reintroduced with each figure.
[0022] [0022]FIG. 1 illustrates a building 20 including a public atrium area 23 and having a conventional building heating, ventilating, and air conditioning (HVAC) system 22 not having any duct isolation equipment in place. HVAC system 22 is illustrated transporting harmful agent 46 through return air ducts 34 and dispersing it as externally released cloud 44 . Air intake 24 and exhaust 26 are connected to a series of ducts including large, usually rectangular chambers or ducts such as chamber 28 , and intermediate sized, usually rectangular, ducts 30 . Intermediate ducts 30 split off into a series of smaller, often circular, ducts 32 , which feed a series of room diffusers 38 . Return air vents 36 and return air ducts 34 return air to either be expelled outside the building or be mixed with fresh air intake. Heating, cooling, humidification, and dehumidification functions are often performed in large chambers such as chamber 28 , and in more local intermediate sized chambers 42 . Mixing and/or recirculation can be performed by a return air duct 48 .
[0023] [0023]FIG. 1 illustrates an internally released harmful agent cloud 46 dispersed in public atrium 23 near return air vents 36 . HVAC system 22 is illustrated transporting harmful agent 46 through return air ducts 34 and dispersing it as externally released cloud 44 . Return air ducts 34 are also connected through return air duct 48 , into intake chamber 28 , and may internally release harmful agent cloud 47 through diffusers 38 . As illustrated, the harmful agent is delivered from a public portion of the building to the private areas of the building by the HVAC system and to the exterior near the building as well.
[0024] [0024]FIG. 2 illustrates a mobile, self-propelled harmful agent detector device 100 , having a chassis or body 102 , a first wheel set 116 , a second wheel set 122 , a harmful agent sensor 104 , a controller 108 , a power source 120 , a motor 118 , and a transmitter 112 . Controller 108 is coupled to agent detector 104 through a data communication line or channel 106 , which can be, for example, any suitable electrical or optical line, wire or channel. As used herein, “harmful agent sensor or detector” means a sensor or detector for sensing, measuring, or detecting agents harmful to humans, including chemical and biological agents. The terms “harmful agent sensor or detector” and “agent sensor or detector” are intended to convey the same meaning as used herein. Although any suitable detector either known or unknown at the present time may be used, the agent detectors can include, for example, spectrographic analyzers including visible, infrared, near infrared, ultraviolet, and/or fluoroscopic. So-called “chemical noses” or “electrical noses” may be used to identify agents. Portable mass spectrometers may also be used. Portable bioassay devices, reagents, and readable test strips may also be used as agent detectors, if desired.
[0025] In some embodiments, a harmful agent trap is included. Agent traps can include vacuum bottles having controllable inlet valves, or other sampling devices, well known in industrial hygiene monitoring applications. Filter traps and adhesive traps may also be included, and can be used to trap samples for later analysis. In some embodiments, a camera is included with, or in place of, harmful agent sensor 104 , with a picture being transmitted either in addition to, or in place of, harmful agent concentration data. In embodiments having only a camera for example, reference numeral 104 may be understood to refer to a camera.
[0026] Controller 108 may be coupled to transmitter 112 through a data line 110 , and is illustrated transmitting data indicated at 114 . Any suitable transmitter may be used, including radio frequency (RF) and optical transmitters. While the term “transmitter” is used to denote one function of the mobile detector, the transmitter in a preferred embodiment is a transceiver, able to both transmit and receive information.
[0027] Power source 120 may be a battery and is preferably coupled to motor 118 . Power sources may be either fixed to the mobile detector, or located apart from the mobile detector and coupled to the detector by wires. Controller 108 can be coupled to motor 118 through a control line 109 , which can be used to control the motor driving the wheel or wheels. In one embodiment, first wheel set 116 are drive wheels and second wheel set 122 are turnable or steerable wheels, under the control of controller 108 . In some embodiments, mobile detector 100 is self-aware of its position, and can transmit that position to a receiver. In other embodiments, mobile detector 100 transmits a signal which can be triangulated upon by multiple receivers. In still other embodiments, mobile detector 100 can count its relative progress along a known route, by inches, clicks or wheel rotations, with the relative progress into the route ascertainable by the mobile detector and/or a central receiving unit. In a preferred embodiment, the ID of the mobile detector is transmitted along with any other data. In one embodiment, the mobile detector includes a transceiver and may be programmed to retransmit data received from other mobile detectors, having different IDs, thereby allowing the mobile detectors to act as relays. This may be useful for embodiments having short transmission ranges, or detectors disposed within metal air ducts.
[0028] Mobile detector 100 utilizes wheels 116 and 122 as traction devices. The wheels may be formed of a rubber material or other polymer suitable for providing traction. Mobile detector 100 may be used to traverse floors, air ducts, crawl spaces, false ceilings, or any surface the wheels are able to engage. In mobile device 100 , motor 118 is mounted on body 102 such that motor 118 travels together with body 102 . In some devices, discussed below, the propelling motor is fixed to another object and remains in one location while propelling the body, for example, through a tether. In either case, the mobile detector may be self-propelled.
[0029] [0029]FIG. 3 illustrates a mobile detector 130 , similar to mobile detector 100 of FIG. 2, but utilizing tracks or treads 139 disposed over three wheel pair sets 132 , 133 , and 134 . Tracks or treads may be more useful in traversing unfriendly terrain than wheels alone. In some devices, tracks are sufficiently long to enable climbing stairs.
[0030] [0030]FIG. 4 illustrates a mobile detector 160 , similar to mobile detector 100 of FIG. 2, but utilizing legs 168 disposed in three pairs on a chassis or body 164 . Legs may be motor driven by a motor 166 to enable the device to crawl over uncertain terrain, and may be more useful in traversing unfriendly terrain than wheels.
[0031] [0031]FIG. 5 illustrates a mobile detector 180 , similar to mobile detector 100 of FIG. 2, but utilizing pulleys or capstans 182 , 184 , 186 , and 188 , which are supported by legs 190 secured to body 102 and disposed about a wire, cable, string, shaft, or ribbon 181 . Wire 181 may be substantially horizontal in some embodiments, and may be strung through air ducts, under computer room raised floors, through crawl spaces, between buildings, and across building atriums. In some embodiments, the gap between the upper and lower wheels, 182 and 184 , and 186 and 188 , respectively, may be relatively large, and gravity relied upon to provide traction between driven upper wheels 182 and 186 and wire 181 . In other embodiments, the gap between the upper and lower wheels, 182 and 184 , and 186 and 188 , respectively, may be relatively small, and a tight fit between wheels and wire is relied upon to provide traction. In embodiments having a tight fit, enabling the wheels to grasp wire 181 , either upper wheels 182 and/or 186 , or lower wheels 184 and/or 188 , or both, may be driven by motor 118 . In some embodiments, mobile detector 180 travels between two extreme limits of travel, reversing direction when either limit is reached. In some devices, a count of wheel revolutions or similar measure is used to measure travel and can be used to calculate relative location along the route.
[0032] [0032]FIG. 6 illustrates a mobile detector 200 , similar to mobile detector 180 of FIG. 5, but utilizing pulleys or disposed about a wire, cable, string, shaft, or ribbon 232 . Wire 232 is illustrated as fixed to support member 230 , which may be a ceiling in some applications. Wire 232 may be substantially vertically disposed in some embodiments, and may be strung through air ducts, wall spaces, elevator shafts, and building atriums. In a preferred embodiment, the gap between wheel pairs, 182 and 184 , and 186 and 188 , may be relatively small, and a tight fit between the wheels and wire 232 is relied upon to provide traction. In embodiments having a tight fit, enabling the wheels to grasp wire 232 , either wheels 182 , 186 , 184 and/or 188 , may be driven by motor 118 . In some embodiments, wire 232 is serrated, having teeth or other demarcations, providing improved traction. In some embodiments, at least some of the driven wheels are also serrated or have teeth to provide better traction. In some devices, both wire or ribbon 232 and the driven wheels have matching sized teeth, to provide a track for the wheel teeth to engage for better traction. In some embodiments, mobile detector 200 travels between two extreme limits of travel, reversing direction when either limit is reached. In some devices, a count of wheel revolutions or similar measure is used to measure travel and can be used to calculate relative location along the route.
[0033] [0033]FIG. 7 illustrates a mobile detector 220 , similar to mobile detector 200 of FIG. 6, but utilizing a take-up pulley or spool 226 to take up a wire, cable, string or ribbon 234 suspended from support member 230 , which may be a ceiling in some applications. Wire 234 may be substantially vertically disposed in some embodiments, and may be strung as discussed with respect to wire 232 or FIG. 6. Motor driven take-up spool or pulley 226 is secured to body 224 , and can wind wire 234 about the spool as the spool is driven, thereby providing the traction, and pulling mobile detector 220 upward. Downward movement may be provided by reversing the motor direction or by allowing take-up spool 226 to unwind, either controllably or rapidly, depending on the embodiment. In some devices, a count of spool revolutions or similar measure is used to measure travel and can be used to calculate relative location along the route.
[0034] [0034]FIG. 8 illustrates a mobile detector 240 , similar to mobile detector 220 of FIG. 7, but utilizing motor 244 driving a take-up pulley or spool 246 to take up wire, cable, string or ribbon 234 suspended from support member 230 , which may be a ceiling in some applications. A control and/or power line 242 may be coupled to motor 244 to provide power and/or control for the device. Motor driven take-up spool or pulley 246 is secured to motor 244 , and can wind wire 234 about the spool as the spool is driven in some embodiments, thereby providing the traction, and pulling mobile detector 240 upward. Downward movement may be provided by reversing the motor direction or by allowing take-up spool 246 to unwind, either controllably or rapidly, depending on the embodiment. Mobile detector 240 may be said to be self-propelled, but having the motor fixed at the opposing end of a tether, rather than moving with the mobile detector. As previously discussed, the location of the detector may be measured and transmitted along with other data related to agent detection.
[0035] [0035]FIG. 9 illustrates a mobile self-propelled harmful agent detector 400 , having lights 446 and wheels 404 mounted on body 402 , the wheels driven by motor 406 . Mobile detector 400 includes a controller 430 coupled to other components through control lines 410 . Unless otherwise indicated, lines 410 illustrated in FIG. 9 are power and/or control lines, which can be used to provide power and/or transmit and receive data between the various components. Controller 430 can be coupled to a transmitter 426 for transmitting and receiving data 428 as illustrated. As previously discussed, the transmissions may be through any suitable medium including RF and IR. In one embodiment, mobile detector 400 is capable of carrying life support equipment for building inhabitants, and of providing assistance during an emergency.
[0036] A camera head 416 having multiple cameras 418 is disposed on a neck member 420 , which can preferably be controllably turned to face directions determined by a remotely located operator. Images provided by cameras 418 may be transmitted back to a receiver. In one embodiment, neck 420 is fixed, with the multiple cameras being selectable to provide different views. In some embodiments, microphones 414 or other sensors are disposed along the body sides to listen for noises, for example, human voices. The sound signals thus received may also be transmitted back to a receiver.
[0037] A sensor head 408 is also illustrated, which may be rotated about a rotatable neck member 412 . Sensor head 408 may include multiple harmful agent sensors including arrays or different sensors to be used in chemical analysis. Sensor head 408 may include air intake or suction ports to be used, for example, to feed chromatographic or other instruments within body 402 . Sensor head 408 is illustrated as coupled to a sensing analysis unit 422 which is in turn coupled to controller 430 . Sensor head 418 may be rotated in some devices, so as to take samples from different directions.
[0038] Mobile detector 400 may include communications devices intended to communicate with humans who may be located within a building, unsure of what to do. In particular, building inhabitants may be unsure if they should attempt to leave a building, or unsure of what route may be safe to take out of a building. To this end, mobile detector 400 may include a changeable message sign 424 , having, for example, a large, light emitting diode (LED) scrolling display with useful information. Such a display may be controlled by a central controller through transceiver 426 .
[0039] Similarly, a loudspeaker 440 may be used to inform building inhabitants as to a safe route to take out of the building, or may inform the inhabitants to remain in place. Loudspeaker 440 may be coupled through transceiver 426 and may be used in conjunction with microphones 414 to allow a remote operator engage in conversations with people.
[0040] Mobile detector 400 may also contain decontamination equipment, for example, a canister of decontamination fluid or foam 436 coupled to a decontamination nozzle 432 through a pipe or tube 434 . In some embodiments, pipe 434 can be controllably rotated and aimed by a remote operator, with the decontamination fluid or foam controllably ejected by a remote operator, or even by a local person following proper instructions.
[0041] A door 444 may be attached to body 402 , and be opened through use of a handle 438 . A sign 442 may be used to indicate to persons located nearby that there is safety equipment inside. In one embodiment, door 444 is attached to body 402 with hinges. Safety gear disposed within body 402 can include oxygen tanks, regulators, air bottles, air packs, respirators, first aid equipment, filter masks, decontamination equipment, protective garments and communication equipment such as portable radios or telephones.
[0042] In one use of mobile agent detector 400 , mobile agent detector, either alone or using externally provided information, locates a safe egress path through a building believed to be otherwise contaminated, or under harmful agent attack. With the route located, mobile agent detector 400 may travel through the building, informing personnel within of the safe egress route. One method includes having mobile agent detector 400 informing people that a safe route is to be had by following the mobile detector to a destination, which may be an outside exit or an inside safe room.
[0043] [0043]FIG. 10 illustrates a mobile agent detector system 300 , including a central controller or computer 302 , and a transceiver 306 with antenna 308 . An operator interface device 310 , for example a CRT or console, is coupled to controller 302 by a communications line or channel 312 . Transceiver 306 is coupled to controller 302 by a data communications line or channel 304 .
[0044] Controller 302 preferably includes a computer, and operator interface device 310 preferably includes a display screen. Controller 302 can be used to coordinate the movement of numerous mobile detectors, for example, mobile detectors 100 , 130 , 160 , 180 , 200 , 220 , 240 , and 400 . In one embodiment, controller 302 directs the mobile detectors to execute preassigned roaming modes, while tracking, recording, and plotting any possible harmful agents detected. When there is a precipitating event, such as a high concentration measured for a harmful agent, controller 302 may take a more active role.
[0045] In one method, controller 302 may assign the more intrusive mobile detectors, for example the wheeled, steerable detectors, to roam the building floors, out in the open, searching for high concentrations of harmful agents. In one method, mobile detectors able to steer themselves toward higher concentrations are allowed to do so. As the detectors gather data, hot spots, or high concentration areas of harmful agents, are searched for, recorded, plotted, and analyzed by controller 302 and, in some embodiments, analyzed by a human operator.
[0046] In one illustrative example, a mobile detector such as detector 240 may detect a harmful agent concentration near a specified floor level of a large, central return vertical air duct, while an elevator shaft mounted detector confirms the specified floor as a high concentration area. One mobile detector such as detector 180 may indicate the presence of an agent in a smaller horizontal return air duct near that floor, at a specific location of travel. At the same time, a mobile detector within a supply duct for that floor may indicate that no agent has been detected. This may rapidly pinpoint the source of the agent.
[0047] In response, the proper air handling motors, dampers, and blowers may be controlled, and turned on or off, in order to limit the spread of the harmful agent, or even force the harmful agent from the building. Mobile detectors such as wheeled detectors 100 , 130 , or 160 may be instructed to roam the specified and adjoining floors, while remote detector 400 may be sent to the specified floor to provide assistance. By way of comparison, the same number of fixed detectors in the same building may only indicate that there is a harmful agent somewhere in the building, later confirmed by reports of people being harmed, after the agent has been allowed to further spread.
[0048] Numerous advantages of the invention covered by this document have been set forth in the foregoing description. It will be understood, however, that this disclosure is, in many respects, only illustrative. Changes may be made in details, particularly in matters of shape, size, and arrangement of parts without exceeding the scope of the invention. The invention's scope is, of course, defined in the language in which the appended claims are expressed. | Systems and methods for monitoring buildings to detect harmful chemical or biological agents. Self-propelled harmful agent detectors are provided that can propel themselves using motors and self-contained power sources. On-board harmful agent sensors can detect the presence of harmful agents and transmit information for reception by a receiving unit. Some sensors can identify the type of agent and transmit the agent type. Some detectors can measure the intensity or concentration of the harmful agent presence and transmit that intensity. Some systems include locating devices for determining positions of the roaming detectors, as well as mapping software to map the location of the individual moving detectors. Systems may include software for plotting the relative concentrations of agents detected to locate the origination of the source within the building. The moving detectors can have motors coupled to wheels, tracks, capstans, pulleys and winches to move the devices along floors, air ducts, and suspended or hanging wires. | 8 |
FIELD OF THE INVENTION
This invention generally relates to apparatus for printing halftone images and more particularly relates to an apparatus and method for modifying halftone dot size for an image processed by an imaging apparatus.
BACKGROUND OF THE INVENTION
In a digital printing workflow there is a need to be able to proof bitmap files used to make printing plates. Presently, customer artwork consisting of contone images, linework, and text, is first sent to a digital halftone proofer or inkjet printer. The artwork is corrected until the proof is approved for the press. In the case were the artwork is proofed on a digital halftone proofer such as described by Baek et al. in U.S. Pat. No. 5,164,742, the raster image processor (RIP) adjusts the input continuous tone data using a calibration dot-gain curve such that the tone-scale of the proof matches the tone-scale of the press-sheet. After the proof is approved, the job is sent to a second RIP which applies a second dot-gain curve for generating the plate used in the press-run.
The first and second RIPs may be the same but are typically separate and may be located apart from each other. The first and second RIPs are preferably the same type and version such that the halftone dots created and algorithms used by each device are an exact match. Many times the two RIPs are not an exact match, which can create problems. Sometimes incorrect dot-gain correction files are used. Sometimes the artwork is changed in-between creating the proof and the plates and the press-run no longer matches the approved proof.
Another disadvantage in the current system is that an error in the creation of the bitmaps for printing is not known until the plates are loaded onto the press and the press-run is started. For a press capable of over 1,000 impressions per hour considerable amount of production is lost if the plates are found to be corrupt and need to be remade.
An important aspect in creating a halftone proof is predicting dot-gain or tone-scale. Dot-gain is a known phenomenon attributable to ink spread, ink absorption by the print media, and optical effects between the ink and the paper. The dot-gain varies with the size and shape of the halftone dots, the printing device, the inks, and the paper used, etc. For a digital proof, halftone dots in a color separation are composed of micro-pixels that give the halftone dot its shape and size. Dot-gain for a digital proof corresponds to increasing dot size by adding micro-pixels. Dot-loss for a digital proof corresponds to decreasing dot size by eliminating micro-pixels. Dot-gain correction consists of adding and subtracting gain to match the response at different percent dot inputs.
In the printer described by Baek et al. many steps are required to match the press. First the exposure for each color plane is adjusted to match the solid area density. Second the dot-gain for each color plane is adjusted to achieve a dot-gain match at different halftone tint levels. Third the dot-gain curves and density levels may be fine tuned to achieve either a good neutral match in the three color overprints or a color match for flesh tones. For some work, other memory colors such as green grass or light blue sky may be matched as the critical color. Finally the dot-gain curves may be further adjusted to deliver better performance in the highlight, or shadow areas. These steps are critical and typically take much iteration between the proof operator and the customer to achieve the look that the customer desires. It is important to be able to adjust the proofer to achieve this look as there are other controls on the press that may be adjusted to effect the dot-gain and tonal control of the press-run. By adjusting the performance of the proofer, the customer is selecting the quality of the proofs that will be used by the pressmen to match.
Once the proofer has been setup to match the press, the customer uses subsequent proofs to setup the press. This is an important point. The proofer setup is used to simulate the press such that the pressman may then use the proofs to setup the press to achieve the customer's intent. Every job going through the proofer will be adjusted with a setup. There may be different setups for each press or press type. There may also be different setups for different customers using the same proofer. Finally there may also be standard setups that are used to simulate jobs across many different presses.
The same job is typically “ripped” again when going to press. This time the RIP is programmed to generate 50% area coverage on plate for the 50% color input. The press is then run to deliver a fixed amount of gain at the 50% input level. Dot-gain is due to the smearing of the ink from the plate to a blanket, the smearing of ink from the blanket to the job paper, and the optical gain of the ink on top of the paper. The control is usually split between the plate making device delivering 50% area coverage for a 50% input, and the press delivering 50% plus its intrinsic dot-gain. Typical dot-gain levels for a Web-fed offset press are 15% to 25% at the 50% input level. Because the dot-gain occurs on the press instead of at the plate writer the bitmaps used to create the plate will not contain enough gain to make the proof. Proofs made from these bitmaps will be washed out and the contrast will be significantly reduced. Colors will also shift, as the gain in each color will be proportional to the dot area coverage.
Other digital halftone printing devices such as that disclosed by Michalson in U.S. Pat. No. 6,204,874 use a binary proofing media that does not allow for adjusting the density level of the solid colorants. A different process is used to adjust these devices for a close press match, including adjusting the tone-scale or dot-gain curve used to make the bitmap file. However the ideal dot-gain curve on these systems is still different from the dot-gain curves used to make the plates. Even if the same machine is imaging the plate and the proof as disclosed by Michalson.
Inkjet printing devices are also sometimes used to make a proof. These devices typically image from 300 dpi to 1440 dpi writing resolutions using multiple cyan, magenta, yellow, and sometimes black inks. In addition software such as “Best Screen Proof” available from Best Gmbh, or Black Magic available from Serendipity Software Pty Ltd., may be used to simulate the printing of a halftone screen. This software attempts to measure the halftone screen and adjust the printed output to achieve a close color match to a given target. Resolution of the inkjet devices does not allow for a good match of the halftone dot structure. The color match developed does simulate the tone-scale or dot-gain correction, but only through the driving of the overlapping colors on the proof. The quality of the halftone in the printed proof is significantly compromised. Dots in the highlight and shadow areas are destroyed in trying to match the overall density level in these systems. This is because the inkjet output drops are too large. Therefore one inkjet drop is used to replace many halftone dots in the highlight or bright areas, while one inkjet hole is used to replace many halftone holes in the shadows.
A halftone screen at 150 lines per inch, 6 lines per mm, covers an area of approximately 28,674 μm 2 . An inkjet printer with a 3 pL drop size will produce a dot with a diameter of about 25 μm covering an area of 625 μm 2 . This may vary depending upon the spread into the paper. A single inkjet drop represents a 2.18% change in area within a 150 line screen halftone. To achieve finer resolution the Best Screen Proof, and Black Magic, software use additional inks to image multi-level colorants. Typically a light cyan and light magenta ink are added to the cyan, magenta, yellow, and black primaries to achieve finer control of the tone-scale. While this creates a proof with a close visual color match, the structure of the halftone dots within the image is seriously degraded.
The conventional proofing solution, using the Kodak Approval Direct Digital Color Halftone Proofer, is to rip the file for proofing separate from ripping the file for printing, adding dot-gain to the proofing file as part of the ripping process. U.S. Pat. No. 5,255,085 describes a method to adjust the tone reproduction curve of a press or output printer. U.S. Pat. No. 5,255,085 creates a target from the press or desired output proof, benchmarks the characteristics of the proofing device, and discloses a method to generate a lookup table to adjust the dot-gain of the original file to achieve the aim on the proofing device. U.S. Pat. No. 5,293,539 adds adaptive process values to interpolate between measured Benchmark and Aim data sets to calibrate the dot-gain tone-scale curve at other screen rulings, screen angles, and dot shapes. Utilizing these techniques to modify the dot-gain curves and hence the tone-scale curves of the proofing device increases the chances for error. The input file and its subsequent components must be available for both rips. The same versions of each file and components must be specified. The same fonts must be available for both rips. The correct dot-gain curve must be specified at both rips. The chances for error to occur increase with each ripping operation, especially when the rips are located at separate sites.
Ripping the file twice is also time consuming. Each rip operation must read the input files, decide where each of the components is to be placed in the output print, convert continuous tone images using the correct dot-gain curve into high resolution halftones, render text and linework, and output a high resolution bitmap which represents the composite image. This is repeated for each color in the output print.
The Kodak Approval Direct Digital Color Halftone Proofer implements dot-gain by modifying the code values being printed through a curve prior to converting the code values into the halftone bitmap with the raster image processor. The dot-gain is only applied to the continuous tone image data and not the line work or text. The dot-gain may be adjusted for each of the primary colors cyan, magenta, yellow, and black. A dot-gain curve may also be specified for spot colors orange, green, red, blue, white, and metallic. A dot-gain curve may also be Murray - Daives Dot Area Calculation
PercentArea = 10 - Dtint - 10 - Dpaper 10 - Dsolid - 10 - Dpaper Equation 1
specified for a recipe color which is imaged using a single bitmap in combination of two or more standard colors at unique exposure levels. A dot-gain curve may also be specified for each colorant within a recipe color. In this last case more than one bitmap is used, however the halftone dots are at the same screen ruling, screen angle, and phase, such that each halftone dot in each color substantially overlap.
A typical example is a target curve. Such a target might specify that the 50% cyan halftone should print at 67%, the 25% cyan halftone should print at 35%, and the 75% cyan halftone should print at 80%. A benchmark proof is then run and measured. Dot area is calculated based on measured density using the equation defined by Murray-Davies. Equation 1 is the Murray-Davies equation is defined in ANSI/CGATS.4-1993; 1993, p. 7. A dot-gain adjustment curve is then created to add the correct amount to cyan to achieve the target values at the target inputs. For instance in this example we might find that an output value of 35% was achieved at an input level of 30% in the benchmark proof. Therefore 5% dot-gain at the 25% input level is added to achieve the 35% target. At the 50% level we may find we achieved the target level of 67% at an input level of 57% requiring us to add 7% at the 50% input. At the 75% level we may find we achieved the 80% target at the 76% input requiring 1% dot-gain. In actual practice we may measure the dot-gain in 5% or 10% steps with some additional measurements between 0 to 10% and 90 to 100%. A spline curve is usually fit to the resulting dot-gain curve to provide a table in 1% input increments or less. Smoothing is sometimes performed on the input target and benchmark data to further reduce artifacts in the adjustment process.
Perup Oskofot has shown a software program, which operates on high resolution scans from their scanners. The program takes a binary high-resolution scan of a halftone film and descreens it to a lower resolution continuous tone image. Typically the scan resolution is 2400 dpi. The resulting continuous tone image may be 8 bits per pixel at 300 dpi resolution. A dot-gain curve is then applied to the descreened image. The adjusted image is then ripped to a bitmap image at 2400 dpi. This software system was disclosed at Drupa 2000, a tradeshow. One problem with this method is that it requires a reripping step. To accomplish this requires a RIP. Plus we need to know what the original halftone screen shape, screen ruling, and screen angle were in order to faithfully reproduce it with the re-ripping step. Another problem is that all RIPs are not the same. There are subtle differences between them such as the method that they use to add noise to hide the quantization affects in screening the image. This means that one RIP may not sufficiently reproduce all the screens that the customer might digitize. Another problem with this method is that it is extremely slow. A small 8×10 inch image at 2400 dpi scanned resolution took more than an hour to process a single color plane.
Additionally, some customers have halftone films, which they would like to use in their digital workflow. These customers scan the film at a high resolution, for example 100 pixels/mm, and quantize each pixel to a binary value. Because the dot-gain is built into the film, there is no method other than descreening the bitmap file, adding dot-gain, and reripping the file, to calibrate the output print. If the original film was made using an optical technique then the dot shape, screen ruling, and screen angle may not be an exact match to a digital RIP. Descreening and rescreening the high resolution scan may not faithfully reproduce the original screens.
Denber et. al. disclose a method of shifting and adding a bitmap image with itself to thin the image displayed in U.S. Pat. No. 5,250,934. Denber discloses a method of setting a bit to an intermediate level if it is diagonally between two active bits using shifting, logical and, and a logical or operation.
U.S. Pat. No. 5,483,351 discloses using a 4×4 input to a lookup table to determine how to operate on the central 2×2 pixels to implement halfbit or fullbit dilation and erosion in U.S. Pat. No. 5,483,351. U.S. Pat. No. 5,483,351 has the advantage of knowing some of the surrounding pixels in deciding how to dilate or erode the pixels in the center. Eschbach teaches us in U.S. Pat. No. 5,258,854 how to resize bitmap images in small amounts less than one full bit in size.
Loce et al. discloses logically combining two morphological filter pairs and an original image to create an output image in U.S. Pat. No. 5,680,485. The morphological filters described are erosion filters, one of which has less erosion than desired and the other having more erosion than desired. Logically combining combinations of the original image with the two eroded images provides for a method of obtaining an intermediate result.
Eschback describes a method of resizing an input bitmap in U.S. Pat. No. 5,208,871, which simulates a scan of an output image from an input bitmap such that the scan resolution is different from the input bitmap. Error diffusion is utilized to quantize the output bitmap into the desired output bit resolution. This example uses error diffusion to spread out the error in the quantization of a multilevel pixel into a reduced number of output states.
U.S. Pat. No. 6,115,140 uses a descreened version of an original image, and dilated and eroded versions of the original image to select a combination of the original, dilated, and eroded images to effect a dot-gain or tone-scale change in an input bitmap image. U.S. Pat. No. 6,115,140, FIG. 5 B shows an original halftone image input into block H 1 along with an eroded version (HE), and two dilated versions (HD 1 and HD 2 ). Then a weight based on descreened versions of the original halftone (CO), the color corrected original (CI), the eroded original (CE), and the two dilated originals (CD 1 and CD 2 ) is calculated. The descreened images are used to select which of the four halftone images, HI, HE, HD 1 , and HD 2 , are transferred into H 1 and H 2 . The weighting function is then used to merge bitmap versions of H 1 and H 2 together into the tone-scaled output bitmap (HO). How to descreen is not disclosed, nor exactly how to calculate which bit of H 1 and H 2 is used to drive the output bit HO. The need to use error diffusion to distribute the error in selecting between H 1 or H 2 is not mentioned.
In U.S. Pat. No. 6,115,140 dilation is described as growing a single pixel completely around the halftone feature. A second dilation grows two pixels completely around the halftone feature. Similarly erosion subtracts a single pixel completely around the halftone feature.
None of the Bressler et al. references teach how to perform descreening. Roetling performs descreening by comparing the number of white and dark pixels within a specified area in U.S. Pat. No. 4,630,125. U.S. Pat. No. 4,630,125 also states that “A partial solution known in the art is to spatially filter the halftone image with a low pass filter.” U.S. Pat. No. 4,630,125 teaches that the spatial filter method is not exact as it tends to blur the original image.
Thus, there exists a need for optimizing the process of adding dot-gain while maintaining dot fidelity. A system that adds dot-gain to bitmaps used to make printing plates, and that proofs these bitmaps so that the press-sheets made with same printing plates are known prior to running the plates on press, does not exist.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method of implementing dot-gain correction to digital halftone bitmap files directly without descreening then reripping the data.
It is an object of the present invention to provide a method of implementing dot-gain correction to digital halftone bitmap files while preserving dot fidelity; wherein halftone dots in the original bitmaps will not be created; wherein halftone dots will not be created in the output proof, where there were none there to begin with; and wherein holes will not be created in solid areas where there were no holes to begin with.
Briefly, according to one aspect of the present invention a system for printing a halftone digital image on both a printing press and a color proofer using the same binary digital data comprises sending the binary digital data to the printing press. The binary digital data is sent to a dot-gain processor for conditioning the binary digital data to introduce a predetermined level of dot-gain. The binary digital data is transmitted to the color proofer and a halftone color proof is printed on the color proofer.
A feature of the present invention is that it uses the same rasterized file for prepress and final press operations. This provides a high measure of confidence for a customer who purchases a printed product based on a digital proof.
It is an advantage of the present invention to allow a straightforward method that compensates for dot-gain in order to predict the final appearance of the digital halftone image. Because it operates on a file that is rasterized once, the method of the present invention allows dot-gain for an image to be adjusted without requiring an additional time consuming rasterization process.
It is an advantage of the present invention to provide a method that can be used to adapt a rasterized file to one or more prepress apparatus.
It is an advantage of the present invention to provide a proofing and printing system, which has the capability to adjust the binary bitmap files to make the proof and the print appear to be visually the same.
It is an advantage of the present invention that the press-sheet may be estimated and approved prior to taking the press down to mount and align the plates.
These and other objects, features, and advantages of the present invention will become apparent to those skilled in the art upon a reading of the following detailed description when taken in conjunction with the drawings wherein there is shown and described an illustrative embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, it is believed that the invention will be better understood from the following description when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a block diagram showing the conventional workflow for digital halftone file processing;
FIG. 2 is a block diagram showing the method of the present invention for adding dot-gain to a digital halftone file;
FIG. 3 is a flow diagram showing the processing steps for adding dot-gain compensation to a rasterized halftone digital image file;
FIG. 4 contains a graph of percent dot out verses percent dot in by threshold value for the dot-gain method described;
FIG. 5 contains a spatial filter used in one example;
FIGS. 6 a-c show an input bitmap ( 6 a ), an output bitmap with gain ( 6 b ), and an output bitmap with dot loss ( 6 c );
FIG. 7 is a block diagram showing the method of the present invention for adding dot-gain to the digital halftone files used to make the printing plates; and
FIG. 8 is a block diagram showing the method of the present invention for adding dot-gain to the digital halftone files for use in making the proof, and adding dot-gain to the same digital halftone files for use in making the plates.
DETAILED DESCRIPTION OF THE INVENTION
The present description is directed in particular to elements forming part of, or cooperating more directly with, apparatus in accordance with the invention. It is to be understood that elements not specifically shown or described may take various forms well known to those skilled in the art.
Referring to FIG. 1, there is shown a prepress workstation 10 , with customer artwork stored on disk 20 . The customer may store images, text and line-work on disk 20 . The customer may use a program such as Quark's QuarkXPress to combine the images, text, and line-work into a job consisting of one or more pages. The QuarkXPress Program running on the prepress workstation 10 may output the job as a postscript or portable document format (PDF), file to either the RIP for proofing 30 , or the RIP for printing 40 . Each RIP may consist of a software RIP running on a PC such as Harlequin “ScriptWorks” by Global Graphics Software LTD.
RIP 30 has a postscript text file, which specifies the dot-gain adjustment for proofing to be applied to all of the continuous tone images within the customer job. This file contains the input and output percent dot relationships for all the colors in the job. The procedure to create this lookup table is described by Spence and implemented in Kodak software, “Dot-gain Manager”, which is available in Kodak Approval Digital Halftone Proofers. The RIP will convert CMYK continuous tone images through the dot-gain lookup table. Then the RIP will convert the continuous tone image into a halftone image at the writing resolution of the proofing system 60 . The halftone bitmap images may be sent directly from RIP 30 to printer 60 or they may be temporarily stored on disk 50 . The proofing system outputs a digital halftone color proof 65 .
RIP 40 will have a similar postscript text file that specifies the dot-gain adjustment for press to be applied to all of the continuous tone images within the customer job. The dot-gain curve on RIP 40 may be used to linearize the plate such that a 50% input creates 50% dot area coverage on plate. The 50% dot area coverage on the plate then produces a press sheet on press with additional gain. The plate writer 70 may have an intrinsic gain associated with it, which is compensated for in the same dot-gain curve in RIP 40 . The plate writing system 70 may be positive or negative writing, such that areas exposed on plate may accept or reject ink on press. The positive or negative sense of the plate writer will typically require negative or positive dot-gain adjustment to create a linear plate. Typically plate writers have a loss or gain of 1% to 3%.
The plate writing system 70 may be co-located in the printing press 80 . In this case the press contains additional capability of being able to image the printing plates which are already mounted on the press.
A digital film writer 100 may precede the plate writing system. The bitmaps used to make the film or plate may be stored temporarily on disk 90 prior to making the film or plate. If a digital film writer is used then the films may be used to make the plate by making an optical contact exposure. This is a well known process in the art. The additional dot-gain or dot loss due to the contact exposure and processing of the plate may be compensated for in the dot-gain curves used to make the film.
It is understood that there may also be iterative steps of making film and plates with the end result of a plate being mounted in the press used to create a press sheet with the customer artwork. The dot-gain curve used in RIP 40 may contain compensation for all of the steps used to create the plate. In addition the dot-gain curve in RIP 40 may also contain compensation for a given press to achieve a desired target.
The plate writing system 70 outputs a set of digital plates 75 used in the printing press 80 to create color halftone press-sheets 85 . Note that the invention may also be used in black and white, single, or multiple color systems and is not limited to process color, Cyan, Magenta, Yellow, and Black, printing systems.
Referring now to FIG. 2 we show one preferred embodiment of our invention. The customer artwork is stored on disk 20 . The customer may store images, text and, line-work on disk 20 . The customer may use a program such as Quark's QuarkXPress to combine the images, text, and line-work into a job consisting of one or more pages. The QuarkXPress Program running on the prepress workstation 10 may output the job as a postscript or portable document format (PDF), file to the RIP 40 for printing and or proofing. The RIP may consist of a software RIP running on a PC such as Harlequin “ScriptWorks” by Global Graphics Software LTD.
RIP 40 will have a postscript text file which will specify the dot-gain adjustment for press to apply to all of the continuous tone images within the customer job. The dot-gain curve on RIP 40 may be used to linearize the plate such that a 50% input creates 50% dot area coverage on plate. The 50% dot area coverage on the plate then produces a press sheet on press with additional gain. The plate writer 70 may have an intrinsic gain associated with it, which is compensated for in the dot-gain curve in RIP 40 . The plate writing system 70 may be positive or negative writing, such that areas exposed on plate may accept or reject ink on press. The positive or negative sense of the plate writer will typically require negative or positive dot-gain adjustment to create a linear plate. Typically plate writers have a loss or gain of 1% to 3%.
The plate writing system 70 may be co-located in the printing press 80 . In this case the press contains additional capability of being able to image the printing plates which are already mounted on the press.
A digital film writer 100 may precede the plate writing system. The bitmaps used to make the film or plate may be stored temporarily on disk 90 prior to making the film or plate. If a digital film writer is used then the films may be used to make the plate by making an optical contact exposure. This is a well known process in the art. The additional dot-gain or dot loss due to the contact exposure and processing of the plate may be compensated for in the dot-gain curves used to make the film.
It is understood that there may also be iterative steps of making film and plates with the end result of a plate being mounted in the press used to create a press sheet with the customer artwork. The dot-gain curve used in RIP 40 may contain compensation for all of the steps used to create the plate. In addition the dot-gain curve in RIP 40 may also contain compensation for a given press to achieve a desired target.
The plate writing system 70 outputs a set of digital plates 75 used in the printing press 80 to create color halftone press-sheets 85 .
The bitmap images stored or copied to disk may also be sent using dot-gain correction box 110 to the proofing system 60 . In this case the dot-gain correction box 110 would be programmed to unbuild the dot-gain curves used to make the plates and add the dot-gain correction required to allow the proofing system 60 to match the target. The unbuild and dot-gain correction is performed in one step using a single combined curve.
To obtain the dot-gain curve used in the dot-gain on bitmap calculation the customer runs a test proof through the RIP 40 to make plates 75 and a press sheet 85 on press 80 . The press sheet 85 made with the test proof is measured and becomes the target press sheet values. The bitmaps made for the test proof are stored in disk 90 . These same bitmaps are pass directly to the proofing system 60 bypassing the dot-gain on bitmap calculation 110 . The resulting proof is called the benchmark proof 65 . The benchmark proof is measured and compared to the target press sheet values. The dot-gain adjustment required to add to the percent dot into the dot-gain on bitmaps calculator 110 are calculated by finding or calculating the input value resulting in an output value on the benchmark proof required to achieve the output value on the target press sheet.
In order to show how this dot-gain adjustment is used we will now discuss one implementation of the dot-gain on bitmaps calculation. One skilled in the art will recognize that this is just one implementation of performing the dot- gain directly on bitmap files and that other implementations such as Bressler et al. may be substituted to accomplish the same effect.
The dot-gain on bitmap calculation is performed as shown in FIG. 3 . The halftone bitmap image on plate writing system disk 90 is convolved through a spatial filter 200 to create a blurred continuous tone image 210 . The halftone bitmap image 90 is simultaneously passed through an averager filter 220 to create a local area averaged image 230 . For each pixel in the image the averaged image 230 is used to estimate the dot area in. The output of the averager 230 is input to a lookup table 240 , which contains a table of threshold levels 250 . For each pixel the level of the blurred image 210 is compared to the threshold value 250 in comparator 260 . The output of the comparator 260 is the dot-gain adjusted halftone bitmap 270 . This bitmap 270 is then sent to the proofer 60 . For this example FIG. 5 is used for the spatial filter 200 . The averager size is 13 pixels by 13 lines.
To compute the table of threshold levels 250 required to achieve the desired dot-gain curve we use a test proof instead of the customer artwork located in disk 20 . The test proof consists of solid tints from 0% to 100%. For each tint, the RIP 40 creates the bitmap on disk 90 . The same bitmap is run through the dot-gain compensation circuit 110 using fixed threshold values from 0 to 53. These values depend on the spatial filter chosen. For our example we used the spatial filter shown in FIG. 5 . The output of the average 210 is also recorded for each tint. For this example we used a 13 pixel by 13 line averager. This is our measure of percent dot in, expressed as averager output. We then print the output bitmap 270 and measure the resulting density on the print. We convert the density to percent dot using the Murray-Davies equation. Dot-gain is calculated by subtracting the percent dot input from the measured percent dot output. We may now plot percent dot-gain verses percent dot input verses threshold level giving us FIG. 4 . We need one more relationship between percent dot input verses averager output to determine the lookup table address for the given percent dot in. This may be obtained by recording the averager output during the processing of each solid tint, or counting the average number of pixels on within an area of the same size as the averager for each tint in bitmap 90 . To estimate the threshold for intermediate points we may perform a spline curve fit.
To compute the table of threshold levels 250 required to achieve the desired dot-gain curve for a scanned halftone bitmap input we repeat the process using a scanned tint scale instead of the customer artwork Note that each screen ruling, screen angle, and-dot shape will have a different response and must be modeled separately. The described embodiment requires numerous calculation steps prior to performing the dot-gain compensation on the customer's bitmaps, however these steps may be performed ahead of time so that the actual dot-gain correction may be replicated quickly on each incoming bitmap file.
A single bit in a 2540 dot per inch, 100 micro-pixels per mm., bitmap file represents an area of 100 um 2 . In a 150 line screen halftone, 6 lines per mm., this represents a 0.34% dot change allowing us to faithfully reproduce a given dot-gain target by adding or subtracting micro-pixels within the bitmap file.
FIGS. 6 a , 6 b , and 6 c , are an example showing how the bitmaps might be modified using this invention. FIG. 6 a shows an input dot with 12 micro-pixels on, 290 . Off micro-pixels are shown as 280 . The 13×13 averager output would be 12 out of a possible 169 for a percent dot input of approximately 7.1%. FIG. 6 b shows an addition of 5 micro-pixels 300 , for an output halftone dot consisting of a total of 17 micro-pixels or approximately 10.1%. FIG. 6 c shows a subtraction of 2 micro-pixels 310 , for a dot loss of 1.1%. It is an invention of our copending application that the spatial filter blurs the incoming bitmap, while the threshold and compare operation defines a new outline of the existing halftone dot. This preserves the halftone dot in the output bitmap while adjusting the apparent tonescale of the output image. To compensate for different halftone screen rulings and angles the size of the averager needs to change. Also the averager may be larger than one halftone cell such that the calculated dot percentage may be based on a fractional output of the averager.
Referring now to FIG. 7 we show another embodiment of our invention. The customer artwork is stored on disk 20 . The customer may store images, text and, line-work on disk 20 . The customer may use a program such as Quark's QuarkXPress to combine the images, text, and line-work into a job consisting of one or more pages. The QuarkXPress Program running on the prepress workstation 10 may output the job as a postscript or portable document format (PDF), file to the RIP 30 for proofing and printing. The RIP may consist of a software RIP running on a PC such as Harlequin “ScriptWorks” by Global Graphics Software LTD. RIP 30 will have a postscript text file which will specify the dot-gain adjustment for proofing to apply to all of the continuous tone images within the customer job. The dot-gain curve on RIP 30 may be used to match a known standard such as the Committee for Graphic Arts Technical Standardization (CGATS) Technical Report 001 (TR001).
Rip 30 will output cyan, magenta, yellow, and black bitmaps to disk 50 on their way to proofer 60 to create proof 65 . The bitmaps for proofing may also be used with our invention 111 to create printing plates 75 . Here our invention, 111 , dot-gain correction box for printing will be programmed to unbuild the dot-gain correction for proofing and build in the dot-gain correction required such that the press-sheet 85 matches the proof 65 .
The plate writing system 70 may be co-located in the printing press 80 . In this case the press contains additional capability of being able to image the printing plates which are already mounted on the press.
A digital film writer 100 may precede the plate writing system. The dot-gain correction device 111 would then be programmed to take into account the additional gain or loss required due to the digital film writer, 100 , and the contact process of making the plates 75 .
It is understood that there may also be iterative steps of making film and plates with the end result of a plate being mounted in the press used to create a press sheet with the customer artwork. The dot-gain curve used in the dot-gain correction device 111 may contain compensation for all of the steps used to create the plate. In addition the dot-gain curve may also contain compensation for a given press to achieve a desired target.
To obtain the dot-gain curve used in the dot-gain on bitmap calculation the customer runs a test proof through the RIP 30 to make plates 75 and a press sheet 85 on press 80 . The press sheet 85 made with the test proof is measured and becomes the benchmark press sheet values. The bitmaps made for the test proof are stored in disk 50 . These same bitmaps are passed directly to the proofing system 60 . The resulting proof is called the target proof 65 . The benchmark proof is measured and compared to the target proof values. The dot- gain adjustment required to add or subtract to the percent dot into the dot-gain on bitmaps calculator 111 are calculated by finding or calculating the input value resulting in an output value on the benchmark proof required to achieve the output value on the target proof.
Referring now to FIG. 8 we show another embodiment of our invention. The customer artwork is stored on disk 20 . The customer may store images, text and, line-work on disk 20 . The customer may use a program such as Quark's QuarkXPress to combine the images, text, and line-work into a job consisting of one or more pages. The QuarkXPress Program running on the prepress workstation 10 may output the job as a postscript or portable document format (PDF), file to the RIP 41 for proofing and printing. The RIP may consist of a software RIP running on a PC such as Harlequin “ScriptWorks” by Global Graphics Software LTD. RIP 41 will have a postscript text file which will specify the dot-gain adjustment to apply to all of the continuous tone images within the customer job. The dot-gain curve on RIP 41 may be used to match a known standard such as the Committee for Graphic Arts Technical Standardization (CGATS) Technical Report 001 (TR001).
Rip 41 will output cyan, magenta, yellow, and black bitmaps to disk 51 on their way to proofer 60 and plate writer 70 .
A high resolution scanner 43 may also be used to generate digital bitmap files from scans of analog films to be stored on disk 51 on their way to the proofer 60 and plate writer 70 .
A dot-gain on bitmaps calculator 110 may be used to modify the bitmaps stored on disk 51 for creating proof 65 with proofer 60 . Another dot-gain on bitmaps calculate 111 may be used to modify the bitmaps stored on disk 51 for creating press-sheet 85 on press 80 using plates 75 from plate writer 70 or digital film writer 100 .
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the scope of the invention as described above, and as noted in the appended claims, by a person of ordinary skill in the art without departing from the scope of the invention.
PARTS LIST
10.
Prepress workstation
20.
Disk with customer artwork
30.
Raster image processor (RIP) for proofing
40.
Raster image processor (RIP) for printing
43.
High resolution film scanner.
50.
Proofing system disk
51.
Proofing and printing system disk
60.
Proofing system
65.
Digital halftone color proof
70.
Plate writer
75.
Plates
80.
Printing press
85.
Color halftone press-sheet
90.
Plate writing system disk
100.
Digital film writer
110.
Dot-gain correction box for proofing
111.
Dot-gain correction box for printing
200.
Spatial filter
210.
Blurred continuous tone image
220.
Averager filter
230.
Local area averaged image
240.
Lookup table
250.
Threshold values
260.
Comparator
270.
Dot-gain adjusted halftone bitmap
280.
Off micro-pixel
290.
On micro-pixel
300.
Additional micro-pixel to add dot-gain
310.
Deleted micro-pixel to subtract dot-gain | An apparatus and method for applying dot-gain ( 110 ) compensation to halftone bitmap files used in printing a digital halftone image. Dot-gain is added by thresholding ( 250 ) the output of a convolution of the original bitmap image with a spatial filter ( 200 ). Averaging ( 220 ) is performed to specify the level of the threshold to be applied. The level of dot-gain applied is a function of the threshold level. | 7 |
BACKGROUND OF THE INVENTION
1. Field of The Invention
The apparatus of the present invention relates to downhole valves. More particularly, the present invention relates to a disc valve, constructed of a breakable material, such as glass, positioned in the flowbore of a tubing string that prevents flow of fluid through the bore from either direction. When flow is desired, the breakable disc is ruptured, and the flow is allowed to commence within the bore.
2. General Background
In the general process for drilling and production of oil and gas wells, at that point in the process where a hydrocarbon formation has been located at a particular depth, normally an exterior casing would be lowered down the borehole through the area of production, known as the production zone. The exterior casing is perforated with the use of a perforating gun or the like. Using electric wireline and setting tools, or some other means, a permanent type packer, referred to as a "sump packer" is usually set below the perforations. Subsequently, an internal tubing string, together with sand screen and blank pipe, packer and packer extension, hydraulic setting tool, cross-over tool, and wash pipe, are positioned within the exterior casing to engage with the "sump packer". The annulus between the sand screen and the exterior perforated casing is packed off, utilizing certain procedures. This packing off is necessary so that the interior tubing would be utilized to carry the recovered hydrocarbons to the surface. The area around the perforations is prepared, so that the flow of hydrocarbons may commence.
For example, the well must be gravel packed, so that the flow of sand or the like out of the formation is prevented during recovery of the hydrocarbons. The present invention would be utilized following the gravel packing procedure, with the assignee company, Completion Services, Inc., would designate as the "Complete Gravel Pack," which would include a hydraulic setting tool and crossover being run into the well with the required sandscreen and blank pipe. The packer assembly would be seated using pump pressure applied to the tubing. After it is seated, the crossover valve may be opened and closed. With the crossover valve closed, the packer may be pressure tested by pumping down the casing. Fluid may be pumped into the formation to establish injection rate. Also, the formation may be acidized, if necessary. With the crossover valve open, sand slurry may be circulated to place sand outside of the screen and into the formation until adequate gravel pack is obtained. After removal of the setting tool and crossover, a production seal assembly is run in for production of the zone.
After gravel packing is complete, oftentimes the well may not necessarily be pressure balanced. The formation, under these conditions, may tend to absorb the well fluid into the production zone or the fluid in the zone may tend to flow into the well. In either case, this could lead to unacceptable (a) loss of expensive well fluid, (b) damage to the formation, (c) danger of a potential well blow-out or co-mingling of formation fluids. In the present state of the art, if there can be a prediction in which direction the pressure differential will exist within the well, a flapper valve can be utilized which would hold pressure in one direction only. However, flapper valves can be easily damaged, activated premature, leak or rupture at too low a pressure differential. Therefore, there is a need in the art for a valve which would prevent the movement of fluids within the well bore in either direction, and under varying degrees of pressure differential within the well.
There have been patents issued in the art which relate to valves in operation downhole, during the recovery of hydrocarbons during production, etc., the most pertinent being as follows:
______________________________________U.S. Pat. No. TITLE ISSUE DATE______________________________________4,658,902 "Surging Fluids Downhole In Apr. 21, 1987 An Earth Borehole"4,651,827 "Hydraulically Controlled Mar. 24, 1987 Safety Valves For Incorporation In Production Tubes Of Hydrocarbon Production Wells"4,691,775 "Isolation Valve With Frangible Sep. 8, 1987 Flapper Element"3,831,680 "Pressure Responsive Auxiliary Aug. 27, 1974 Disc Valve And The Like For Well Cleaning, Testing And Other Operations"3,599,713 "Method And Apparatus For Aug. 17, 1971 Controlling The Filling Of Drill Pipe Or The Like With Mud During Lowering Thereof"3,024,846 "Dual Completion Packer Tool" Nov. 15, 19572,855,943 "Circulation Port Assemblies Oct. 14, 1958 For Tubing Or Well Pipe"2,626,177 "Tool For Hydraulically Jan. 20, 1953 Displacing Well Materials"2,565,731 "Disk Perforator For Pipes Aug. 28, 1951 In Wells"2,545,504 "Completion Shoe" Mar. 20, 1951______________________________________
Other objects of the invention will be obvious to those skilled in the art from the following description of the invention.
SUMMARY OF THE PRESENT INVENTION
The apparatus of the present invention solves the problems in the art in a simple and straightforward manner. What is provided is a travelling disc valve apparatus, positionable within the bore of a tubing string, to control differential pressures from above or below the position of the valve. The valve is engaged to the wash pipe and used during gravel packing operation. When gravel packing is concluded, the valve is then placed in position by raising the wash pipe to the upper seal bore, latching the valve in position. The wash pipe is then sheared from the safety valve, and the valve is sealing fluid flow in either direction. Upon lowering of a tool on a wireline, the glass travelling disc valve is then ruptured, and production flow up the string is allowed to proceed.
Therefore, it is a principal object of the present invention to provide a travelling disc valve positioned in a tubing string to provide control of differential pressures from above or below the valve;
It is a further object of the present invention to provide a valve which can be positioned in varied locations within the tubing string, and effects a positive seal when latched into position;
It is still a further object of the present invention to provide a disc valve which, prevents loss of contaminating fluids, and prevents loss of the expensive completion fluids involved in the completion of an oil or gas well; and
It is still a further object of the present invention to provide a disc valve which is flexible in its use downhole, and eliminates the difficulties of spring activated metal to metal, or metal to o-ring seal valves, such as flapper valves.
BRIEF DESCRIPTION OF THE DRAWINGS
For a further understanding of the nature and objects of the present invention, reference should be had to the following detailed description taken in conjunction with the accompanying drawings, in which like parts are given like reference numerals, and wherein:
FIG. 1A through 1G illustrated cross-section views of isolated components making up the upper and lower sections of the lower circulation configuration utilizing the present invention;
FIG. 1H is an overall view of the components of the assembly as illustrated in FIGS. 1A through 1G, including the components in the tubing string situation directly above the assembly components that are illustrated in FIG. 1H;
FIGS. 2A through 2D illustrate in cross-section views, the isolated components of the assembly during upper circulation following the raising of the top seal ring out of sealing engagement with the bottom seal bore;
FIGS. 2E through 2G illustrate in cross-section views, the isolated components of the assembly further illustrating the upper section of the assembly after the wash pipe has been sheared and withdrawn from borehole and the disc valve is locked in position;
FIG. 3 illustrates a cross-section view of the manner in which the travelling disc valve of the present invention is ruptured and removed to allow flow as illustrated in FIGS. 4A and 4B; and
FIGS. 4A and 4B illustrate cross-section views of isolated components of the system utilizing the present invention, with the disc valve ruptured to allow production flow in the system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The apparatus of the present invention referred to as a travelling disc valve is illustrated in the figures by the numeral 10. As best seen in the drawings, the entire assembly housing the travelling disc valve assembly during lower circulation is shown in FIGS. 1A through 1G. The upper section of the assembly is illustrated in FIGS. 1A through 1D, and the lower section of the assembly illustrated in FIGS. 1E through 1G.
In FIG. 1H there is illustrated an overall composite view of the disc valve assembly as seen in its isolated components in FIGS. 1A through 1G, and the components in the tubing string positioned directly above the disc valve assembly. These would comprise upper setting tool and crossover assembly 114, with the compset packer 116 positioned directly below. Furthermore, there is illustrated the perforated extension 118, which is attached directly to the seal bore 120, which is positioned directly below the perforated extension 118. Furthermore, there is illustrated the indicator collet 122, and the no-go housing 124 for the disc valve 10. Directly below the no-go housing for the disc valve is a seal bore 126 for the disc valve 10, and thence the production screen 32 as illustrated in the isolated views, the top seal bore member 30, and thence the disc valve assembly 10 as will be discussed further.
As seen in FIG. 1G, travelling disc valve 10 comprises a solid piece of material, preferably glass, which may be of various thicknesses depending on the pressures downhole that may be encountered and various diameters depending on the size of the tubing in which the disc valve 10 is positioned. Disc 10 is positioned within a groove 12 in the wall of a collet member 14, as illustrated in FIG. 1G. Groove 12 is formed on its lower end by a circular end piece 18 threadably secured on the lower end of collet 14 which serves as the lower shoulder upon which the disc valve 10 rests in groove 12.
Turning now to the system in which travelling disc valve 10 functions, reference is made to FIG. 1A-1G, which comprise a series of isolated views of the system, extending from the upper packer extension 20 down to the lower most component, the sump packer 22. As seen in the FIGS. 1A through 1D, the packer extension 20 is threadably engaged to a top locator 24 which engages on its lowermost end a collet locator 26. The collet locator 26 interconnects to an elongated spacer 28, which, at its lower end engages the top seal bore member 30, to which bank tubing and the production screen 32 is suspended. Production screen 32, as illustrated in FIG. 1E would be a typical production screen having an outer screen layer 33, positioned around the screen support wall 33A. The support wall 33A would include a plurality of ports 33B so that production flow through the ports 35 in the wall of the production casing 36 into the annulus 37 of the production casing 36 , would flow into the internal bore of the production screen and up to the surface as will be described further. As seen in FIG. 1D and 1E, when production is commenced the hydrocarbon flow would move through the perforations in the wall of casing 36, into the annulus between the wall of casing 36 and the production screen 32, and then to the surface through the bore in the production string.
As seen further in FIGS. 1E through 1G, the lower end of production screen 32 would be connected to a bottom seal bore 40, for connecting to, at its lower end 41, a second screen, or a telltale screen 44, which would be connected to a bottom locator 50 and then to the lowest component, the sump packer 22, which would pack off the lowest most point of the assembly so that fluid or production flow could not pass that point during production.
As is illustrated in FIGS. 1A-1G, the components previously recited, referred collectively hereinafter as outer production assembly 100, further comprise a continuous internal bore 54 therethrough, in which there is housed the internal system for carrying the travelling disc valve 10, and will be referred to as the travelling disc valve assembly 102. Continuing to refer to FIGS. 1A through 1G, the assembly 102 would comprise an upper length of wash pipe 58 extending down the internal bore 54 of the outer assembly 100, and would extend and interconnect to a shear joint 56 the lower end of which would interconnect to a collet 57. The collet 57 would further include a first top seal ring 60 which would form a seal between the outer wall 59 of collet 57 and the inner wall of bottom seal bore member 40, to prevent fluid flow therebetween. Further, as seen in FIG. 1G, collet 57 would further interconnect to a spacer 59 which would in turn interconnect to second bottom seal rings 62 again for sealing against fluid flow as will be discussed further. Directly positioned below second bottom seal rings 62 traveling disc valve member 10, as discussed earlier. As seen in the FIGURES, during the process of lower circulation, the travelling disc valve 10 is positioned along the length of telltale screen 44, to prevent the travelling disc valve from interfering with lower or upper circulation.
Having discussed the components of the system, as illustrated in the Figures, a discussion will be had regarding the function of the travelling disc valve 10 in the system, which lends itself to the novelty of the valve 10. FIGS. 1A-1G comprise the series of figures showing the operation of the system and the location of the disc valve 10 during lower circulation. As illustrated in the Figures, the travelling disc valve 10 and related components have been positioned below the upper packer, not illustrated, with the crossover tool raised to the lower circulation position. While in this position, the sand slurry, following the packing off process as discussed, is pumped down the tubing, through the crossover ports into the casing annulus 37 below the packer 20, as seen by arrows 21, between the outer casing 36 and the outer assembly 100. The sand slurry flow, would then enter the telltale screen 44, through the plurality of ports 80 in the wall of the screen above the disc valve 10, up the bore 43 of the wash pipe 58 in the direction of Arrows 23, through the concentric passage 82 of the crossover tool and would continue to travel up the passage through the ports which would communicate with the casing annulus above the packer, not illustrated.
During the lower circulation process as described, the point at which sand has begun to accumulate against the ports in the telltale screen 44, would result in the retardation of the circulation of the fluid as previously described. Therefore, the pump pressure, at the surface would increase, would indicate that the crossover tool as in position as seen in FIGS. 1A through 1G should be raised by raising the wash pipe 44 in the hole, to the position that the first top seal ring 60 would be pulled from the position within the bottom seal bore 40, as seen more clearly in FIGS. 2D and 2E, and in position adjacent production screen 32 and through ports 45 in spacer 59. When this is accomplished in the process, the circulation through the production screen 32 would then be permitted through the ports 33B below the first top seal ring 60, allowing the flow to enter into the wash pipe in the direction of Arrows 23.
As in the earlier part of the process during lower circulation, when the sand has begun to accumulate against the production screen 32, again the pump pressure will increase which will force the sand slurry into the casing perforations 35, and then into the formation 104, surround the casing at the point of the perforations. The pressure would then be released and the crossover tool would then be raised until the crossover ports are above the packer. In this position, the excess sand slurry can then be circulated and returned back to the well surface by pumping down the annulus between the casing 36 and the tubing that extends to the surface of the well above the hydraulic setting tool and crossover tool. The fluid would then be received at the surface of the well through the tubing bore.
Upon the completion of the reverse circulation as seen and described, again reference is made to FIGS. 2D-2G where it is illustrated that the crossover tool and the wash pipe 44 are raised until the shear joint 56 positioned above the collet 57 is stopped in the top locator 24. At this point, shear screws 56A in the shear joint 56 will be sheared off, leaving the disc valve assembly, comprising the components below the shear joint 56 down to the disc valve 10 held in place by lower end piece 18 of the assembly. In this position, the second bottom seal rings 62 together with disc valve 10 provide a means to prevent fluid flow from entering into the formation from above the disc valve 10, or from preventing fluid or gas production to enter from the surrounding formation. At the point that the shear pins are sheared, the crossover tool and the wash pipe are then withdrawn from the hole, leaving the disc valve assembly as described. Although a shear joint is utilized in this preferred embodiment, any means for disconnecting the disc valve assembly from the washpipe 44.
Following the running of the production tubing and the seals into the well and stabbing to secure the packer, the disc valve 10 must be ruptured in order to clear the way for production of the well. Therefore, there is a means to rupture the valve. This means would comprise, preferably, a long, slender, pointed sinker bar 108, as illustrated in FIG. 3, which would be lowered on a wire line 110 through bore 43 in the assembly 102, in the direction of Arrows 112, and by raising and dropping the bar 108 against the glass disc 10, the impact would rupture the disc 10, thus clearing the passage within the assembly 102, in order to allow the well to begin producing through the production screen through the internal bore of the disc valve assembly 102, as seen in FIGS. 4A-4B. In addition, mere fluid pressure in the bore may be used to rupture the disc valve, without the need for a sinker bar or the like.
As seen in those FIGS., 4A and 4B illustrate isolated views of the component of the travelling disc valve assembly 102, which illustrates the upper portion of the assembly having the gap 12 where the ruptured disc was once in position, and has been ruptured by the impact of tool 108, as illustrated in FIG. 3. Therefore, as seen, fluid which has traveled through ports 35 in casing 36 into the annular space 37 are then free to enter into production screen 32, through the ports 33B in the production casing, of the concentric passage 82 in the direction of Arrows 23 to be collected at the surface of the assembly. It is at this particular point that the production of the well has commenced, and the upward pressure of the production from the surrounding formation 104 is able to take place.
List of Parts and Reference Numbers
travelling disc valve 10
groove 12
circular end piece 18
collet 14
upper packer extension 20
sump packer 20
top locator 24
collet locator 26
elongated spacer 28
top seal bore member 30
production screen 32
outer screen layer 33
screen support wall 33A
plurality of ports 33B
casing perforations 35
production casing 36
annulus 37
string 11
bottom seal bore 40
lower end 41
telltale screen 44
bottom locator 50
outer production assembly 100
internal bore 54
traveling disc valve assembly 102
wash pipe 58
shear joint 56
shear screws 56A
collet 57
space 59
first top seal ring 60
outer wall 63
bottom seal bore member 61
bottom seal rings 62
casing annulus 37
arrows 21
ports 80
bore 43
concentric passage 82
ports 61
formation 104
wireline 110
bar 108
arrows 112
crossover assembly 114
compset packer 116
perforated extension 118
seal bore 120
indicator collet 122
no-go housing 124
seal bore 126
Because many varying and different embodiments may be made within the scope of the inventive concept herein taught, and because many modifications may be made in the embodiments herein detailed in accordance with the descriptive requirement of the law, it is to be understood that the details herein are to be interpreted as illustrative and not in a limiting sense. | A travelling disc valve assembly, comprising a length of tubing lowered down a cased wellbore; a crossover tool secured to the lower end of the length of tubing; a length of wash pipe secured to the lower end of the crossover tool; a disc valve assembly secured to the wash pipe and positioned to a lower circulation position in the well bore; a disc valve secured in a bore of the assembly; in the upper portion of the assembly for shearing off the connection between the wash pipe and the disc valve assembly, when the disc valve assembly is in an upper position, providing to prevent fluid from flowing into the formation below the disc valve and to prevent production flow to the surface; and a to rupture the disc valve at a predetermined time so that the production within the formation is allowed to flow through the assembly bore to the surface. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION DATA
[0001] Provisional Application No. 61/395,367, filed on May 12, 2010
FEDERALLY SPONSORED RESEARCH
[0002] None
SEQUENCE LISTING
[0003] None
FIELD OF THE INVENTION
[0004] The invention relates to methods of applying coatings especially layers of materials for electrochemical devices for use as electrodes in electrochemical energy generation and storage devices such as batteries, supercapacitors, photovoltaic cells, and the like.
BACKGROUND OF THE INVENTION
[0005] The invention relates to chemical power sources and solar cells. In particular, the invention relates to chemical power sources with non-aqueous electrolyte. The positive electrodes of these power sources could be based on lithiated oxides of cobalt, of manganese, and of iron, and the negative electrodes, in which an active substance uses composites, which could be based on graphite. For example, the negative electrode of Li-ion batteries with non-aqueous electrolyte could be based on the composite of the graphite and silicon. Most known technologies for the electrodes production are using the composites of the active material, electronic conductive additive, and binder. Conductive additive provides the conductivity of the electrode mass; the binder provides mechanical strength of the electrode mass and its adhesion to the substrate.
[0006] Methods of electrode fabrication, which could ensure the strength of the mass of the electrode without binder, are very promising. Also important is the ability to provide the conductivity of the electrode mass without conductive additives.
[0007] One of the most perspective technologies for formation the thin layers of the different material is the gas detonation deposition (GDD). The GDD technology is aimed at creating a new technological generation for producing the coatings that posses unique operating characteristics. In GDD technology the powder of material, which is deposited, is subjected of action of the plasma or detonation products flow. As a result, the powder particles gain a high kinetic energy and are deposited on a substrate, forming a high quality coating. The coating, which has the required properties, can be obtained by varying the chemical composition of initial powders, gas mixture, flow energy, etc.
[0008] The main advantages of GDD method are as follows:
high productivity and opportunity of obtaining the coatings on substrates of large area (up to a few square meters); opportunity to deposit a layer of various thickness (from a few micrometers to millimeters); a chance to change the deposited layer composition and its porosity over a wide range; low substrate temperature during the GDD process (less then 100° C.) that makes it possible to deposit the layers of the materials on the polymer substrate or low-melting-point metal substrates; low cost and low power-consuming, high productivity of GDD equipment, and, as a result, low cost price of the fabricated layers; possibility to vary the GDD process parameters and obtain the layers possessing the required properties; high adhesion of deposited layer to substrate.
[0016] The GDD method also enables one to vary and monitor the electrode structure (single or multilayer with required distribution of phase composition), chemical composition of the materials, which are obtained, porosity of the functional layer, etc. Besides, this technology provides an excellent adhesion of carbon material to the metal current collector. It is important to emphasize once more that layers can further be modified by using the post-deposition treatment.
BRIEF DESCRIPTION OF THE INVENTION
[0017] Known methods of the deposition of electrode materials do not provide the possibility to obtain the electrode layers with desired properties. It is because known methods do not allow obtain the targeted form the structure of the electrode material, and the morphology of the surface, to provide the necessary adhesion between the electrode material and the metal substrate—current collector, and do not provide required electrochemical properties of the electrode.
[0018] The purpose of this invention is fabrication the electrodes layers with high-speed forming, high specific charge-discharge characteristics, good adhesion to the substrate, and low cost.
[0019] The problem is solved by the fact that the method of producing the layer of electrodes for battery, is characterized in that in order to improve the performance of the method, to improve the adhesion layer to the substrate, and the electrochemical characteristics of electrodes, the layers of electrode material are formed using the gas detonation deposition, and this method does not require lengthy procedures for processing the initial powders, and the layers, which obtained; and after deposition of the layers the treatment of the layers with a high plasma or high-temperature annealing, chemical or electrochemical etching, depending on the type of material is followed.
BRIEF DESCRIPTION OF DRAWINGS
[0020] FIG. 1 . Schematic design of the setup for realization the method of deposition, using the gas detonation.
[0021] FIG. 2 Work timing diagram of setup for gas detonation deposition.
[0022] FIG. 3 . Profilograms of the surface of a stainless steel substrate after treatment using abrading particles of silicon carbide. Slope profilograms is caused due the deflection of the plate.
[0023] FIG. 4 . X-ray diffraction patterns of the carbon based coatings (80% graphite+20% silicon in initial powder), which was deposited onto nickel substrate. Figures denote corresponding crystallographic index.
[0024] FIG. 5 X-ray diffraction patterns of carbon based coatings (80% graphite+20% silicon in initial powder), which was deposited onto stainless steel substrate. Figures denote corresponding crystallographic.
[0025] FIG. 6 . Dynamics of change the discharge capacity of the electrode based on carbon-silicon composition. The electrode layer was obtained by gas detonation deposition (gas detonation explosion). Electrode was modified by heat treatment Electrode mass composition includes 80 mass % of graphite and 20 mass % of silicon (Si). The weight of the active material is 0.0011 g. Electrolyte is EC, DMC, LiClO4. Discharge and charge currents are 0.1 mA/cm2.
[0026] FIG. 7 . Dynamics of change the charge ( 701 ) and discharge ( 702 ) capacity of the electrode based on carbon-silicon composition. The electrode layer was obtained by gas detonation deposition (gas detonation explosion). Electrode was modified by heat treatment. Electrode mass composition includes 90 mass % of graphite and 10 mass % of silicon (Si). The weight of the active material is 0.0019 g. Electrode area is 15 cm 2 . Electrolyte is EC, DMC, and LiClO4. Discharge and charge currents are 1.5 mA/cm 2 .
[0027] FIG. 8 . Charge and discharge characteristic of the electrode based on carbon-silicon composition. The electrode composition was obtained by gas detonation deposition (gas detonation explosion). Electrode was modified by heat treatment. Electrode mass composition includes 90 mass % of graphite and 10 mass % of silicon (Si). The weight of the active material is 0.0019 g. Electrode area is 15 cm 2 . Electrolyte is EC, DMC, LiClO 4 . Discharge and charge currents are 1.5 mA/cm 2 . Numbers on the curves correspond to the cycle number
[0028] FIG. 9 . Charge ( 901 ) and discharge ( 902 ) characteristic of the electrode based on carbon-titanium oxide composition. The electrode composition was obtained by gas detonation deposition (gas detonation explosion). Electrode mass composition includes 80 mass % of graphite and 20 mass % of titanium oxide (TiO 2 ). The weight of the active material is 0.0226 g. Electrode area is 2 cm 2 . Electrolyte is EC, DMC, LiClO 4 . Discharge and charge currents are 2 mA;
DETAILED DESCRIPTION OF THE INVENTION
[0029] Method, which is claimed in this invention, is a method of gas detonation deposition (gas detonation explosion) with subsequent processing of the obtained layers in the frequency plasma or high-temperature annealing, chemical or electrochemical etching, depending on the type of material, which is deposited.
[0030] In specification, which is presented below, a detailed description of the invention is presented using the example of the electrode, which is a composite material of carbon and silicon. This electrode is particularly promising for use as an anode in lithium ion batteries.
[0031] At the same time in the examples and the tables below, presents data that confirm the possibility to use the invention for other anode and cathode materials for power sources, and also the material for solar cells.
[0032] The properties of the anode to a large extent affect on the specific discharge characteristics of lithium batteries, in particular, its specific energy per unit weight and unit volume, cycle life, self discharge, and other.
[0033] Efficiency of the work of lithium electrode in the secondary batteries is limited by the formation of passivating layers and dendrites, which significantly affects the quality of sludge during the charge process, and reduces the efficiency of cycling. In addition, dendrites, which could accompany the deposition of lithium, create an increased risk for cycling due to short circuits.
[0034] Intercalation compounds of lithium with carbon possess good reversibility during the cycling of the Li-ion batteries. However these compounds have a low specific discharge capacity and energy per unit weight. Specific charge-discharge characteristics of electrodes based on graphite or other modification of the carbon are limited by the theoretical limit of 372 Ah/kg.
[0035] One of the ways to enhance specific discharge characteristics of anodes based on graphite or other carbon modifications is to use following composition: graphite-silicon; graphite-lead; graphite-tin, and other. Carbon-silicon composite material has a high theoretical specific energy per volume, and per weight, because the silicon has high energy parameters.
[0036] At the same time for the composite structures of the graphite-silicon one of the problems is to change the mechanical strength during cycling. This problem is caused by a significant increase the volume of the silicon during intercalation of lithium into the silicon structure when the charging process takes place.
[0037] Thus, when receiving the electrodes on the based on composite graphite-silicon it is important to form a structure that would provide high mechanical strength combined with high electrochemical characteristics. In this case, the most important task is to develop methods of forming sufficiently thin layers of active substance on the metal substrates.
[0038] The disadvantages of these methods should, first and foremost, include the low specific characteristics of layers, which is due to a highly disordered or even the amorphous structure of the films. Furthermore, the presence of significant internal stresses in films of carbon limits their critical thickness values of a few micrometers.
[0039] Necessity to use the vacuum equipment limits the size of electrode which will be received, by a size of the equipment for vacuum deposition. On the other hand, these solutions require significant investment of time, due to the necessity of loading substrates into the vacuum chamber, providing a working vacuum, and a sufficiently long deposition process to produce layers of at least a several microns thick.
[0040] There is a way to create a layer of the graphite electrode on a metal substrate, which is based on thermal (pyrolytic) destruction of graphite materials and deposition of the graphite layer with a high degree of crystallinity of the metal substrate. A disadvantage of this method is the inability to obtain the electrode layers with charge-discharge characteristics higher than the theoretical limit for crystalline graphite because with the increase of crystallinity of graphite the electrochemical characteristics decrease.
[0041] In addition, the graphite layer, which is obtained by this method, has low adhesion to metal substrate. This is characteristic of pyrolytic deposition methods, and this limits the scope of the resulting electrode structures. Particularly negative affect of low adhesion of the graphite layer to the metallic substrate is shown on the characteristics in the case of electrode with roll type structure. The elements of roll type require substantial curvature of the bending of the electrode and, accordingly, are required ensuring a good adhesion of the coating to the substrate to prevent delaminating of the active layer.
[0042] The literature describes a process which uses a mixture of silicon particles and polyvinyl chloride (PVC), followed by heat treatment in argon for 1 hour, grinding in a ball mill for 2-10 hours, and forming an electrode in accordance with the following procedure:
mixing of obtained active material (80 wt. %) with the acetylene carbon black (8 wt. %), and the binder polyvinylidene fluoride (PVDF) (12 wt. %). the resulting mixture then homogeneously stirred in solution 1-metil-2-pirolidon (NMP), the resulting slurry coated on a nickel substrate, and dried at a temperature of 120° C. in a vacuum.
[0046] The maximum specific discharge capacity of ˜900 mAh/g was obtained within 40 cycles.
[0047] Disadvantages of this method include as following: very complex and lengthy procedures for the preparation of initial powders and the formation of electrodes, the need for complex reagents, procedures and vacuum thermal treatments and, consequently, low productivity and high cost of received electrodes
[0048] The literature also describes the mechanochemical methods of obtaining of negative electrodes for lithium batteries based on the graphite and silicon composite. When using such methods the mixture of the powders of the graphite and silicon in various ratios have placed in a ball mill and have milled in an atmosphere of pure argon for 150 hours.
[0049] The resulting mixture is added to the suspension of the binder polytetrafluoroethylene (PTFE) in dehydrated alcohol. Mixture, which is prepared, then is applied to metallic substrate, such as nickel, with a rough surface (“foam nickel”). After that, the electrode is dried, pressed and dried again at 150° C. in vacuum overnight. In some examples, the total mass of the active ingredient was 16 mg.
[0050] For the comparison, the results of manufacturing the electrode of a mixture of graphite (60 at. %) and silicon (40 at. %) when using the same procedure without grinding inside a ball mill are presented in technical literature.
[0051] The maximum discharge specific capacity of electrodes, which were prepared from powders of the milled graphite (80 at. %) and the silicon (20 at. %) totaled about 1000 mAh/g in the first 4 cycles of charge-discharge, and then decreases to around 400 mA*h/g at the 20th cycle. For the electrodes based on the powders of the graphite and silicon, which did not grinded inside a ball mill, the discharge capacity does not exceed 200 mAh/g. These results clearly confirm the influence of structure on the characteristics of the composite electrodes.
[0052] The main disadvantages of mechanochemical methods are as follows:
The need for complicated and lengthy procedures preliminary preparation of powders (grinding in a ball mill for tens to hundreds of hours), a multistage and time-consuming procedure of thermal treatment of the initial mixture and the electrode on the metal substrate. As a result, method is quite expensive, has low productivity because requires a long time (tens of hours to several days); Poor adhesion of these layers to the substrate, which leads to delaminating of the active layer from the substrate due to changes in volume of the active layer during cycling. In addition, area of application of this electrode structures is limited, for example due the problem to use these electrode structure in roll-type batteries, which require a high curvature of the bending of the anode; Insufficiently high and stable specific characteristics of the electrode, due to the large number of grain boundaries in the layer, which is formed from the powder, which is subjected to grinding for a long time.
[0056] The objective of the present invention is to forming electrodes based on composite materials with a high rate of formation, the high specific charge-discharge characteristics, excellent adhesion to metal substrates which is the conductor of the current, and low cost. In particular, the object of the invention is to provide composite electrodes based on silicon.
[0057] The problem is solved by the fact that for the production of the electrode for lithium batteries on the surface of the metal substrate, the method based on the gas detonation deposition is used. This method allows to form the layers of the active materials by deposition of particles of the powder of a various composition and size on the substrate.
[0058] The method is characterized in that in order to improve the performance of the method, to improve the adhesion of the layer of active electrode material to the substrate, the electrochemical characteristics of the electrode based on the layer of active material, and a cycling efficiency of a power source with electrodes which is based for example on the composite of the graphite and silicon, this composite is formed by using gas detonation deposition that does not require time-consuming processing of the initial powders and the layers, which are obtained.
[0059] The layer of deposited material undergoes further processing in the high-frequency plasma or high-temperature annealing, chemical or electrochemical etching depending of the type of the materials, for examples, the type of the graphite.
[0060] The electrode active material in accordance with the current invention could comprises a composition of graphite and silicon with a silicon content 1-90 wt. %.
[0061] The metal oxides MexOy or their composites MexIMeyIIOz (Me=Ti, Sn, Ag, V, Mn . . . ), as well as the micro- or nanoparticles of metals could be added to the composite of the graphite and silicon.
[0062] The layers of the active electrode materials could be deposited on the substrate that includes the metal base, or on the substrate that includes the metal base and a fixed metal grid.
[0063] The method of the gas detonation deposition, which is presented in the current invention, could be used for the forming layers of the different types of the active materials. Examples of using this method for the forming the layers of different electrode materials are presented below in tables.
[0064] The essence of the method of the gas detonation deposition, which is presented in the current invention, is as follows: the layers of deposited active material are formed by deposition of particles of the powder of a various composition and size on the substrate when the process of the deposition of these particles is accelerated by detonation wave.
[0065] The detonation wave arises as a result of ignition of an explosive mixture of oxygen and combustible gas such as hydrogen, acetylene and propane-butane, which are in the specified proportion in the explosive chamber. Wave propagates in the detonation gun barrel where a portion of the powder of the active deposited material is introduced. The particles of the materials are accelerated to speeds equal ˜5M (M—Mach number), and as results acquire the considerable kinetic energy.
[0066] As a result of physico-chemical interaction of the particle of the active materials with the substrate material a continuous coating on the basis of the starting material is formed.
[0067] The forming of the coatings on substrates of large area is achieved either by moving of the detonation gun relative of substrate, or by moving the substrate relative to the gas detonation gun.
[0068] Significant advantages of the method of gas detonation deposition, which is present in the current invention versus a well-known methods of the forming the electrode structures, are as follows:
[0000] 1. The high performance of the method, due to the following:
the method does not require lengthy preparation process procedures for the powders and the substrates before deposition; a method provides a high speed coating formation, which, depending on the type of powder can reach for example the following values of 0.1-0.5 cm 2/s at a coating thickness of 40-100 microns; the method does not require after the deposition the additional long-term treatment of coated layers, which are deposited.
2. The high adhesion of the coated layers of the active electrode material to the substrate; which provided due the following: high speed of the particles, which are deposited, their physical-chemical interaction with the substrate material, and the formation of transition layers at the interface of the coating-substrate. An additional increasing in adhesion can be achieved by treatment of the substrate with the abrasive powder using the gas detonation method before the deposition of the active layers. As result, the rough surface of the substrate is formatted (roughness depends on the size of the abrasive particles), and effective surface coverage of interaction of the active materials with the substrate is increased.
3. Deposition of coatings is carried out in air or inert gas flow, i.e. eliminates the need for vacuum chambers and pumping systems.
4. The relative simplicity and low cost. In the method of gas detonation deposition cheap industrial gases (oxygen, propane, butane, acetylene, and hydrogen) are used.
[0072] Power consumption is only required for the support of the electromagnetic gas valves, compressors, engines, systems, to move the gun control unit, and is minimal. The total power consumption does not exceed 1 kW for the rate of deposition which is presented above.
[0000] 5. Possibility of deposition of coatings on large areas of the substrate. This is achieved either by moving of the detonation gun relative of substrate, or by moving the substrate relative to the gas detonation gun. The area of coverage can reach units m2. When using the regime of the roll moving of substrate material, the size of working surface, on which the deposition of the electrode material, is practically unlimited.
6. The possibility of a wide range change the parameters of the process of gas detonation deposition; this provides the possibility of varying the characteristics of coatings, and obtain active layers with desired properties
[0073] The main parameters of the process of gas detonation deposition, which may vary depending on the tasks, are as follows:
composition of the explosive mixture; the frequency of cycles of process of gas detonation deposition the distance between the outlet of the gas detonation gun and substrate; magnitude of gas transport flow, which determines the amount of powder, which must to be introduced in each cycle of the detonation wave place, where the powder is supplied, and which determines the residence time of powder particles in the detonation wave, and hence their speed and temperature.
[0079] In the case of composite of the active material, such as active materials of the electrodes of Li-ion batteries, the active material is produced in the form of a continuous coating, which can have multiple versions of compositions of tracks:
composition of graphite and silicon; composition of graphite and silicon with the inclusion of micro- or nano particles of metals, for example. Ni or Cu; oxides or sulfides of metals or their composites, such as LiMn 2 O 4 , LiFePO 4 , LiCoO2, LiMnPO 4 , TiO 2 SnO 2 , FeS 2 , CFx with the inclusion of micro- or nano particles of metals, for example. Ni or Cu;
[0083] The thickness of the electrode can reach 150 microns. The structure of the electrode allows provide the bending without breaking the contact between the active mass and current collectors in the range of bending radius from 500 microns to 5 mm.
[0084] In addition, useful new features are added to the invention which is presented here, if the quantity of active material of the anode is increased by the use of substrate mounted on a metal grid. Metal mesh can increase the number of active material, while maintaining high mechanical strength of the electrode.
[0085] Undertake additional heat treatments after the coating process of gas detonation deposition allows optimizing their structure in the direction of regulating the crystallinity of the active layer.
[0086] Chemical or electrochemical processing of electrode layers, which are deposited, allows optimizing the morphology of the electrode surface, for example, to increase the porosity of the surface of the electrode layer. As a consequence, the properties of the interface electrode-electrolyte are improved. This is especially important in the manufacture of current sources with a solid electrolyte, which is deposited by vacuum deposition onto the electrode surface. The increasing of the porosity of the surface of the electrode layer allows of the vapor of solid electrolyte to penetrate into the pores of the electrode material. Vapor of solid electrolyte is uniformly distributed into the volume of layer of the electrode before cooling down and then passing into the solid phase.
[0087] Conducting plasma treatment in a hydrogen atmosphere, contribute to the additional cleaning of the electrode surface and improving its electrochemical properties. In addition, due the hydrogen diffusion along grain boundaries, the passivation of the energy traps at these boundaries is carried out, which further improves the quality of the electrode, for example, the anode lithium ion battery based on a composition of silicon and carbon.
[0088] During the deposition of anodic layers, which is based on the composition of the graphite and silicon, the substrate temperature does not exceed 80° C. However, depending on the type of substrate the temperature could be reduced using the cooling, or increased due to additional heating.
[0089] Process of the deposition, which is based on the gas detonation, involves several steps that are repeated in each cycle of deposition. These steps include
filling a barrel of a detonation gun blast chamber with an explosive mixture ( 113 on the FIG. 1 ) with an explosive mixture through valves ( 107 and 108 on the FIG. 1 ); cutting off of the explosive mixture with inert gas; applying the powder of the substance to be deposited on the substrate through batchers ( 111 and 112 on the FIG. 1 ); igniting the explosive mixture by a candle, and the explosion of the explosive mixture ( 106 on the FIG. 1 ); purging a gun barrel using the neutral gas through one of the valves ( 109 on the FIG. 1 ).
[0095] Management of the process of the deposition, which is based on the gas detonation, is carried out by the control unit ( 101 on the FIG. 1 ). The time of the intervals, which are describing the stages of the process of the deposition, which is based on the gas detonation, are shown in sequence diagram ( FIG. 2 ).
[0096] The treatment of the surface of the substrate with abrasive powder using the gas detonation method could be held for increasing the efficiency of the process of the deposition of the active electrode material on a metallic substrate. As example the silicon carbide could be as the abrasive powder.
[0097] As an example, in FIG. 3 shows the measured surface roughness of stainless steel after abrasive machining of silicon carbide particles with a grain size <40 microns. Measurements have been conducted using the profilometer. Relief, which was formed after this treatment, has a size of about 50 microns.
[0098] For electrodes based on carbon-silicon composites, obtained using the technology presented in this patent application, the crystalline structure of raw materials is preserved. This is evidenced by the presence of peaks characteristic of graphite and silicon on the X-ray diffraction spectra of coatings ( FIG. 4 , 5 ).
[0099] As an example, in the present invention the electrodes based on graphite and silicon, as well as composites of the graphite and silicon (C—Si) with the addition of metal oxides or metal micro- or nanoparticles, obtained by the method of the gas detonation deposition are presented. Electrodes, which are fabricated by this method, have high specific characteristics when used as anodes in lithium ion batteries.
[0100] Useful advantages of this method and of the electrodes based on the composition of the graphite and silicon, which are obtained by this method, are as follows:
the method is inexpensive and expeditious as does not require of the long technological procedures for the preparation of powders, substrates, processing of the electrodes, and provides a high rate of formation of the active layer; the electrodes, which are obtained using this method, possess high mechanical strength and adhesion to the metal substrate; the electrodes which are obtained, are characterized by high specific charge and discharge characteristics when used as anodes in Li-ion batteries.
[0104] The main factors that affect the structure, mechanical and electrochemical properties of the layer of electrode material, are as follows:
parameters of the process of the deposition based on the gas detonation
amount of material, which is injected into the detonation wave; composition of the explosive mixture; the frequency of cycles of process of gas detonation deposition; the distance between the outlet of the gas detonation gun and substrate; the place, where the powder is supplied, and which determines the residence time of powder particles in the detonation wave, and hence their speed and temperature
composition and dispersion of the initial powder of the active materials; temperature of the substrate during the process of the deposition
EXAMPLES
[0113] The Examples described below are provided for illustration purposes only and are not intended to limit the scope of the invention.
[0114] The following examples describe the novelty, practical value, and non-obviousness of the claimed invention.
Example 1
[0115] 1. The substrate of the stainless steel is placed in the device for conducting the deposition of the active materials using the method of gas detonation. The diameter of the substrate is 20 mm
2. The surface of the stainless steel substrate is subjected to abrasive machining using the method of gas detonation with the silicon carbide particles. The size of the particle is less then 40 microns. In the resulting of this process on the surface of the substrate the relief is formed with profile of 50 mm.
3. The mixture of the powder of the graphite (80%) and silicon (20%) is loaded in the batcher of the device.
4. Then process of the deposition of the active layers, which is based on the composition of the graphite and silicon, was conducted under the following conditions:
the distance between the outlet of the gas detonation gun and substrate was 10 cm; the frequency of the cycles of the deposition process based on the gas detonation was 6 Hz; the ratio of the combustible gas (propane-butane) and oxidizer (oxygen) was 1:10
[0119] Analysis of the layer of the active materials, which was deposited, has shown its high adhesion to the substrate.
[0120] Investigation of electrochemical properties of the layer, which was deposited, showed that there is a gradual decrease in specific discharge capacity values up to ˜800 mAh/g at the 50th cycle of charge-discharge while maintaining its trend towards further reduction.
Example 2
[0121] According to the procedure, which is described in Example 1, a layer of the composition of the graphite (90%) and silicon (10%) was obtained. The layer, which was obtained, was subjected to ion-plasma treatment
[0122] The ion-plasma treatment was conducted under the following conditions:
[0123] The sample was placed in the vacuum system, and the high-frequency processing was conducted under ambient temperature:
at 13.56 MHz in argon plasma discharge power at 250 W, under argon pressure of 100 Pa for 10 minutes,
then
in hydrogen plasma in the discharge power 250 W, under hydrogen pressure of 100 Pa in for 15 minutes
[0129] Analysis of the electrochemical properties of this layer showed that there is a gradual decrease in the specific discharge capacity. At the 80th cycle the value of the specific discharge capacity was 600 mAh/g. Then was a gradual decreasing of the discharge capacity to the constant value 500 mAh/g at the 150th charge-discharge cycle.
Example 3
[0130] According to the procedure, which is described in Example 1, a layer of the composition of the graphite (80%) and silicon (20%) was obtained, i.e. with increased silicon content.
[0131] The layer, which was obtained, was subjected to ion-plasma treatment according to the procedure, which is described in Example 2.
[0132] Analysis of the electrochemical properties of this layer showed that there is a gradual decrease in the specific discharge capacity with a gradual saturates at a value of 750 mAh/g at the 80th cycle of charge-discharge
[0133] Thus, increasing the silicon content in the composition of the layer graphite-silicon, which was deposited using the method of gas detonation, improves the electrochemical characteristics of the electrode.
Example 4
[0134] According to the procedure, which is described in Example 1, a layer of the composition of the graphite (90%) and silicon (10%) was obtained.
[0135] The layer, which was obtained, is subjected to heat treatment in a special furnace in air at 350° C. for 60 minutes.
[0136] Analysis of the electrochemical properties of the layer, which was obtained, showed that there is a gradual decrease of the specific discharge capacity values up to 750 mAh/g for a 100 cycle charge-discharge. From the slope of the specific discharge capacity via the number of cycles can be seen that the trend towards further reduction is preserved
Example 5
[0137] According to the procedure, which is described in Example 1, a layer of the composition of the graphite (80%) and silicon (20%) was obtained, i.e. with increased silicon content.
[0138] The layer, which was obtained, is subjected to heat treatment according to the procedure, which is described in Example 4.
[0139] Analysis of the electrochemical properties of the layer, which was obtained, showed that there is a gradual decrease of the specific discharge capacity values up to 1200 mAh/g for a 150 cycle charge-discharge. ( FIG. 6 ) From the slope of the specific discharge capacity via the number of cycles can be seen that the trend towards further reduction is preserved.
[0140] This value is maintained until the 200th cycle, indicating the high stability of the electrochemical properties of the layer, which was obtained in accordance with the parameters, presented in Example 4.
[0141] This confirms the conclusion of Example 3 that the increasing the silicon content in the composition of anode can improve the electrochemical characteristics of anode. Heat treatment of these layers, which have been obtained using the method of gas detonation, allows obtaining of the anodes with very high and stable characteristics.
Example 6
[0142] According to the procedure, which is described in Example 1, a layer of the composition of the graphite (80%) and titanium dioxide, TiO2 (20%) was obtained. I.e. the silicon is replaced with the titanium dioxide.
[0143] Analysis of the electrochemical properties of this layer showed that after decreasing the specific discharge capacity values at the 5th cycle of charge-discharge up to 400 mAh/g, in the following cycles this value is stored to the 20th cycle. This demonstrates the high stability of the characteristics of the layer, which was deposited using the method of the gas detonation. ( FIG. 9 ).
[0144] This value of the specific discharge capacity is significantly higher than achieved for pure graphite (372 Ah/kg) or titanium dioxide.
[0145] The weight of the layer, which was deposited in accordance with Example 6, was 23 mg. This is more than an order of magnitude higher than the values obtained in Examples 1-5. This indicates a high density of the resulting material. Last allows significantly increase the values of the energy, which could be accumulated by this electrode.
[0146] Examples, which are presented above, are illustrated by results, which are presented in Tables 1 and 2, and the Figures.
[0000]
TABLE 1
Characterization of electrodes, obtained by gas detonation explosion
Size of substrate 55 mm × 31 mm. The area of the deposited layer 52 × 27 mm
Weight of
Weight of substrate
materials,
Weight of
with material,
Composition of deposited
which
No. n/n
substrate, g
which deposited, g
materials
deposited, g
Substrate from the aluminum
1
0.8143
1.1194
LiCoO 2
0.3051
2
0.8419
1.0192
FeS 2
0.1773
3
0.8337
0.9320
MnO 2
0.0983
Substrate from the copper
2
2.6810
2.6872
Graphite GCM, 90% mass +
0.0062
Si, 10% mass %. Deposition
on one side
3
2.6480
2.6625
Graphite GCM, 90% mass +
0.0145
Si, 10% mass. Deposition on
two sides
4
2.7785
2.7863
Graphite GCM, 90% mass +
0.0078
Si, 10% mass. Deposition on
one side
6
2.7604
2.7723
Graphite GAK 90% mass, +
0.0119
Si, 10% mass.. Deposition on
one side.
5
2.7776
2.7923
Graphite GAK 90 mass % +
0.0147
Si, 10 mass %. Deposition on
two sides.
7
2.7260
2.7386
Graphite GAK 90 mass % +
0.0126
Si, 10 mass %. Deposition on
one side.
8
2.7945
2.8205
Graphite GAK 90% mass. +
0.026
Si, 10 % mass. Deposition on
two sides.
9
2.7592
2.7848
Graphite GAK 90 mass % +
0.0256
Si, 10 mass %. Deposition from
two sides.
Substrate from stainless steel
2
1.1484
1.3188
FeS 2
0.1704
3
1.1311
1.2564
MnO 2
0.1253
[0000]
TABLE 2
Characterization of electrodes, obtained by gas detonation explosion
Frequency of shots-6 shots per a second
Weight of
the Substrate/
Weight of the
# electrode
electrode
electrode
Weight
time
Electrode
Electrode
current
collectors
of electrode
of deposition
composition
size
collector
and mass
mass
#112
Graphite GCM,
Coin
0.3905
0.3918
0.0013
20 seconds
80%
D-16 mm
SS
Si, 20%
#118
Graphite GCM,
Coin
0.4195
0.4212
0.0017
20 seconds
80%
D-16 mm
SS
Si, 20%
#117
Graphite GCM.
Coin
0.3860
0.3883
0.0023
20 seconds
80%
D-16 mm
SS
Si, 20%
#161
Graphite GCM,
Coin
0.4340
0.4351
0.0011
10 seconds
90%
D-16 mm
SS
Si, 10%
#210
Li 4 Ti 5 O 12. , 70% +
Coin
0.3900
0.3910
0.0010
5 seconds
graphite,
D-16 mm
SS
30% C
#230
FeS2
Coin
0.3855
0.4382
0.0527
D-16 mm
SS
#7
Graphite GCM,
Coin
0.3971
0.4028
0.0057
40 seconds
80% +
D-16 mm
SS
Si, 10% +
TiO2, 10%
#33
MnO2, 90% +
Coin
0.181
0.1952
0.0141
20 seconds
Graphite, 10%
D-16 mm
Al
#10
Graphite GCM,
31*54
2.7312
2.7692
0.038
60 seconds
80% +
mm
Cu
scanning
TiO2, 20%
#11
Graphite GCM,
31*54
2.7734
2.7945
0.0211
60 seconds
80% +
mm
Cu
scanning
Si, 20%,
#12
Graphite GCM,
31*54
2.6894
2.7348
0.0454
60 seconds
80% +
mm
Cu
scanning
Si, 10% +
TiO2, 10%
#9
FeS2, 90% +
31*54
0.8467
0.9292
0.0825
60 seconds
graphite, 10%
mm
Al
scanning
CLOSURE
[0147] While various embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover all such changes and modifications as fall within the true spirit and scope of the invention. | The invention relates to methods of gas detonation deposition (gas detonation explosion) applying coatings, especially layers of materials for electrochemical devices for use as electrodes in electrochemical energy generation and storage devices such as batteries, supercapacitors, photovoltaic cells, and the like. In the method of the gas detonation deposition the powders of the materials, which are deposited, are subjected to detonation with the explosion products flow. As a result, the powder particles gain a high kinetic energy and are deposited on a substrate, forming a high quality coating. | 8 |
This application claims the benefit of Korean Patent Application No. 1998-53122, filed on Dec. 4, 1998, which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an optical detecting sensor and, more particularly, to a thin film transistor (TFT) type optical detecting sensor.
2. Description of the Related Art
Generally, optical detecting sensors are used in facsimile and digital copying machines, and in fingerprint recognition systems as an image reader. In recent years, a TFT type optical detecting sensor has been suggested. The TFT changes its electrical characteristics in response to incident light. A TFT type optical detecting sensor is a system using such a TFT having such a characteristic.
FIG. 1 shows a plan view of a conventional TFT type optical detecting sensor and FIG. 2 shows a sectional view taken along line II—II of FIG. 1 .
As shown in the drawings, an optical detecting sensor 100 comprises a window 8 through which light generated from a light source 102 passes and a sensor TFT 6 for generating optical current by detecting the light which is transmitted through the window 8 and then reflected from an object 12 .
Since the optical detecting sensor 100 is designed to detect the light passing through the window and reflected from the object 12 , it is essential that the window 8 has a sufficient light passing area. In addition, since a storage capacitor 4 for storing charges generated by the reflected light has to maintain a predetermined capacity, it is also essential to provide a sufficient storage area to the storage capacitor 4 .
As shown in FIG. 1, a pixel of the optical detecting sensor 100 is comprised of a storage capacitor 4 and a switching TFT 2 in addition to the window 8 and the sensor TFT 6 . Generally, an area of one pixel defined by A 1 *(B 1 +2B 1 ′), where A 1 is defined by a sum of C 1 , D 1 , E 1 , and F 1 . Accordingly, an area of the window 8 can be defined by (B 1 +2B 1 ′)*F 1 , and an area of the storage capacitor 4 can be defined by (B 1 +2B 1 ′)*D 1 .
The optical detecting sensor 100 will be described more in detail with reference to FIG. 2 .
In FIG. 2, the switching TFT, the storage capacitor, the sensor TFT, and window are defined by regions 2 , 4 , 6 and 8 , respectively.
A first metal layer is formed on a substrate 1 . The first metal layer comprises a gate electrode 20 of the switching TFT 2 , a first storage electrode 30 of the storage capacitor 4 , and a gate electrode of the sensor TFT 6 . The first metal layer is made of a material selected from the group consisting of W, Mo, Cr and Al.
In addition, a gate insulating layer 14 is disposed on the first metal layer, and a semiconductor layer is deposited on the gate insulating layer 14 . The semiconductor layer is patterned such that semiconductor elements 26 and 46 are formed to act as an active layer of the switching TFT 2 and the sensor TFT 6 , respectively.
A second metal layer is deposited and patterned to form drain electrode 24 and source electrode 22 on the active layer of the switching TFT 2 , a second storage electrode 34 for the storage capacitor 4 , and drain electrode 44 and source electrode 42 on the active layer of the sensor TFT 6 .
An insulating layer 16 is formed to protect the switching TFT 2 , the storage capacitor 4 and the sensor TFT 6 . A light interrupting layer 18 is formed on a portion of the protecting insulating layer 16 corresponding to the switching TFT 2 to block light scattered from the object 12 , and a protecting layer 10 is deposited on the insulating layer 16 and covers the light interrupting layer 18 .
Generally, an active layer 46 of the sensor TFT 6 is made of a-Si:H which has a low dark conductivity and a high optical conductivity.
Since the sensor TFT 6 is operated by optical current in accordance with the intensity of incident light in an off-state, negative voltage is always applied to the gate electrode 40 to maintain the off-state. An optical current is generated in proportion to the intensity of the incident light, and is directed to the second storage electrode 34 of the storage capacitor 4 through the source electrode 42 , and then stored in the storage capacitor 4 as charges.
Furthermore, when a bias voltage is applied to the gate electrode 20 of the switching TFT, the charges stored in the storage capacitor 4 are conducted to the source electrode 22 through the drain electrode 24 of the switching TFT 2 .
In the above-described sensor, in order to receive more light, the area of the window 8 should be maximized.
It is also necessary to increase the capacity of the storage capacitor in order to store more charges.
SUMMARY OF THE INVENTION
Accordingly, the present invention is directed to thin film transistor (TFT) type photo sensor that substantially obviates one or more of the problems due to limitations and disadvantages of the related art.
Therefore, it is an object of the present invention to provide a TFT type optical detecting sensor in which the areas of a storage capacitor and a window are maximized, thereby improving the signal to noise ratio (S/N).
To achieve the above object, the present invention provides a TFT type optical detecting sensor which can read an image of an object by reflected light from the object, comprising a light source, a sensor TFT for generating optical current by detecting light reflected from the object, a storage capacitor for transmitting light from the light source to the object and for storing charges of the optical current, and a switching TFT for controlling the release of the charges stored in the storage capacitor, wherein the storage capacitor is made of a transparent conductive material.
Preferably, the transparent conductive material is selected from the group consisting of ITO, TiO and SnO 2 .
The sensor TFT is preferably disposed on a central portion of the storage capacitor.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWING
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention.
In the drawings:
FIG. 1 is a plan view illustrating a pixel of a conventional optical detecting sensor;
FIG. 2 is a sectional view taken along line II—II of FIG. 1;
FIG. 3 is a plan view illustrating a pixel of a TFT type optical detecting sensor according to a first embodiment of the present invention;
FIG. 4 is a sectional view taken along line IV—IV of FIG. 3;
FIG. 5 is a plan view illustrating a pixel of a TFT type optical detecting sensor according to a second embodiment of the present invention; and
FIG. 6 is a sectional view taken along line VI—VI of FIG. 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to the preferred embodiment of the present invention, example of which is illustrated in the accompanying drawings.
FIG. 3 shows a plan view illustrating a pixel of a TFT type optical detecting sensor according to a first embodiment of the present invention, and FIG. 4 shows a sectional view taken along line IV—IV of FIG. 3 .
As shown in FIG. 3, a switching TFT 2 is formed along one side of a pixel of an optical detecting sensor. A gate wire 7 which is connected to a sensor TFT 6 by a gate connection line 7 ′ is formed along another side of the pixel. The sensor TFT 6 is preferably disposed near the center of the pixel.
A window 8 and a storage capacitor 4 are defined by a portion excluding the switching TFT 2 , the gate wire 7 and the gate electrode 7 ′. The storage capacitor 4 functions as the window 8 .
The optical detecting sensor of the first embodiment of the present invention will be described in greater detail with reference to FIG. 4 .
The switching TFT 2 is comprised of a gate electrode 20 , a gate insulating layer 14 , a semiconductor layer 26 , a drain electrode 24 ,and a source electrode 22 . The sensor TFT 6 is also comprised of a gate electrode 40 , a gate insulating layer 14 , a semiconductor layer 46 , a drain electrode 44 , and a source electrode 42 .
In addition, the switching TFT 2 is further provided with a light shielding layer 18 disposed on an insulating layer 16 over the semiconductor layer 26 , to block light.
Preferably, the semiconductor layer 26 of the switching TFT 2 is made of polysilicon, which has a high electric field effect mobility when compared with amorphous silicon. The high electric field effect mobility allows the switching TFT 2 to be small, allowing an increase in the area of the window 8 /storage capacitor 4 .
The storage capacitor 4 is comprised of first and second storage electrodes 30 and 34 made of a transparent material, and a dielectric layer 14 disposed between the first and second storage electrodes 30 and 34 . Charges stored in the storage capacitor 4 contain image information of the object. The transparent material is selected from the group consisting of ITO, TiO, and SnO 2 .
In FIG. 3, when assuming that each length of A 2 , D 2 , C 2 ′ and F 2 is 10 μm each length of B 2 , C 2 , E 2 , and G 2 is 15 μm, the area of the window 8 (and the storage capacitor 4 ) becomes about 825 μm 2 . Thus that the area of the window 8 and storage capacitor 4 are each increased by 40% when compared with a conventional device having the same overall size, as shown in FIG. 1 .
Accordingly, in FIGS. 3 and 4, since the amount of light which can pass through the window can be increased, the sensor TFT 6 can generate a large amount of optical current. And since a large amount of charges are stored in the storage capacitor 4 , the signal to noise ratio (S/N) is increased.
Also, the gate wire 7 and gate electrode 7 ′ connected to the sensor TFT 6 can be made of a transparent material in order to increase the transparent area of the pixel or window.
Furthermore, if the sensor TFT 6 is designed to be positioned in a central portion of the storage capacitor 4 /window 8 by lengthening the gate electrode 7 ′, light interference from the adjacent pixel can be reduced.
FIGS. 5 and 6 show a TFT type optical detecting sensor according to a second embodiment of the present invention.
Referring first FIG. 5, a switching TFT 2 and a sensor TFT 6 are formed respectively at each comer a pixel of an optical detecting sensor, respectively. The switching TFT 2 is comprised of a gate wire 20 , a semiconductor layer 26 , and a source electrode 22 . The sensor TFT 6 is comprised of a gate electrode 40 , a semiconductor layer 46 , and a drain electrode 42 . A storage capacitor 4 comprising first storage electrode 30 and second storage electrode 34 is formed between the switching TFT 2 and the sensor TFT and 6 .
The storage capacitor 4 is formed of a transparent material so that the storage capacitor 4 can also function as a window.
The optical detecting sensor of this second embodiment will be described in greater detail with reference to FIG. 6 taken along line VI—VI of FIG. 5 .
First, a transparent material such as ITO, TiO and SnO 2 are deposited on a substrate 1 , then patterned to form the first storage electrode 30 .
Next, a first metal layer is deposited to form the gate electrodes 20 and 40 of the switching and sensor TFTs. The first metal layer is made of a material selected from the group consisting of Cr, Mo, Al, Ti, Sn, W and Cu.
At this point, the gate wire 7 connected to the sensor TFT 6 can be made of a transparent material in order to increase the transparent area of the pixel or window.
Next, an insulating layer 14 , amorphous silicon (a-Si:H), and amorphous silicon doped with impurities are consecutively deposited, then patterned to form the semiconductor layers 26 and 46 .
The semiconductor layers 26 and 46 each function as a path by which current flows through the TFTs 2 and 6 , respectively.
In addition, the insulating layer 14 functions as a dielectric layer of the storage capacitor 4 and a gate insulating layer of the switching TFT 2 and sensor TFT 6 .
Next, a transparent conductive material is deposited, then patterned to form the storage capacitor 4 . That is, the patterned transparent conductive material functions as the second electrode 34 of the storage capacitor 4 . The transparent conductive material is also selected from the group consisting of ITO, TiO and SnO 2 .
Next, a second metal layer is deposited, then patterned to form the source electrodes 44 , 24 and drain electrodes 22 , 24 on the semiconductor layers 46 and 26 , respectively. The second metal layer is also selected from the group consisting of Cr, Mo, Al, Sn, Ti, W and Cu. However, the second metal layer may be made of transparent material to increase light transmittivity.
Finally, an insulating layer 16 and a light shielding layer 18 are consecutively deposited.
A protecting layer may be further formed on the light shielding layer.
In this second embodiment, since the first and second storage electrodes 30 and 34 of the storage capacitor 4 are made of transparent conductive material, light from a light source can pass through the storage capacitor 4 . Thus, a separate region dedicated for a window is not necessary and the whole area of the capacitor 4 serves as a window. This allows the sensor TFT 6 to generate a large amount of optical current, and a large amount of charges can be stored in the storage capacitor.
It will be apparent to those skilled in the art that various modifications and variation can be made in the thin film transistor type photo sensor of the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. | A TFT type optical detecting sensor includes a sensor TFT for generating optical current by detecting light reflected from an object, a storage capacitor for storing charges of the optical current, and a switching TFT for controlling releasing of the charges stored in the storage capacitor. The storage capacitor is made of a transparent conductive material, such that light is transmitted from a light source through the storage capacitor to the object. | 7 |
This application is a continuation application of Ser. No. 10/829,291 filed on Apr. 22, 2004, now U.S. Pat. No. 7,255,807, issued Aug. 14, 2007.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a ferrite magnetic powder including an alkaline-earth metal constituent, more specifically to a ferrite magnetic powder for bond magnet that experiences only small decrease in coercivity when molded into a bond magnet.
2. Background Art
In order to obtain a bond magnet molded of ferrite magnetic powder and binder that has high magnetic force, it is necessary to increase the ferrite magnetic powder filling factor. JP-Hei9-106904A (Reference) teaches that a bond magnet molded using a ferrite magnetic powder at a filling factor with respect to the binder of 93 wt % achieves (BH) max of 2.5 MGOe or greater.
Moreover, high magnetic force bond magnets are used in audio-video and office automation equipment, small motors employed in automotive and other electrical components, magnet rolls of copying machines and various other applications in which low-temperature demagnetization is a problem, so that maintenance of high coercivity is desirable.
Although, as taught by Reference, the filling factor with respect to the binder can be increased to achieve high magnetic force by appropriately blending fine and coarse powders, the coercivity is liable to decrease when the filling factor is increased too far. Reference points out that high fluidity is maintained and a molded product having high (BH)max can be obtained even when the filling factor is increased. However, it does not offer any useful teaching regarding how to prevent decrease in coercivity (iHc) when the filling factor is increased.
SUMMARY OF THE INVENTION
An object of the present invention is therefore to overcome this problem
It achieves this object by providing a ferrite magnetic powder for bond magnet, which is a ferrite magnetic powder that includes an alkaline-earth metal constituent and exhibits a decrease in coercivity of not greater than 600 Oe when a specimen thereof is subjected to a molding test consisting of:
(1) placing in a mixer and mixing 90 parts by weight of the magnetic powder specimen, 0.4 parts by weight of silane coupling agent, 0.12 parts by weight of lubricant, and 9.48 parts by weight of nylon 6 powder, (2) kneading the obtained mixture at 230° C. and forming it into pellets of an average diameter of about 2 mm, (3) injection molding the obtained pellets at a temperature of 290° C. and molding pressure of 85 kgf/cm 2 under a magnetic field orientation of 10 kOe to obtain a cylindrical molded product of 15 mm diameter and 8 mm height (whose direction of magnetic field orientation lies along the center axis of the cylinder), and (4) finding the difference between the coercivity of the molded product measured with a BH tracer and the coercivity of the magnetic powder specimen.
The test can be carried out using a mixer sold by Kyoritsu-rikou Co., Ltd. under the product designation Sample Mill SK-M10, a silane coupling agent sold by Nihonunica Corporation under the product designation A-1122, calcium stearate as lubricant, nylon 6 sold by Ube Industries, Ltd. under the product designation P-1010, and a kneader sold by Toyoseiki Co., Ltd. under the product designation LaboPlust Mill (biaxial batch kneader).
The ferrite magnetic powder exhibiting a decrease in coercive force or coercivity of not greater than 600 Oe when subjected to the molding test preferably has a coercivity in the powder state of 3600 Oe or greater and the molded product obtained by the test preferably has a coercivity 3200 Oe or greater and a residual flux density of 2980 G or greater. The ferrite magnetic powder can be obtained by preparing a fine powder of ferrite magnetic powder having an average particle diameter of greater than 0.50 to 1.0 μm and a coarse powder-thereof having an average particle diameter of greater than 2.50 to 5.0 μm and mixing the two powders to incorporate the fine powder at a rate of 15-40 wt %.
DESCRIPTION OF THE PREFERRED EMBODIMENT
When a ferrite magnetic powder is incorporated in a binder at a high filling factor and the result is kneaded, the large shearing load it receives during the kneading and ensuing molding imparts strain to the ferrite crystals. The bond magnet after molding is therefore lowered in coercivity relative to the ferrite powder before molding.
The inventors conducted extensive research and experimentation in search of a way to mitigate this decline in coercivity and learned that by using fine and coarse powders within a different range from that taught by Reference, the decline in coercivity at molding of a bond magnet can be made slight.
Ferrite magnetic powder comes in varying compositions and grain forms. When produced by the dry method, the sequence of the processes is generally: Starting material blending→Pelletizing→Firing→Pulverizing→Washing→Dewatering/Drying→Crushing→Annealing→Product. The final “Annealing” step is conducted for relieving crystal strain arising during pulverizing after firing (and also during crushing after drying), because the crystal strain occurring during pulverizing and crushing degrades the magnetic properties, particularly coercivity.
After annealing, the ferrite magnetic powder including alkaline-earth metal constituent has a pH of 10-12. This makes its compatibility with binder poor and has a large adverse effect on the viscosity and fluidity of the powder-binder compound. It is therefore preferable to lower the powder pH of the annealed ferrite magnetic powder. Methods available for lowering the powder pH include that of suspending the magnetic powder in water, stirring it well and, as circumstances require, adding a mineral acid to the suspension, and that of stirring the magnetic powder and carbon dioxide gas in the presence of moisture (water).
When the ferrite magnetic powder is used to produce a bond magnet, the filling factor with respect to the binder can be increased by optimizing the ratio between fine and coarse powders as taught by Reference. However, while this makes it possible to obtain high magnetic force, it unavoidably results in the coercivity maintained by the ferrite magnetic powder being lowered at the time of bond magnet molding. The inventors carried out a series of experiments with regard to this point and learned that the decline in coercivity at molding becomes slight when fine powder and coarse powder are mixed within a prescribed ratio range different from the levels taught as preferable by Reference.
The decline in coercivity at molding of a bond magnet can be assessed by a molding test consisting of the steps (1)-(4) set out earlier. When the mixed powder of fine and coarse powders according to the present invention set out above is used, the value obtained by subtracting the coercivity of the molded product acquired in the molding test from the coercivity of the magnetic powder specimen before molding is 600 Oe or less.
The annealing can be conducted before blending the fine and coarse powders but is more conveniently conducted after. The annealing relieves the strain arising within the crystal grains when the fine and coarse powders are obtained by pulverization in the course of production. An annealing temperature of 800-1100° C. is preferable. At lower than 800°C., the effect of the annealing does not reach a sufficient level, resulting in low coercivity and saturation magnetization. At higher than 1100° C., firing proceeds to degrade compression density and orientation.
EXAMPLES
Example 1
(1) Fine powder production
Iron oxide and strontium carbonate were weighed out and mixed at a mole ratio of 1:5.5. The mixture was pelletized using water, dried and then fired for two hours at 950° C. in an electric furnace. The fired product was pulverized in a hammer mill (marketed as Sample Mill) and further wet-pulverized in a wet pulverizer (marketed as WetMill) to obtain a fine powder of an average particle diameter of 0.59 μm.
(2) Coarse powder production
Iron oxide and strontium carbonate were weighed out and mixed at a mole ratio of 1:5.75. The mixture was pelletized using water, dried and then fired for four hours at 1290° C. in an electric furnace. The fired product was pulverized in the Sample Mill to obtain a coarse powder of an average particle diameter of 3.3 μm.
(3) Mixed powder preparation
The fine powder, 30 wt %, and the coarse powder, 70 wt %, were blended by the wet method, filtered, washed with water, dried, crushed and fired (annealed) for one hour at 990° C. in an electric furnace. The powder pH of the fired product was adjusted using carbon dioxide gas and water. A strontium ferrite powder of the following description was obtained as the final dry powder product. The specific surface area shown is that by BET and the compression density value is that under compression at a force of 1 ton/cm 2 .
Average particle diameter
1.17
μm
Specific surface area
2.23
m 2 /g
Compression density
3.50
g/cm 2
Powder pH
9.4
Powder iHc
3707
(Oe)
(4) Bond magnet production
Under stirring in a mixer (Sample Mill SK-M10, Kyoritsu-rikou Co., Ltd.), 90 parts by weight of the strontium ferrite powder obtained in (3) was surface treated with 0.4 parts by weight of silane coupling agent (A-1122, Nihonunica Corporation), mixed with 9.48 parts by weight of nylon 6 powder (P-1010, Ube Industries, Ltd.), and further added with 0.12 parts by weight of lubricant (calcium stearate).
The obtained mixture was formed into kneaded pellets of an average diameter of about 2 mm at 230° C. using a kneader (LaboPlus Mill biaxial batch kneader, Toyoseiki Co., Ltd.) and then injection molded at a temperature of 290° C. and molding pressure of 85 kgf/cm 2 under a magnetic field orientation of 10 kOe to obtain a 15 mm diameter×8 mm height cylindrical anisotropic bond magnet.
The magnetic properties of the magnet were measured with a BH tracer. It had a maximum energy product (BH)max of 2.20 MGOe and an iHc of 3308 Oe. The decline in coercivity iHc between that before molding and that of the molded product was thus 399 Oe. The properties of the ferrite powder and the properties of the bond magnet obtained in this Example are summarized in Tables 1 and 2.
Comparative Example 1
A strontium ferrite powder was produced under the same conditions as in Example 1, except that 100 wt % of coarse powder was used with no addition of fine powder. Specifically, only the coarse powder obtained in (2) of Example 1 was wet-pulverized, filtered, washed, dried, crushed and fired (annealed) for 1 hour at 990° C. The powder pH of the fired product was adjusted using carbon dioxide gas and water to obtain a strontium ferrite powder of an average particle diameter of 1.49 μm as the final dry powder product.
The obtained powder was used to fabricate a bond magnet as in Example 1, and the properties of the ferrite powder and bond magnet were assessed as in Example 1. The results of the assessment are shown in Tables 1 and 2 in comparison with those of Example 1. As shown in Table 2, the decline in coercivity iHc between that before molding and that of the molded product was 1041 Oe.
Comparative Example 2
(1) Fine powder production
Iron oxide and strontium carbonate were weighed out at a mole ratio of 1: 5.75 and mixed with the additives. The mixture was pelletized using water, dried and then fired for four hours at 1290° C. in an electric furnace. The fired product was pulverized in a hammer mill (marketed as Sample Mill) and further wet-pulverized in a wet pulverizer (marketed as WetMill) to obtain a fine powder of an average particle diameter of 1.20 μm.
(2) Coarse powder production
Iron oxide and strontium carbonate were weighed out at a mole ratio of 1:5.75 and mixed with the additives. The mixture was pelletized using water, dried and then fired for four hours at 1290° C. in an electric furnace. The fired product was pulverized in the Sample Mill to obtain a coarse powder of an average particle diameter of 4.4 μm.
(3) Mixed powder preparation The fine powder, 30 wt %, and the coarse powder, 70 wt %, were blended by the wet method, filtered, washed with water, dried, crushed and fired (annealed) for one hour at 990° C. in an electric furnace. The powder pH of the fired product was adjusted using carbon dioxide gas and water. A strontium ferrite powder of an average particle diameter of 1.44 μm was obtained as the final dry powder product
The obtained powder was used to fabricate a bond magnet as in Example 1, and the properties of the ferrite powder and bond magnet were assessed as in Example 1. The results of the assessment are shown in Tables 1 and 2. As shown in Table 2, the decline in coercivity iHc between that before molding and that of the molded product was 811 Oe.
TABLE 1
Fine powder
Ferrite powder properties
Average
Average
Specific
particle
Content
particle
surface
Compression
Powder
diameter
ratio
diameter
area
density
iHc
(μm)
(%)
(μm)
(m 2 /g)
(g/cm 2 )
(Oe)
Example
0.59
30
1.17
2.23
3.50
3707
Comp. Exmp. 1
No fine powder
1.49
1.61
3.38
3641
Comp. Exmp. 2
1.20
30
1.44
1.73
3.44
3280
TABLE 2
Bond magnet magnetic properties (nylon 6, ferrite 90 wt %)
Max.
Coercivity
Residual
energy
difference
Molding
flux density
Coercivity
product
before/after
density
Br
iHc
(BH)max
molding
(g/cm 3 )
(G)
(Oe)
(MGOe)
(Oe)
Example
3.76
2989
3308
2.20
399
Comp. Exmp. 1
3.76
2977
2600
2.19
1041
Comp. Exmp. 2
3.76
2988
2469
2.18
811
As can be seen from the results shown in Tables 1 and 2, the bond magnet of Example 1 has about the same molding density, residual flux density and maximum energy product as those of Comparative Examples 1 and 2. However, its difference in coercivity between before and after molding is, at 399 Oe, well within 600 Oe, in contrast to the high differences of 1041 Oe and 811 Oe for those of Comparative Examples 1 and 2. The decline in coercivity at the time of bond magnet molding is thus smaller in the case of the ferrite magnetic powder of Example 1 than in the case of the ferrite magnetic powders of Comparative Examples 1 and 2.
As is clear from the foregoing explanation, the present invention provides a ferrite magnetic powder for bond magnet that experiences only small decrease in coercivity when molded into a bond magnet and that, as such, is useful in applications requiring high coercivity. | A ferrite magnetic powder for bond magnet that experiences only small decrease in coercivity when molded into a bond magnet is provided, which is a ferrite magnetic powder that includes an alkaline-earth metal constituent and exhibits a decrease in coercivity of not greater than 600 Oe when subjected to a prescribed molding test. The magnetic powder can be obtained by mixing a fine ferrite powder of an average particle diameter of greater than 0.50 to 1.0 μm and a coarse ferrite powder of an average particle diameter of greater than 2.50 to 5.0 μm at ratio to incorporate the fine powder at a content ratio of 15-40 wt %. | 2 |
FIELD OF THE INVENTION
[0001] This invention relates to supporting and firmly anchoring vertical posts, such as fence posts and the like, in the ground.
REFERENCE TO EARLIER FILED APPLICATION
[0002] This application claims priority from Canadian patent application No. 2,563,135 filed Oct. 11, 2006 and Canadian patent application No. 2,573,995 filed Jan. 16, 2007.
BACKGROUND OF THE INVENTION
[0003] It is desirable to be able to securely fasten various objects to the ground. One object that is commonly secured to the ground is a vertical post.
[0004] When installing a vertical post, such as a fence post, it is common to support the post in the ground by one of: (1) burying one end of the post in a hole dug in the ground; (2) filling the area around the base of the post with concrete; or (3) securing the post to a ground spike that, in turn, is secured into the ground.
[0005] Burying one end of the post in the ground is often unsatisfactory for various reasons, including that digging out a suitable hole and burying the post may be difficult and the ground may not provide suitable support. This may result in a wobbly post that is not well suited for anchoring a fence or the like. A buried post may also be susceptible to rot.
[0006] Filling the area around the base of the post with concrete has its own limitations. This requires digging suitable holes around each post, acquiring sufficient concrete to set each post, mixing concrete, pouring concrete into holes around each post, and ensuring that the post is held straight while the concrete sets.
[0007] Securing posts to post support means, such as metal ground spikes, is a relatively easy and cost efficient alternative for securing a post to the ground.
[0008] Metal ground spike post supports of varying shapes have been used to secure posts to the ground. U.S. Pat. No. 4,271,646 to Mills discloses a prior art metal post support ( 2 ) having a ground engaging blade portion ( 4 ) and a post supporting hollow box portion ( 6 ) as shown in FIGS. 1 and 2 . Mills discloses four blades ( 8 ) disposed in a cross-shaped cross-section, meeting at a central joint ( 10 ). Each of the four blades ( 8 ) is welded to a flat plate ( 16 ), which in turn is welded onto the sides ( 12 ) of the hollow box portion ( 6 ). The Mills post support is made of mild steel plate of one-eighth inch thickness ( 3 . 2 mm). To allow drainage of water entering the box-section ( 14 ), drain holes may be drilled in the plate ( 16 ). To secure a post to the Mills post support, holes may drilled in the sides ( 12 ), through which bolts can be inserted.
[0009] A second common ground spike post support ( 20 ) is illustrated in FIG. 3 . The common ground spike ( 20 ) has a blade portion ( 21 ) comprising four blades ( 22 ), and a post socket portion ( 30 ). The blade portion may be made by cutting two pieces of metal, then bending the two halves of each piece of the metal into a perpendicular arrangement along a longitudinal fold line ( 23 or 24 ). The two pieces of metal are then attached along the respective fold lines by a welded connection ( 25 ).
[0010] The post socket portion ( 30 ) is made from a unitary piece of metal. Three perpendicular bends (along bend lines 32 ) form four walls ( 31 ) to the post socket ( 30 ). Perpendicular bends (along bend lines 34 ) enable base tabs ( 35 ) to form a partially closed lower surface of the post socket ( 30 ). Clamping tabs ( 36 ) are formed in one corner of the post socket ( 30 ) by additional bends (along lines 33 ) in the metal. Apertures ( 38 ) for bolt connectors appear in the clamping tabs ( 36 ).
[0011] The blade portion ( 21 ) is attached to the post socket portion ( 30 ) by a welded connection ( 28 ) between the top of each blade ( 22 ) and the lower face of the base tabs ( 35 ).
[0012] The blade portion ( 21 ) and post socket portion ( 30 ) of the common ground spike ( 20 ) are typically made of the same metal material, often having a thickness of between 2.5 mm and 3.5 mm. Mills discloses use of steel having a thickness of one-eighth inch (3.2 mm). The cost of the metal starting material is a major component of the cost of producing a ground spike. Reducing the thickness of metal for the prior art ground spike designs result in premature deformations and failures under normal to heavy wear conditions.
[0013] There exists a need for stronger, improved blades for a ground spike post support. There exists a need for a stronger, improved ground spike design, preferably that requires less metal such that it can be manufactured for a lower cost without sacrificing product quality.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The invention will be described with reference to the detailed description of the invention and to the drawings thereof in which:
[0015] FIG. 1 is a perspective view of a first prior art ground spike post support;
[0016] FIG. 2 is a bottom plan view of the first prior art ground spike post support;
[0017] FIG. 3 is a perspective view of a second prior art ground spike post support;
[0018] FIG. 4 is a perspective view of an embodiment of the invention;
[0019] FIG. 5 is a perspective view of an embodiment of the invention;
[0020] FIG. 6 is an exploded perspective view of an embodiment of the invention;
[0021] FIG. 7 is a perspective view of an embodiment of the invention;
[0022] FIG. 8 is a top plan view of an embodiment of the invention;
[0023] FIG. 9 is a bottom plan view of an embodiment of the invention;
[0024] FIG. 10 is a top plan view of an embodiment of the invention;
[0025] FIG. 11 is a bottom plan view of an embodiment of the invention;
[0026] FIG. 12 is a perspective view of a portion of blade material according to an embodiment of the invention;
[0027] FIG. 13 is a cross-sectional top plan view of a blade portion according to an embodiment of the invention;
[0028] FIG. 14 is a plan view of starting material used in the construction of a blade portion of an embodiment of the invention;
[0029] FIG. 15 is a plan view of starting material used in the construction of a base plate of an embodiment of the invention;
[0030] FIG. 16 is a plan view of starting material used in the construction of a socket portion of an embodiment of the invention;
[0031] FIG. 17 is a plan view of starting material used in the construction of a blade portion of an embodiment of the invention;
[0032] FIG. 18 is a plan view of starting material used in the construction of a socket portion of an embodiment of the invention;
[0033] FIG. 19 is a plan view of starting material used in the construction of a base plate of an embodiment of the invention;
[0034] FIG. 20 is an enlarged partial perspective view of the socket portion of an embodiment of the invention;
[0035] FIG. 21 is a partial perspective view of the socket portion of an embodiment of the invention;
[0036] FIG. 22 is a partial perspective view of the socket portion of an embodiment of the invention;
[0037] FIG. 23 is a partial perspective view of the socket portion of an embodiment of the invention;
[0038] FIG. 24 is a partial perspective view of the socket portion of an embodiment of the invention;
[0039] FIG. 25 is a bottom view of an embodiment of the invention;
[0040] FIG. 26 is a bottom view of an embodiment of the invention;
[0041] FIG. 27 is a bottom view of an embodiment of the invention;
[0042] FIG. 28 is a bottom view of an embodiment of the invention;
[0043] FIG. 29 is a side view of an embodiment of the invention;
[0044] FIG. 30 is a top view of an embodiment of the invention;
[0045] FIG. 31 is a top view of an embodiment of the invention;
[0046] FIG. 32 is a side view of an embodiment of the invention;
[0047] FIG. 33 is a bottom view of an embodiment of the invention;
[0048] FIG. 34 is a top view of an embodiment of the invention;
[0049] FIG. 35 is a perspective view of an embodiment of the invention;
[0050] FIG. 36 is a bottom view of an embodiment of the invention;
[0051] FIG. 37 is a bottom view of an embodiment of the invention;
[0052] FIG. 38 is a bottom view of an embodiment of the invention;
[0053] FIG. 39 is a bottom view of an embodiment of the invention;
[0054] FIG. 40 is a bottom view of an embodiment of the invention;
[0055] FIG. 41 is a bottom view of an embodiment of the invention;
[0056] FIG. 42 is a bottom view of an embodiment of the invention;
[0057] FIG. 43 is a bottom view of an embodiment of the invention;
[0058] FIG. 44 is a bottom perspective view of an embodiment of the invention;
[0059] FIG. 45 is a top perspective view of an embodiment of the invention;
[0060] FIG. 46 is a bottom perspective view of an embodiment of the invention;
[0061] FIG. 47 is an perspective view of an embodiment of the invention;
[0062] FIG. 48 is a perspective view of an embodiment of the invention;
[0063] FIG. 49 is a perspective view of an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0064] Throughout the following description specific details are set out to provide a more thorough understanding of the invention. However, the invention may be practiced without these particulars. In other instances, well known elements have not been shown or described in detail to avoid unnecessarily obscuring the present invention. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
[0065] With reference to FIG. 4 and subsequent figures, embodiment 200 comprises a ground engaging blade portion 41 and a base plate 60 .
[0066] The blade portion 41 comprises a plurality of blades 42 designed for driving into the ground. In embodiment 40 , there are four blades 42 , though alternate embodiments may have two, three, five, six or more blades. The blades have a reinforcement deformation proximal to a longitudinal outer edge thereof. In embodiment 200 the reinforcement deformation comprises a bent outer edge 110 . In certain other embodiments, such as embodiments 40 ′, 104 and 106 , reinforcement deformations are illustrated as reinforcement lines that have been stamped or otherwise marked as lines 46 , 47 into the blades. Each reinforcement line has a convex portion 46 on one side of the blade and a corresponding concave portion 47 on the other side of the blade.
[0067] Where the reinforcement deformation comprises a bent outer edge 110 , the blade may be bent proximal to a longitudinal outer edge thereof. At the top end of the blade, the distance 111 from the edge of the blade and the bend line may be any suitable distance. To minimize material the need for extra material, a distance between 2.5 mm and 10 mm may be suitable, and a distance of approximately 5 mm may be preferable. In many embodiments the blades taper from the top end of the blade down to the tip 48 . This may make folding the blade difficult near the tip. The fold line may taper closer to the edge of the blade closer to the blade tip 48 . The bent outer edge 110 may be not run the entire length of the blade, but rather stop at point 201 short of the tip of the blade by as much as 5% to 35% as shown in FIG. 4 . In embodiment 200 , the bent outer edge 110 terminates about 10% to 20% of the length L of the blade away from the tip 43 of the blade, and particularly about 15% away from the tip 43 .
[0068] The bend for the edge portion 110 may be any suitable angle 164 , such as 45 degrees to 120 degrees, or preferably between 80 degrees and 100 degrees, and most preferably approximately 90 degrees. Other angles less than 45 degrees or greater than 120 degrees may also be suitable for enhancing the strength of the blade to resist torsion forces when in use.
[0069] The blade portion 41 may be made from two pieces of metal, each having been cut, for example as shown in FIG. 14 , 17 or 6 . Bending of the edges of the blades or stamping of reinforcement lines 46 , 47 on the blades 42 may occur before, after or contemporaneously with the cutting of the blade material. The material is then bent at a substantially perpendicular angle along fold line 43 to form two blades 42 A and 42 B. This is repeated for a second piece of blade material which is folded to form two blades 42 C and 42 D along fold line 44 . The two pieces of blade material may then be welded together along join 45 . Welding may be applied in 2, 3, 4 or more discrete portions of the join 45 , or it may be applied along the entire join.
[0070] The welds may comprise spot welds. In certain embodiments, regular welds are applied at the top and bottom of the join 45 and spot welds are applied in 1, 2, 3, 4, 5, or more positions along join 45 .
[0071] As shown in FIG. 12 , multiple holes 120 may be cut in the blade material along fold line 43 to facilitate the welding process. In this case regular welds can be applied in each hole. FIG. 12 illustrates 4 holes, although 2, 3, 5 or more holes may also be provided in accordance with this invention.
[0072] To facilitate the welding process, discrete apertures may be cut along fold lines 43 and 44 . The discrete apertures can coincide with the portions to be welded so that the weld may be applied from a single side of the blades.
[0073] If the outer edges of the blades are bent due to the stamping of reinforcement lines, the edge of the blades may be straightened, such as by mechanical straightening. This can occur before or after the bending of the blade material.
[0074] In alternate embodiments, the blade portion may be constructed without folding by welding individual blade pieces together along join 45 .
[0075] Base plate 60 is preferably formed of a unitary piece of metal. The base plate 60 may comprise apertures 203 for securing means to the ground spike. Any item that is desired to be secured to the ground could be secured to the base plate. For example, a metal fence could be bolted to the base plate, possibly via a foot joint for securing the post to the plate 60 . Other items could also be secured to the base plate 60 such as floodlights, sprinkler systems, lawn ornaments, etc. The size of the base plate 60 can vary significantly depending upon the desired use. Apertures 203 may also be of different shape, such as oblong if the ability to laterally position an object away from the centre of the ground spike is desired. The rotational positioning of the blades with respect to the base plate may also be varied as shown with reference to FIGS. 8-11 and embodiments 200 and 208 .
[0076] The base plate may be reinforced with reinforcement deformations. The reinforcement deformation may comprise a bent outer edge 206 or may comprise reinforcement lines 62 .
[0077] In certain embodiments, such as embodiment 40 , the base plate is secured to each of the sides of the socket portion 50 . As shown in FIGS. 15 and 19 , socket base plate 60 has four main sides 65 that define a square in the approximate dimensions of the inside of the socket portion 50 . Each of the four corners of the square may be cut out. Socket base plate 60 has three removed corners 66 of equal size, and a larger removed corner 68 to correspond with the corner in which the clamping tabs 56 are located in embodiment 40 . Socket base plate 60 may have a central aperture 64 . The central aperture 64 and the cut-out corners 66 may assist in the drainage of water or liquids when in use, and may assist in powder coating or painting during manufacture. Bent edges 206 may assist with reinforcement of the plate 60 , particularly against torsion forces when the ground spike is in use.
[0078] Reinforcement lines 62 may be stamped into socket base plate 60 for increased strength and rigidity, which may increase the resistance of the base plate 60 to torsion forces.
[0079] With reference to FIG. 13 , where the blade portion 41 has four blades, made from two pieces of metal, the angles 160 and 162 may be varied away from 90 degrees. Where two blades are made out of a unitary piece of metal such as shown in FIGS. 12 and 13 , and where the two edges 110 are bent towards each other, arranging four blades at 90 degrees to each other would result in uneven soil displacement/working areas. For example, where angles 160 and 162 are 90 degrees, the distance 166 that could exert pressure on surrounding ground would be less than the distance 168 , and will be much less than the distance 170 . Distance 166 forms the shortest footprint distance of the ground spike. Depending upon which direction external forces pressure the ground spike when it is bearing a load in the ground, it may be desirable to maximize the shortest footprint distance, such as by making distance 166 approximately equivalent to distance 168 . This can be done by varying the angles 160 and 162 as necessary. For example, an angle of about 95 degrees for 160 and a resulting angle of about 85 degrees for 162 may result in distance 166 approximately equaling distance 168 .
[0080] Embodiment 40 further comprises a post receiving socket portion 50 . The post supporting socket portion 50 comprises four side walls 51 that are in a substantially perpendicular arrangement to each other. Reinforcement lines 55 may be stamped or otherwise marked in each side wall 51 . The reinforcement lines 55 may be concentrated on the lower portion of the socket portion 50 , or may extend further up the side walls 51 . One, two, three, or more reinforcement lines 55 may be applied to each side wall 51 .
[0081] Clamping tabs 56 may be provided on one or more corners of the socket portion 50 . The clamping tabs may take one of various forms known in the art. Examples of differently shaped clamping mechanisms can be seen with reference to embodiments 80 , 82 , and 84 . Clamping tabs have apertures 58 to allow a bolt to pass therethrough for tightening the socket portion 50 on a post placed therein during installation. Clamping tabs may have one, two, three, or more apertures 58 to allow various numbers of bolts to secure the socket portion 50 to a post.
[0082] Once the blade portion 41 , the socket portion 50 , and the socket base plate 60 have been manufactured as described above, embodiment 40 is further assembled by welding each of the four sides 65 of the socket base plate to a side wall 51 of the socket portion 50 . For example, side 65 A may be welded to side wall 51 A, and side 65 B may be welded to side wall 51 B, etc. The length of the weld between each side 65 and side wall 51 is almost the entire depth D of each side wall 51 .
[0083] The length L of the blades may be any suitable length, for example between 40 and 10 inches, or more preferably between 32 and 24 inches. The length of the blades portion 41 may be varied according to the soil conditions of the application.
[0084] The width W of the blades may be any suitable length for a given application. Where the application is for supporting a 4×4 post, which is generally 3.5″ by 3.5″ wide, the inside depth D of each side wall 51 of the socket portion 50 may be slightly more than 3.5″. In this case the width W will be the same or less than the distance between opposing sides 65 of the square 61 defined by plate 60 if the blades 42 are welded to the plate 60 at angles parallel to the sides 65 . In embodiments where the blades 42 are parallel to the sides 65 , width W will be between 3.5″ and 2.5″, and more preferably between 3.5″ and 3″, and most preferably between 3.5″ and 3.3″. In embodiments where the blades 42 are welded to the plate 60 at approximately 45 degree angles to the sides 65 (i.e. the top surface of the blades extend towards the corners of square 61 ), then width W must be the same or less than the length of a diagonal line that would extend from corner to opposite corner of the square 61 . For supporting a 4×4 post that is 3.5″ by 3.5″ wide, the diagonal line 69 extending between opposite corners of square 61 may be about 5″. For embodiments with blades welded to plate 60 generally along diagonal line 69 , the width W will be between 5″ and 2.5″, preferably between 5″ and 4″ and more preferably between 4.9″ and 4.5″.
[0085] The blades taper from the top to the bottom, such that the width T at the tip of the blades is significantly less than the width W at the top of the blade portion.
[0086] It is noted that the width W, which is illustrated as being the width of the piece of material that is bent to form blades 42 A and 42 B, is approximately the same as the width of the top portion of the assembled blade portion 41 . Similarly the width T is generally the same as the width of the tip portion 48 of the assembled blade portion 41 . Although in practice these widths may vary, particularly due to variations in the curvature of bends 43 and 44 and in the welds joint 45 , for ease of reference in this section widths W and T are treated as equivalent and therefore reference to one of these widths may be applied to either width value.
[0087] Height H of the socket portion 50 may be any suitable height. If height H is too high, the post support will not be suitable for constructing certain fences because dogs, raccoons or other animals may fit under the fence. For 4×4 post installations, height H may be between 6.5″ to 4″ or more preferably between 4.75″ and 5.75″, and most preferably between 5″ and 5.5″.
[0088] Alternate embodiments of the blade portion 41 ′, the socket portion 50 ′ and the plate 60 ′ are within the scope of the invention. Blade portion 41 ′ has cut outs 49 which protrude from one side of the blade. Other alterations to the surface of the blades, including stamped out portions or alternative reinforcement mechanisms are understood to fall within the scope of the invention. The blade tip 48 may be of any suitable shape, including having a rounded end, having tips cut off, or with the tips square (not shown).
[0089] Plate 60 ′ has tabs 74 that may be folded perpendicular to the flat surface 70 along lines 72 . Plate 60 ′ may be welded to the side walls 51 of the socket portion 50 along one or both of the fold line 72 and the outer edge of tab 74 .
[0090] Socket portion 50 ′ shows alternate embodiments for clamping tabs 56 ′ in which the entire tab, that may have two apertures 58 , remains as a single piece of material. The corners 59 of the clamping tabs 56 ′ may or may not be removed. Rounded corners may increase the safety of handling the ground spike.
[0091] FIG. 20 shows an enlarged perspective view of the underside of the socket portion 50 of embodiment 40 . Plate 60 is welded a distance 76 away from the lower edge of the side walls 51 . Distance 76 may be between 30 mm and 0 mm, preferably between 15 mm and 2 mm, and more preferably between 10 mm and 3 mm. One consideration in choosing a suitable distance 76 may be the distance that can be filled entirely with weld material.
[0092] Width W of the blade portion 41 may be varied to fit on plate 60 . The distance 78 between the closest top edge corner of the blade portion 41 and the side wall 51 (measured along a line that continues in the plane of the blade) may be between 0 mm and 40 mm, preferably between 0 mm and 25 mm, and more preferably between 0 mm and 15 mm.
[0093] Although various clamping mechanisms have been described, embodiment 86 illustrates a post support with no clamping mechanism. The side walls can be welded together to form a join in place of the clamping mechanism.
[0094] Different orientations of the blades are within the scope of the invention. Embodiments 40 and 82 show an X-shaped design wherein the blades extend towards the corners of the socket. Embodiment 92 shows a +-shaped cross-section where the blades extend towards the mid sections of the walls 51 . Embodiment 90 shows an orientation of the blades that is intermediate between the X-shape and the +-shape cross-sections. The distance 78 can be varied, such as from approximately 0 mm shown in embodiment 82 to between 5 and 25 mm shown in embodiment 40 .
[0095] Embodiment 40 has two reinforcement lines on the plate 60 , whereas embodiments 82 , 90 and 92 do not have reinforcement lines on the plate.
[0096] The corners and aperture 64 that may be cut from the plate 60 may allow drainage of powder during powder coating and may allow drainage of fluid after installation.
[0097] Embodiment 92 has the blade portion 41 oriented 90 degrees from the orientation shown in embodiment 40 .
[0098] Embodiments 94 and 140 are adjustable ground spikes, having two domes 96 and 97 sitting in place of the base plate 60 . A bolt 99 and nut 98 arrangement allows adjustment of the orientation of the socket from the blades portion during installation. This may be advantageous during installation, particularly if the blades are not driven into the ground straight. The socket may have an opening 95 to allow access by a wrench or other device to adjust and tighten the head of the bolt during installation. Domes 96 and 97 may be any suitable thickness, such as between 3.0 mm and 9.0 mm, and more preferably between 5.0 mm and 7.5 mm. The domes 96 and 97 may be stamped with reinforcement lines, whether concentric circles or lines that radiate outward. Reinforcement lines can be stamped in the blades and in the socket.
[0099] For embodiments 94 and 140 , base plate 60 is a domed surface, namely lower dome 97 . In alternate embodiments of adjustable ground spikes, the base plate 60 may be a flat surface with a circular shape configured so that an upper dome can slide thereupon to adjust the angle and position of the post-receiving socket.
[0100] Embodiment 100 is an example of a post support that could be set in concrete. This type of post support does not require a blade portion. However the socket 50 and the plate 60 could be constructed in the same manner.
[0101] Embodiment 102 is an example of a post support that can be bolted down to a surface, such as a concrete surface or a wooden deck. The socket may be constructed as in embodiment 40 . The plate may extend outward beyond the socket walls.
[0102] Embodiments 104 and 106 are examples of post supports having plates 108 that extend outward beyond the socket walls. Embodiment 106 also shows an alternate pattern for the construction of the blade elements. Reinforcement lines can be placed in some or all of the blades, socket and plate 108 in embodiments 104 and 106 .
[0103] Post support ground spikes are installed by placing a short post segment into the post socket, then hammering the post segment, which in turn drives the post support into the ground. No digging or mixing concrete is involved.
[0104] Different portions of the ground spike may be made of different types of metal, whether that be different alloys, different coatings on the metal, different treatments of the metal, and/or different thicknesses of metal. Early test results of the invention indicate that the portion of the ground spike that requires the thickest and/or strongest material is the base plate 60 . Test results further indicate that the portion of the ground spike that requires the least strength and/or may permit the least thickness is the socket portion 50 , with the blade portion 41 requiring an intermediate strength and/or thickness of metal.
[0105] Test results also indicate that the socket portion 50 requires the most strength at and near the weld to the base plate 60 . For this reason, the reinforcement lines 55 in embodiment 40 only appear at or near the area in which the side walls 51 are welded to the base plate 60 . The reinforcement lines 55 may be raised slightly above the area in which the base plate 60 is welded so that there is no gap in the weld between the plate 60 and the side walls 51 .
[0106] The top one to two thirds of the blade portion require the most rigidity and the most resistance to torsion. The tips of the blades 48 also must be relatively strong to avoid distortion when hitting rocks or other hard items when driven into the ground.
[0107] It is possible to weld additional pieces onto the blades, below the reinforcement lines, to add extra rigidity to the blade portion. This may be particularly useful when trying to minimize the thickness of the blades and yet are unable to stamp suitable reinforcement lines in certain sections of the blades, or where certain portions of the blades require extra reinforcement.
[0108] In alternate embodiments, reinforcement lines may be added, where practicable, to any portion of the ground spike without departing from the invention. The nature and pattern of the reinforcement lines, as well as the thickness of the lines and the depths of the contours may be varied.
[0109] Typically ground spike post supports are used to support posts that are generally square in cross section, for example a 4×4 post (which has side dimensions in cross section of 3.5 inches). However it is also possible to attach a suitable post socket for supporting posts with non-square cross sections, such as a rectangular cross-section, a triangular cross-section, a circular cross-section or an oval cross-section. Other examples of supportable posts include 2×2, 3×3 and 5×5 in the imperial system, and 9×9, 7×7 and 5×5 posts in the metric system (i.e. 9 cm×9 cm). The dimensions of the socket of the ground spike would vary accordingly, for example may be 91 mm to hold a 9 cm×9 cm post, 71 mm to hold a 7 cm×7 cm post, or similar suitable variations. The distance between the edge of the post and the edge of the post support socket may be varied to correspond with the type of fastening mechanism chosen for the socket. For example a socket without a clamping mechanism which merely has holes for placing one or two anchoring bolts through the post and socket might be a closer fit than a socket having wedge grips.
[0110] Ground spikes without lumber supporting sockets can be used to secure outdoor lighting, such as flood lamps or garden lights, garden ornaments, and water sprinkler hoses and nozzles.
[0111] Although ground spikes according to this invention have been primarily described as being comprised of metal, it is within the scope of the invention that the ground spike may comprise other suitable material such as plastic. Accordingly, ground spikes according to this invention may be made from injection molding. In such cases references to welding would clearly not apply. The ground spike may be made of a unitary piece of plastic, such as PVC, or may comprise more than one piece of plastic and attached together by adhesion methods known in the art.
[0112] It will be appreciated by those skilled in the art that although certain embodiments have been described above in some detail, many modifications may be practiced without departing from the principles of the invention. | A ground spike is disclosed having a plurality of blades and a flat plate secured thereto. The blades each have a reinforcement deformation proximal to a longitudinal outer edge. The reinforcement deformation may be a reinforcement line stamped therein, may be a bent outer edge, or the like. Objects may be attached to the flat plate, thereby securing such objects to the ground when the ground spike is used. The ground spike may have a post receiving socket secured to the flat plate. Each component may comprise metals of varying thickness and rigidity or other suitable materials. | 4 |
This invention was made with at least partial support of the United State Government which has certain rights in this invention.
This application is a division of U.S. patent application Ser. No. 08/137,093, filed Nov. 19, 1995 U.S. Pat No. 5,543,078 which is the U.S. National Stage of PCT Application US92/03427, filed Apr. 24, 1993, abandoned, which is a divisional of U.S. patent application Ser. No. 07/690,633, filed Apr. 24, 1991, now abandoned. U.S. patent application Ser. No. 08/137,093 is incorporated by reference in its entirety herein.
FIELD OF THE INVENTION
The present invention relates to liquid crystal compounds possessing molecular and supermolecular structure providing large bulk electronic second order nonlinear optical hyperpolarizability X.sup.(2) in easily processible optical quality films. These materials, which are ferroelectric liquid crystals (FLCs), have application in fast optical processing and switching devices.
BACKGROUND OF THE INVENTION
The bulk electrical polarization P of a material in an electric field (or the electric part of an optical field) may be expanded in powers of the field according to equ 1, where P S is the spontaneous polarization (i.e. polarization present in the absence of applied field, X.sup.(1) is the linear polarizability, X.sup.(2) is the second order nonlinear hyperpolarizability, or second order nonlinear susceptibility, X.sup.(3) is the third order nonlinear hyperpolarizability or third order nonlinear susceptibility. The subscripts i, j, k etc. correspond to the Cartesian coordinates x, y, or z for the system (Williams, D. J., (1984) Angew. Chem. Int. Ed. Engl. 23:690-703).
P--P.sub.S +X.sub.ij.sup.(1) E.sub.j +X.sub.ijk.sup.(2) E.sub.j E.sub.k +X.sub.ijkl.sup.(3) E.sub.j E.sub.k E.sub.l + equ 1
The sum of all terms to the right of P S in equ 1 give the induced bulk polarization in response to an applied field or fields. The spontaneous polarization P S is a vector, while the susceptibilities X.sup.(1) etc. are tensors with component values which are dependent upon the frequency of the applied fields. The square of X.sup.(1) driven by a DC or low frequency AC field is proportional to the dielectric constant of the material, while the square of X.sup.(1) driven by an optical frequency AC field is proportional to the refractive index of the material. All materials possess non-zero X.sup.(1) and X.sup.(3). There are certain symmetry requirements for P S and for X.sup.(2), however. Thus, in order to possess non-zero P S , the system must have polar symmetry. Furthermore, within the electronic dipolar model, X.sup.(2) is zero unless the system possesses noncentrosymmetric symmetry (acentric). All materials with polar symmetry are acentric, but not all acentric materials are polar. Thus it is possible for a material to possess strictly zero P S by symmetry, but non-zero X.sup.(2) in the electronic dipolar model.
Materials possessing non-zero X.sup.(2) exhibit many effects of great current and potential utility. These include but are not limited to: 1) Second harmonic generation (SHG); 2) Sum and difference frequency generation; 3) Optical parametric amplification; 4) Optical rectification; and 5) A linear electrooptic effect (Pockel's effect). Effects 1, 2 and 3 depend upon the induction of optical frequency AC polarizations (or charge flow in the material changing in sign or magnitude at optical frequencies) in the material in response to optical frequency AC applied fields, and therefore derive from optical frequency X.sup.(2) values. These values of X.sup.(2) may be termed "ultrafast".
In general, the ultrafast X.sup.(2) is a lower limit, and the induced polarization in response to lower frequency applied fields will in general be larger (i.e. X.sup.(2) generally increases with decreasing driving field frequency, though the increase is not monotonic). Very large increases in X.sup.(2) occur at frequencies where resonant absorption of the driving radiation occurs. For the applications of interest in this invention, however, non-resonant interactions of the material with driving and induced fields are preferred.
Currently X.sup.(2) materials are utilized extensively for frequency conversion (effects 1 and 2 above), and more experimentally in electro-optic modulators (effect 5). Typically these materials are inorganic single crystals (for example single crystals of potassium dihydrogen phosphate (KDP) or lithium niobate (LiNbO 3 ). For many applications, particularly in the emerging opto-electronics and photonics industry, easily processible thin films possessing X.sup.(2) are of great potential utility. Uses of X.sup.(2) thin films include, for example, electro-optic switching and frequency processing in guided-wave geometries. Guided-wave geometries are useful in, for example, integrated optical circuits or specialized devices such as optical parametric amplifiers or electro-optic modulators.
For some of these potential applications, the film must work in concert with other materials, such as silicon or other semiconductor integrated circuits. This requires that the film be processed onto or with the semiconductor or other material in a controlled way, affording a hybrid device. In some thin film applications inorganic crystals are relatively difficult to utilize, being difficult to hybridize with semiconductors.
It has been known for some time that organic materials possess potential advantages in X.sup.(2) applications (see Prasad, P. N., (1990) Chem. Mater. 2(6):660-669). These include: 1) Easy processibility relative to inorganic crystals; and 2) Potentially large and relatively easily tuned values of the X.sup.(2) components. The potential for easy processibility derives by analogy to the relatively easy creation of, for example, organic polymer and liquid crystal films of optical quality. The potential for large X.sup.(2) derives in part from experimentally determined values of the molecular susceptibilities of organic molecules. Thus, the polarization of a molecule in the presence of applied electric fields is given by equ 2, where μ is the molecular dipole moment, α is the molecular linear polarizability, β is the molecular second order hyperpolarizability, etc.
P--μ+α.sub.ij.sup.(1) E.sub.j +β.sub.ijk.sup.(2) E.sub.j E.sub.k +γ.sub.ijkl.sup.(3) E.sub.j E.sub.k E.sub.l +equ 2
Using the technique of, for example, electric field induced second harmonic generation (EFISH) in isotropic solutions, it is possible to measure the magnitude of certain components of β for many organic molecules. A fairly good estimate of X.sup.(2) may be made based upon these β values, and using such estimates, it may be shown that X.sup.(2) for organic materials may in principle be much larger than those exhibited by inorganic crystals (Prasad, P. N., (1990) supra).
Finally, the potential for tunability derives from the great structural diversity of organic molecules combined with some relatively simple models for the molecular origins of β. Thus, while the level of understanding of the molecular origins of β is not quantitative, it is easy to predict qualitatively the magnitude of β expected for new organic molecules using the "two-state model" (Williams, D. J., (1984) supra and Prasad, P. N., (1990) supra). In this model, using the valence bond structures of the ground and first electronically excited states one may calculate the expected β value in response to driving fields far from resonance. At the current state of the art, these calculations give only a qualitative picture of the hyperpolarizability of the molecules.
More simply, it is generally appreciated that the molecular β increases with increasing difference in molecular dipole moment of the ground state and first electronically excited state of the molecule. Furthermore it is generally known that this occurs when a donor group and an acceptor group are oriented ortho or para on a benzene ring. Donor and acceptor refer to the ability of the group to either donate electron density (donor) or donate positive charge density (acceptor) to an aromatic ring. When the donor and acceptor are regiochemically placed on the benzene ring such that negative charge transfer from the donor to the acceptor can occur according to simple resonance arguments (i.e. they are conjugated), then a large β should result. With a single benzene ring the conjugated substituents are ortho or para, as indicated in the following diagram for p-nitroaniline--a prototypical organic NLO molecule. An axis, termed here the "β axis", may be defined for such molecules. This axis is along the line connecting the donor substituent with the acceptor substituent. If the molecular coordinate system is defined such that the β axis is along y, then β y ,yy will be a large component of the β tensor. ##STR2## Furthermore, it is understood that the larger the distance between the donor and acceptor, the larger the β which will result for a given donor-acceptor pair (β goes up approximately as the square of the distance separating the donor and acceptor). Thus, para nitroaniline has a larger β than the ortho isomer. Furthermore, conjugation between the donor and acceptor can be across a larger grouping than one benzene ring, as long as the conjugation is not broken. Thus, stilbenes, tolanes, and diphenyl azo compounds substituted at the p-p' positions with donor and acceptor groups possess very large β values, with the β axis on the line between the donor and acceptor, stilbenes and azo compounds larger than tolanes. The prototypical organic molecule with very large β is disperse red 1, a diphenyl azo compound, whose ground state structure and charge transfer resonance structure are: ##STR3##
Furthermore, it is known that when β gets large with increasing conjugation, then the farthest red resonant electronic absorption peak (λ max ) is red-shifted, leading to increased resonant absorption at longer wavelengths close to λ max relative to a molecule with less conjugation or a smaller conjugation length. For some applications blue-shifted resonant absorption (i.e. towards the UV, affording more visible clarity) is advantageous, such as frequency doubling into the blue part of the visible spectrum. For some applications, such as electro-optic modulators which typically operate at wavelengths where glass fiber has the minimum dispersion (>1.0 μm) the red shift in λ max for the NLO molecules may not be a disadvantage.
From the above discussion and data it can be seen that organic molecules may be designed qualitatively to possess a given β value consistent with a given λ max . It is not the subject of this invention to teach new donor-acceptor pairs or new conjugating spacers. Rather, this invention can take advantage of most known or new donor-acceptor pairs, and also known or new conjugating spacers.
It is known that in order to possess useful X.sup.(2) the NLO molecules must be combined to create a material, in some cases a thin film, and in some cases a bulk sample, typically much larger than the size of the molecules, but possessing acentric symmetry (Williams, D. J., (1984) supra and Prasad, P. N. (1990) supra). Furthermore, it is sufficient but not necessary for the material to possess polar order. Furthermore, it is understood that when the donor, acceptor and conjugating spacer (the β axis) lie on or close to a polar axis of a medium with polar order, and are oriented along the polar axis in a polar fashion, then the X.sup.(2) of the material is optimized for that donor-conjugating spacer-acceptor unit.
Several methods for achieving the combination of the NLO molecules into the desired X.sup.(2) material are known. These include: 1) Single crystals or oriented microcrystalline solids (see for example Marder, S. R., et al., (1989) Science 245:626-628); 2) Langmuir-Blodgett multilayers or self-assembling multilayers (see for example Popovitz-Biro, R., et al., (1988) J. Am. Chem. Soc. 110(8):2672-2674) and Tillman, N., et al., (1988) J. Am. Chem. Soc. 110:6136-6144); and 3) Electrically poled polymer films (see for example Williams, D. J. (1984) supra, Dembek, A. A., et al., (1990) Chemistry of Materials 2(2):97-99, and Park, J., et al., (1990) Chem. Mater. 2:229-231). The present invention provides a new method for achieving the NLO material by combining donor-conjugating spacer-acceptor arrays (the β axis) oriented with good polar order along the polar axis of ferroelectric liquid crystal samples, which are typically but not necessarily thin films. Furthermore, the method of the present invention possesses important advantages over any of the previously existing methods.
It is known that often the molecular β impart a large molecular dipole moment in the ground state along the β axis, and that upon crystallization, these units often orient antiparallel to afford centrosymmetric symmetry in the crystal. Thus, for example, p-nitroaniline, while possessing a useful β value, gives centrosymmetric crystals with very small or zero X.sup.(2) (exactly zero in the electronic dipolar model).
It is also known that it is often possible by relatively small modifications to the structure of the molecules, to obtain polar crystals with good polar orientation of the β axis along the polar axis. Thus, for example, when the p-nitroaniline molecule is substituted with a methyl group ortho to the nitro grouping, the resulting methyl nitroaniline (MNA) fortuitously crystallizes with appropriate symmetry for X.sup.(2), and indeed MNA crystals have a very large X.sup.(2) value with moderate resonant visible absorption.
It is also known that organic single crystals, especially those formed from non-ionic molecules, often called Van der Waals crystals, are typically difficult to process into optical quality materials. This may be due to the fact that crystal growth is a kinetic, rather than a thermodynamic phenomenon, and crystal nucleation at multiple sites leads to the formation of domain wall defects which scatter light. The scattering of light from defects is highly undesirable in NLO materials. Furthermore, it is also difficult to control the organic crystal growth in thin film applications, especially for hybrid devices where the organic film must be oriented correctly on a specific substrate surface.
This lack of processibility presents a major disadvantage of organic crystals for X.sup.(2) applications. The problems with crystals led to the invention of several alternative approaches, especially for thin film applications. Two such approaches involve growing a crystalline or non-crystalline film from a substrate one molecular monolayer at a time. In the Langmuir-Blodgett method, NLO molecules are synthesized such that they also form monolayers (LB films) on water. This is achieved by controlling the hydrophilicity and hydrophoebicity of parts of the molecules, and can lead to excellent control over the orientation of molecular fragments, including the functional arrays affording large β, in the monolayers on water.
By careful dipping of a substrate into the monolayer film it is possible to deposit the monolayer with good structural control onto the surface of the substrate. Additional dipping cycles, with additional methods needed to achieve bulk polar order, can afford multilayers with appropriate structure for X.sup.(2). In a somewhat related process, it is possible with correctly designed NLO molecules possessing reactive functional groupings to dip a substrate into an isotropic solution of NLO molecules, and obtain a structurally well-defined monolayer covalently bound to the substrate. Chemical modification of the resulting new surface to introduce appropriate reactivity at the surface, followed by another dipping cycle, etc., can afford multilayers with structure appropriate for NLO applications.
In both of these approaches, many dipping cycles (>1,000) are required to achieve materials of good utility for NLO applications. Furthermore, the structural stability of the resulting multilayers, especially the LB multilayers, is not currently known. In addition, the optical quality achievable for such films is not known. Finally, these techniques are inefficient in time, and presumably cost, and limit the possible geometries of the β axis relative to the substrate surface since for all known examples the polar axis must be normal to the substrate surface. These factors represent disadvantages of the multilayer approaches for creation of X.sup.(2) thin films.
Molecules possessing a dipole moment and β axis (typically colinear) cam be either doped into a polymer matrix, or covalently attached to the polymer matrix. When such polymer matrix is then heated to a temperature above a glass transition temperature and subjected to an electric field, the NLO molecules will tend to align with their dipoles parallel to the field, affording the bulk polar order giving X.sup.(2). If the field is removed, the NLO molecules rapidly revert to their random state, destroying the X.sup.(2) of the sample. However, if the sample is cooled with the field applied below the polymer glass transition, then the polar order induced by the field can be "frozen" into the sample. The field can then be removed to give an optical quality film with useful X.sup.(2).
It is known that such films are typically unstable over time. That is, the NLO molecules, whether covalently attached to the polymer molecules, or doped into the polymer, will over time randomize their orientation, destroying some of the X.sup.(2) of the sample. While many approaches for stabilizing the polar order present in such films are being explored (chiefly cross-linking of the polymer lattice to stabilize the positions of the molecules temporally), the polar order in such films in the absence of applied fields is inherently unstable thermodynamically. In addition, the degree of orientation of the molecular β axis along the polar axis achievable with the largest possible poling electric fields is relatively poor. The good optical quality of non-crystalline or microcrystalline polymer films, and their relative ease of manufacture, are advantages of the poled polymer method for creating X.sup.(2) films. The thermodynamic instability of X.sup.(2) poled polymers and the poor degree of structural control in the films are disadvantages of the method.
In liquid crystals (LCs), mesogen molecules spontaneously self-assemble into true fluids which are anisotropic. Typically, the mesogens are rod-shapped molecules. The long axis of the molecules, and also the optic axis of the LC phase, is called the director, which is represented by the unit vector n. It is relevant for the present invention that for all known LC phases, all properties of the phases are invariant with sign of the director (often represented as n→n). Thus, there is no spontaneous polar order along the director for any known LC phases.
When the liquid crystal is such that the molecules self-assemble into a layered structure, the liquid crystal phase is called smectic. Smectic LCs may be considered as a stack of 2-dimensional fluid phases each approximately one molecular length in thickness. There are many smectic LC structures. In some of these, the director is tilted coherently with respect to the layer normal (z), affording a tilted, layered structure. In this case, the thickness of the molecular layers is typically smaller than the molecular length. The plane containing n and z is termed the tilt plane.
While there is no fundamental reason why smectic C phases cannot possess spontaneous polar order, to our knowledge no smectic C phase possessing such order has ever been reported. Thus, all known smectic C phases possess the following symmetry elements for the phase: 1) A C 2 axis of symmetry normal to the tilt plane (satisfying the empirical fact that n→-n); and 2) A σ (mirror) plane congruent with the tilt plane. Thus, known smectic C phases possess a center of symmetry, i.e. they are centrosymmetric, and therefore possess zero X.sup.(2) in the electronic dipolar model.
When a medium is composed of chirally asymmetric molecules, such medium must be acentric, since the medium cannot possess any reflection symmetry. This is true for all media, including specifically isotropic liquids, all LC phases, and all crystalline or amorphous materials (Giordmaine, J. A., (1965) Phys. Rev. 138(6A):A1599-A1606, Rentzepis, P. M., et al., (1966) Phys. Rev. Lett. 16(18):792-794). The chirality does not, however, force polar order on the system.
For example, it has been demonstrated that chiral, isotropic liquids such as solutions of sugar molecules in water possess non-zero X.sup.(2) due to the acentricity of the medium (Rentzepis, P. M. (1966) supra). In such isotropic liquids there is no polar order, and thus no possibility for orientation of a molecular β axis along a polar axis. In general, it is known that orientation of a large β axis along a polar axis is a valid method for achieving large X.sup.(2). It is known that the X.sup.(2) occurring in acentric isotropic liquids is small.
Furthermore, chiral molecules possessing large β are often utilized for growth of crystals for X.sup.(2) applications. Such crystals must be acentric, and may or may not possess polar order. However, even when polar order exists, in order to achieve large X.sup.(2) it is generally appreciated that the β axis should be oriented along the polar axis. If the β axis is not oriented along the polar axis, small X.sup.(2) will result.
When molecules in the smectic C or any other tilted smectic phase are made chirally asymmetric, then by symmetry considerations the phase must possess polar order in addition to acentricity. That is, all chiral fluid media (and non-fluid media) are acentric, but for known fluids, only in the tilted, layered LC case does the chirality also impart polar order upon the system (Walba, D. M. (1991) Ferroelectric Liquid Crystals: A Unique State of Matter. In: Mallouk T. E., ed. Advances in the Synthesis and Reactivity of Solids, Vol 1. Greenwich, Conn.: JAI Press Ltd 173-235). In the case of the smectic C phase, such a chiral smectic C phase is denoted as the smectic C* phase, which must possess polar order, its symmetry elements being limited to one C 2 axis of symmetry, congruent with the polar axis of the phase, and oriented normal to the tilt plane. Such chiral, tilted, layered LCs are the only known fluids possessing thermodynamically stable polar order.
Typically, the polar order occurring smectic C* phases causes the spontaneous formation of a macroscopic electric dipole moment for the phase. The direction of this macroscopic dipole moment switches upon application of an external electric field, though external fields are not required for the macroscopic dipole to exist. Chiral smectic C* phases, and other chiral tilted, layered LC phases, are thus typically ferroelectric, and are often termed ferroelectric liquid crystals (FLCs) (Walba, D. M. (1991) supra). It is understood that this term includes all chiral, tilted, layered LC phases.
The macroscopic dipole moment of the phase present in the absence of applied electric fields is termed the ferroelectric polarization, P, which is the same as P S in equation 1. This polarization derives from the orientation of molecular dipoles (μ in equation 2) along the polar axis of the phase. The polarization P has a sign, which by arbitrary convention is positive when P (from negative to positive poles) points along the unit vector z×n, and negative when P is opposed to z×n. Enantiomeric (i.e. mirror image) FLC phases possess exactly equal magnitude but opposite sign of P (Walba, D. M. (1991) supra).
The experimental fact that FLCs possess polar order means that FLCs must possess non-zero X.sup.(2) in the electronic dipolar model. In addition, may FLC mesogens, including, for example, DOBAMBC, the first FLC ever reported, also possess functional arrays expected to have large β. Thus, DOBAMBC and many other FLCs possess polar order and are composed of molecules with large β.
However, the measured values of the ultrafast X.sup.(2) in previously known FLCs are very small. Table 1 lists the values of X.sup.(2) for several exemplary known FLC materials as measured by the angle phase-matched SHG technique (see Taguchi, A., et al., (1989) Jpn. J. Appl. Phys. 28(6):L 997-L 999. and Liu, J. Y., et al., (1990) Optics Letters 15(5):267-269). Here, X.sup.(2) is given as values for the d-tensor coefficients (d=X.sup.(2) for SHG). For DOBAMBC and the commercial mixture ZLI 3654, only d eff is given. This value derives from a geometrical combination of various d coefficients, and the square of d eff is proportional to the intensity of second harmonic light output from the sample at the top on an angle phase-matched peak. Experiments providing the values of all non-zero components of the d tensor for the commercial mixture SCE 9 in the homeotropic alignment geometry have been accomplished, said values given in the table (Liu (1990) supra). Note that there is some correlation between the polarization of the sample and the observed d eff . This correlation can be indicative, but is not rigorous.
TABLE 1______________________________________Values of the ferroelectric polarization, SHG efficiency, andχ.sup.(2) (d.sub.eff and dcoefficients), for representative previously known FLCs. Values for somecommon inorganic NLO crystals are included for comparison. SHG dEntry p arb d.sub.eff coefficientsnumber compound (nC/cm.sup.2) units* (pm/V) (pm/V)______________________________________1 DOBAMBC.sup.a -3 1 0.00082 ZLI 3654.sup.b -29 40 0.0053 SCE 9.sup.c +33.6 160 0.01 d.sub.2,3 = 0.073 d.sub.2,2 = 0.027 d.sub.2,1 = 0.0026 d.sub.2,5 = 0.00094 KDP.sup.d d.sub.3,6 = 0.385 5% d.sub.3,1 = -4.7 MgO:LiNbO.sub.3.sup.d______________________________________ *intensity of the second harmonic light at the top of the type 1 eeo angl phasematched peak. .sup.a Vtyurin, A. N., et al., (1981) Phys. Status Solidi B 107(2):397-402. .sup.b Taguchi (1989) supra. .sup.c Liu (1990) supra. .sup.d Eckardt, R. C., et al., (1990) IEEE Journal of Quantum Electronics 26(5):922-933.
As can be seen from Table 1, the values of the largest d coefficients (one measure of X.sup.(2)) for the known FLCs which have been evaluated for X.sup.(2) are small relative to the known X.sup.(2) crystal KDP. This may be due to a combination of two factors: 1) The β axis in FLCs is generally oriented along n, and there is no polar order along n; and 2) The degree of net polar order, as evidenced by the magnitude of the macroscopic polarization, is poor.
In this invention we provide a general approach for obtaining molecules which, when introduced into an FLC phase either as a pure mesogen, or component of an FLC mixture, will impart large X.sup.(2) to the FLC phase by orientation of a β axis of the molecules along the polar axis in the FLC phase, and by achieving a high degree of polar order.
Typical thermotropic LC mesogens or components possess structures combining a rigid core with two relatively "floppy" tails (see Demus et at. (1974) Flussige Kristalle in Taballen, VEB Deutscher Verlag fur Grundstoffindustrie, Liebzig for a compilation of the molecular structures of LC molecules). FLC materials have been prepared by introduction of at least one stereocenter in at least of of the tails. Thus, referring to the general formula A, the rigid core can be, for example, benzylideneamino cinnamyl, biphenyl, phenylbenzoate, phenylpyrimidine or biphenylbenzoate, X and/or Y can be oxygen or CH 2 , R' is an achiral alkyl grouping with from five to twelve carbon atoms, and R* is a chiral moiety. ##STR4##
The FLCs reported to date are generally designed for use in the Clark-Lagerwaal surface stabilized FLC light valve (Clark, N. A., et al., (1980) Appl. Phys. Lett. 36(11):899-901), or other similar light modulation technology involving large nuclear motions of the FLC molecules for switching in response to applied DC fields or low frequency AC fields (<100 MHz). For such FLCs, an important figure of merit is the characteristic response time of the cell (τ), given approximately by equ 3: ##EQU1## where η is the orientational viscosity and P is the magnitude of the ferroelectric polarization density. The polarization typically derives from the type of chiral tail used, while the viscosity is a function of the core and chiral tail. The first FLC compound to be characterized was DOBAMBC, which contains a benzylideneaminocinnamyl core, a n-decyloxy achiral tail and 2-methylbutyloxy chiral tail. As shown in Table 1, pure DOBAMBC exhibits a smectic C* phase with a ferroelectric polarization of -3 nC/cm 2 .
There are a number of reports of compounds containing phenylbenzoate, biphenylbenzoate, tolane, diphenyldiacetylene and related cores coupled to 1-methylalkyloxy or lactate chiral tail units which possess monotropic smectic C* phases affording useful switching properties in the Clark-Lagerwaal SSFLC light valve, or which can be employed as FLC dopants to induce high polarization, fast switching speeds, high tilt angle, high birefringence, or other useful properties when combined in mixtures with FLC host materials.
The following are exemplary reports of such FLC compounds:
Furukawa, K. et al. (1988) Ferroelectrics 85:451-459 refers to chiral smectic C compounds having an ester group in the core and an optically active tail group, either alkoxy or alkoxy carbonyl, with an electronegative substituent, either halogen or cyano group, ortho to the chiral tail, for example: ##STR5## where m=2, X=H, Halogen or CN.
Walba, et. al. (1991) Ferroelectrics 113:21-36 and Walba and Otterholm, U.S. patent application Ser. No. 542,838 refers to FLC components possessing the 1-methylheptyloxy chiral tail unit in combination with pyridine and pyridine-N-oxide core units, where the nitrogen atom of the pyridine ring is adjacent to the point of attachment of the chiral tail, with formula: ##STR6## where X=an electron lone pair or oxygen.
It has been demonstrated in Walba, et. al., (1989) J. Am. Chem. Soc. 111:8273-8274 and U.S. patent application Ser. No. 07/543,160 that for some side-chain ferroelectric liquid crystal polymers composed of a polymer backbone substituted with mesogenic units wherein the achiral tail provides the connection between the polymer backbone and the mesogenic units, the mesogenic unit in the polymer imparts ferroelectric polarization similarly to the low molar mass mesogen itself, though the switching speeds and alignment properties of such polymers are different than the low molar mass mesogens, the switching speeds generally being slower. An exemplary FLC side chain polymer has formula: ##STR7##
Kapitza et al., (1990) Adv. Mater. 2:539-543 have disclosed side chain FLC siloxane polymers and copolymers of formula: ##STR8##
While a number of FLCs (both pure compounds and mixtures) useful in the Clark-Lagerwaal device geometry and other related devices involving large nuclear motions in response to applied fields have been reported, there has been very little work aimed at creating FLCs for electronic NLO applications. Indeed, it has been commonly known in the art of NLO materials design that FLCs are not useful in applications where the medium must respond strongly and quickly to applied fields (either respond to DC or low frequency fields in times less than 10 nsec, or respond to AC fields with frequencies larger than 100 MHz). Such applications require response with small or no nuclear motions. For example, SHG requires response of the material to optical frequency AC applied fields, at which frequencies the molecular nuclei cannot respond.
SUMMARY OF THE INVENTION
It is the object of the present invention to provide new classes of LC and FLC compounds with large X.sup.(2). The present invention provides FLC compounds and/or components of the formula: ##STR9## where Z is either an electron donor or acceptor, and cannot be H, where X is H, a donor, or acceptor grouping, and when Z is an acceptor, X is H or is a donor, and when Z is a donor, X is H or an acceptor,
where j=0, or j=1 and A is 0, (NM 1 ), (O 2 C), (CO), (CO 2 ), (N(M 1 )CO), or (CON(M 1 )) and M 1 =H, or small alkyl,
where n=0, or n=1,
where k=0, or k=1 and (B) is (O 2 C), (CO 2 ), (N(M 2 )CO), (CON(R 2 )), (C═N) or (N═C), and M 2 =H or small alkyl,
where m=0, or m=from 1 to 4 and (D) is (C═C), (C═N), (N═C), (N═N) or (C.tbd.C), and when m≠0, then (B)≠CO 2 or (CON(M 2 ),
where the Rigid Core is a liquid crystal core unit, including but not limited to 1,4-phenylene, 4,4'-biphenyl and substituted aryl rings such as phenylbenzoate rings, an aromatic heterocyclic ring or rings and substituted rings such as phenylpyridines and phenylpyrimidines, 1,4-disubstituted cyclohexyl, [2,2,2]-bicyclooctane ring or rings, [1,1,1]-bicyclopentane ring or rings, cubane ring or rings, or any combination of such ring or rings,
and where R' is a straight chain or branched alkyl group having from 1 to 20 carbon atoms which can be chiral or achiral, and R* is a chiral grouping. For use as liquid crystal materials, R', which is an alkyl group or mono alkenyl group, preferably contains 5 to 12 carbon atoms, and where one or more of the non-neighboring carbon atoms in R' can be O, S, or Si(CH 3 ) 2 , and R* is a chiral grouping which affords core coupling such that the functional array (Z--Ar--X) is oriented in a polar fashion in the FLC phase, close to the polar axis of the FLC phase.
Where R* is ((Y) n C*H(CH 3 )R) where n=0, or n=1 and Y is O, NR 3 , or (CO), where R 3 is H or small alkyl, where the tetrahedral stereocenter indicated by the asterisk is enriched in one configuration, and where R is a straight chain or branched alkyl having from 2 to 15 carbon atoms and where one or more of the non-neighboring carbon atoms in R can be O, S, or Si(CH 3 ) 2 , or where R is (CO 2 R 4 ) where R 4 is methyl or an alkyl with from 2 to 13 carbon atoms and where one or more of the non-neighboring carbon atoms in R 4 can be O, S, or Si(CH 3 ) 2 , or
where R* is ((Y)CH 2 C*HFC*HFR), where Y is O NR 5 , where R 5 is H or small alkyl, R is a straight chain or branched alkyl having from 2 to about 11 carbon atoms and where one or more of the non-neighboring carbon atoms in R can be O, S, or Si(CH 3 ) 2 and where the indicated stereocenters considered together are enriched in either the (S),(S) or (R),(R) configurations.
The acceptor groupings useful for X and Z include any grouping known in the art to be an electron acceptor (for example, any grouping causing deactivation of an aromatic ring relative to benzene in an electrophilic aromatic substitution reaction), which includes halogen, (CN), (COR 1 ), (CO 2 R 1 ), (CON(R 1 ) 2 ), (SO 2 R 2 ), and (NO 2 ) where R 1 is H or small alkyl, and R 2 is small alkyl. It is known in the art that for obtaining large molecular β the NO 2 grouping is preferred to halogen or (CN). In addition, the (SO 2 CF 2 R 3 ) grouping, where R 3 is alkyl, is a preferred acceptor, and the tricyanovinyl grouping (C(CN)=C(CN) 2 ) is a preferred acceptor. For ferroelectric liquid crystals, the NO 2 and (SO 2 CF 3 ) are preferred. Furthermore, the (NHCOCH 3 ) grouping can be an acceptor if the lone pair on nitrogen is unable to interact with the aromatic ring in a resonance sense.
The donor groupings useful for X and Z include any grouping known in the art to be an electron donor (for example any grouping causing activation of an aromatic ring relative to benzene in an electrophilic aromatic substitution reaction), which includes (OR 4 ), (N(R 4 ) 2 ), (N(R 4 )CO(R 5 )), (OCOR), where R 1 and R 5 are H or small alkyl, or other atom less electronegative than halogen and where the atom connected to the aromatic ring possesses a lone pair able to interact with the aromatic ring in a resonance sense.
When Z is an acceptor grouping, then when n=1, Y=O or NR 3 is preferred. When Z is a donor grouping, then when n=1, Y=(CO) is preferred.
Preferred D is (C.tbd.C) and preferred B are CO 2 , O 2 C except that if m≠O, then B≠CO 2 .
The present invention also provides FLC compounds and/or components of the formula: ##STR10## Where Z, X, B and D are as defined above, where Q and T are both H; T is H or an electron donor when Q is an electron acceptor or T is H or an electron acceptor when Q is an electron donor;
where R 2 must be a chiral R' group or R* and R 1 can be R' or R* where R' and R* are as defined above;
when R 1 =R 2 , then Z and Q are either both donors or both acceptors, and T and X are independently H or an acceptor when Q and Z are donors, or H and a donor when Q and Z are acceptors, and
when both R 1 and R 2 are chiral, but R 1 ≠R 2 , and R 1 and R 2 both impart the same sign of P when used individually, then Z and Q are either both donors or both acceptors, and T and X are independently H or an acceptor when Q and Z are donors, and T is H or a donor when Q and Z are acceptors, or
when both R 1 and R 2 are chiral, R 1 ≠R 2 and R 1 and R 2 afford opposite sign of P when used individually, then Z is a donor when Q is an acceptor, and Z is an acceptor when Q is a donor, and T is H or an acceptor when Q is a donor, and T is H or a donor when Q is an acceptor, and X is H or an acceptor when Z is a donor, and X is H or a donor when T is an acceptor, and
where n=0 or 1 and g=0 or 1, and
where E and F are defined as D and B above, respectively, and where h can be 0 or 1 to 4 and m can be 0 or 1 to 4 independently, and where i and k can be 0 or 1, independently.
Preferably h+m≦4, k=0 when m≠0, i=0 when h≠0, m=0 when k=1, and h=0 when i=1. More preferably, k and h=1 while i and m are both 0 or i and m=1 while both k and h=0.
The rigid core is preferably a 1,4-phenylene ##STR11## or a 4,4'biphenylene ##STR12## Preferably the numbers of rings in the compound is 3 or 4.
In a specific embodiment, this invention provides chiral, nonracemic compounds of formula I: ##STR13## where k=0 or 1, when k=1, B=COO; n and m, independently of one another are 0 or 1;
R 1 and R 2 are an OR a , --COOR b or an R* group such that at least one of R 1 or R 2 is an R* group wherein:
R a is a straight-chain or branched alkyl or monoalkene group having from 2 to 16 carbon atoms;
R b is a straight-chain or branched alkyl or monoalkene group having from 2 to 15 carbon atoms;
R* is a chiral nonracemic tail group selected from the group consisting of OC*H(CH 3 )R c , O--C*H(CH 3 )COOR d and OCH 2 C*HFC*HFR e in which the * indicates an asymmetric carbon enriched in one stereoconfiguration which for OCH 2 C*HFC*HFR e is either the (S,S) or (R,R) stereoconfiguration and wherein:
R c is a straight-chain or branched alkyl or monoalkene group having from two to fifteen carbon atoms, R d is a straight-chain or branched alkyl or monoalkene group having from 2 to 13 carbon atoms and R e is a straight-chain or branched alkyl or monoalkene group having from 2 to 11 carbon atoms and wherein for each of R a , R b , R c , R d , R e one or more of the non-neighboring carbon atoms, except any unsaturated carbon atoms, can be substituted with an O, S, or Si(CH 3 ) 2 group; and
X 1 , X 2 , X 3 , and X 4 are either H, an electron donor or an electron acceptor; such that when X 1 is an acceptor, X 3 is either H or a donor and when X 1 is a donor, X 3 is either H or an acceptor, and when X 2 is an acceptor, X 4 is either H or a donor and when X 2 is a donor, X 4 is either H or an acceptor and such that when R 2 is R*, X 1 cannot be H and when R 1 is R* X 2 cannot be H.
In a more specific embodiment, this invention provides chiral, nonracemic o-nitroakoxyaromatic compounds of formula I:
wherein n=0 or 1, m=0 or 1, X 1 is an NO 2 grouping, X 2 , X 3 and X 4 are H, R 2 is a chiral nonracemic group, and R 1 is an alkyl group having from 5 to 15 carbon atoms;
or wherein n=0 or 1, m=0 or 1, X 2 is NO 2 , X 1 , X 3 and X 4 are H, R 1 is a chiral nonracemic group, and R 2 is an alkyl group having from 6 to 12 carbon atoms;
or wherein n=0 or 1, m=0, X 1 is NO 2 , X 3 is NR 4 R 5 , X 2 and X4 are H, R 2 is a chiral nonracemic group, and R 1 is an alkyl group having from 6 to 12 carbon atoms, and where R 4 is H or CH 3 , and R 5 is H, CH 3 , or (COCH 3 );
or wherein n=0 or 1, m=0 or 1, X 1 and X 2 are NO 2 groups, X 3 and X 4 are H, R 1 is a chiral nonracemic group, and R 2 is a chiral non-racemic group;
or wherein n=0, m=0 or 1, X 2 is NO 2 , X 4 is NR 4 R 5 , X 1 and X3 are H, R 1 is a chiral nonracemic group, and R 2 is an alkyl group having from 6 to 12 carbon atoms, and where R 4 is H or CH 3 , and R 5 is H, CH 3 or NHCOCH 3 (but R 5 is NHCOCH 3 only when R 4 is not H);
or wherein n=0, m=0 or 1, X 2 is NH 2 , X 4 is NHCOCH 3 , X 1 and X 3 are H, R 1 is a chiral nonracemic group, and R 2 is an alkyl group having from 6 to 12 carbon atoms.
Also provided is the m-nitroalkoxyaromatic compound of formula I wherein n=0 or 1, m=0, X 3 is NO 2 , X 1 , X 2 and X 4 are H, R 2 is a chiral nonracemic group, and R 1 is an alkyl group having from 6 to 12 carbon atoms, and the m-nitroalkoxyaromatic compound of formula I wherein n=0, m=0 or 1, X 4 is NO 2 , X 1 , X 2 , and X 3 are H, R 1 is a chiral nonracemic group, and R 2 is an alkyl group having from 6 to 12 carbon atoms. These compound are provided as a test and control compounds. While such compounds, specifically where X 1 is H when R 2 is chiral, and where X 2 is H when R 1 is chiral, and where only one chiral tail is present, are not expected to possess large X.sup.(2), they are useful as, for example, FLC host materials or components of FLC mixtures.
In a further embodiment, this invention provides chiral, nonracemic compounds with tolane cores of formula II: ##STR14## where n=1 or 2, and where R 1 and R 2 are an OR a , --COOR b or an R* group such that at least one of R 1 or R 2 is an R* group wherein:
R a is a straight-chain or branched alkyl or monoalkene group having from 2 to 16 carbon atoms;
R b is a straight-chain or branched alkyl or monoalkene group having from 2 to 15 carbon atoms;
R* is a chiral nonracemic tail group selected from the group consisting of OC*H(CH 3 )R c , O--C*H(CH 3 )COOR d and OCH 2 C*HFC*HFR e in which the * indicates an asymmetric carbon enriched in one stereoconfiguration which for OCH 2 C*HFC*HFR e is either the (S,S) or (R,R) stereoconfiguration and wherein:
R c is a straight-chain or branched alkyl or monoalkene group having from two to fifteen carbon atoms, R d is a straight-chain or branched alkyl or monoalkene group having from 2 to 13 carbon atoms and R e is a straight-chain or branched alkyl or monoalkene group having from 2 to 11 carbon atoms and wherein for each of R a , R b , R c , R d , R e one or more of the non-neighboring carbon atoms, except any unsaturated carbon atoms, can be substituted with an O, S, or Si(CH 3 ) 2 group; and
X 1 , X 2 , X 3 , and X 4 are either H, an electron donor or an electron acceptor; such that when X 1 is an acceptor, X 3 is either H or a donor and when X 1 is a donor, X 3 is either H or an acceptor, and when X 2 is an acceptor, X 4 is either H or a donor and when X 2 is a donor, X 4 is either H or an acceptor and such that when R 2 is R*, X 1 cannot be H and when R 1 is R* X 2 cannot be H.
In a more specific embodiment, this invention provides chiral, nonracemic lactate esters with tolane cores of formula II:
wherein X 1 is NO 2 , X 2 and X 3 are H, R 2 is a chiral nonracemic group and R 1 is an alkoxy group with from 6 to 12 carbon atoms, and n=1 or 2;
wherein X 1 is NO 2 , and X 3 is NR 4 R 5 , R 2 is a chiral nonracemic group, and R 1 is an alkyl group having from 6 to 12 carbon atoms, and where R 4 is H or CH 3 , and R 5 is H, CH 3 , or (COCH 3 ), and;
wherein X 3 is NO 2 , and X 1 is NR 4 R 5 , R 2 is a chiral nonracemic group, and R 1 is an alkyl group having from 6 to 12 carbon atoms, and where R 4 is H or CH 3 , and R 5 is H, CH 3 , or (COCH 3 ); and wherein X 1 and X 2 are NO 2 , X 3 is H, n=2, and R 1 and R 2 are both chiral nonracemic groups and are both the same group.
Also provided is the compound of formula II wherein X 1 and X 3 are H, R 2 is a chiral nonracemic group, and R 1 is an alkyl group with from 6 to 12 carbon atoms. While such compounds, specifically where X 1 is H when R 2 is chiral, and where X 2 is H when R 1 is chiral, and where only one chiral tail is present, are not expected to possess large X.sup.(2), they are useful as, for example, FLC host materials or components of FLC mixtures.
Specifically, the present invention provides compounds of formula II: ##STR15## where Z, X, B, D, E, F, Q, T, R 1 , R 2 , and h, i, k and m are defined as above.
Particularly useful for obtaining large X.sup.(2) are compounds of formula IV in which one or both of Z or Q is a NO 2 group. Preferred compounds of formula 1 are those in which E and D can be --C.tbd.C-- and B and F can be CO 2 or O 2 C except that B≠CO 2 when m≠0 and F≠O 2 C when h≠0. ##STR16## where Z'=NO 2 and Q' can be H or NO 2 ; R 2 * must be a chiral group either R* or a chiral R' group and R 1 can be a chiral or nonchiral R' group. It is preferred that if R 1 O is a chiral group that Q' is NO 2 .
Preferred chiral nonracemic groups R 1 or R 2 are those which afford a high degree of core coupling, as described in U.S. patent application Ser. No. 542,838, when ortho substituents are present. Such chiral tails generally cause an increase in ferroelectric polarization when one ortho substituent is electronegative relative to the same structure where both ortho substituents are H. That is, the ferroelectric polarization of compounds of formulas I-IV would be larger when X 1 is NO 2 or other electronegative substituent and X 2 and X 3 are H, than when X 1 is H and X 2 and X 3 are H. Such chiral tails include the nonracemic 1-methylalkyloxy grouping (R=(CH(CH 3 )C n H 2n+1 )), where n is greater than 1, and where the 1-methylheptyloxy grouping (n=6) is more preferred, and the nonracemic 1-methylcarbonyloxy grouping (R=(CH(CH 3 )CO 2 C n H 2n+1 )) where n is an alkyl group with from 1 to 10 carbon atoms. In general, the groups C n H 2n+1 in both of these tails can also have one or more stereocenters, and can also possess heteroatom substituents at stereocenters or at non-stereogenic carbon atoms, and where non-neighboring carbon atoms can be replaced by S, O or Si(CH 3 ) 2 .
In general, the compounds of the present invention are useful as components of liquid crystal materials. In particular, chirally asymmetric molecules Of this invention are useful as components of ferroelectric liquid crystal materials. Certain of these compounds can impart high X.sup.(2) to ferroelectric liquid crystals, either as pure compounds or as components of mixtures. Certain of the compounds in this invention can be employed as FLC host materials. Certain of the compounds of this invention exhibit liquid crystal phases, including smectic C phases.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the present invention can be prepared by a variety of techniques known in the art. In particular, compounds of formula B and C can be prepared by those of ordinary skill in the art employing techniques will known in the art and following the procedures provided hereinafter. Some details of the present invention have been provided in: Walba, D. M., et al. (1991) ACS Symp Ser #455:484. Walba et al., (1991) Mol. Cryst. Liq. Cryst. 198:51.
The general synthesis of chiral and achiral compounds of formula I having k=1, R 1 and R 2 alkoxy, and X 1 =NO 2 , n=0 or 1, and m=0, is illustrated in Scheme I. The hydroxyl group of biphenol (1) is protected as the acetate by treatment with acetic anhydride in pyridine to give 2. Acetate 2 is functionalized in the p' position by, Friedel-Crafts acylation using oxalyl chloride/AlCl 3 to give the p' acid chloride, which is hydrolyzed to the acid in an aqueous workup. This acid is then treated with hydroxide to deprotect the phenolic hydroxyl grouping, affording 3. Alkylation of the phenolic hydroxyl grouping of 3 is accomplished by Williamson etherification to give 4, which is then converted to acid chloride 5 by treatment with oxalyl chloride in benzene/DMF.
Phenol 11 is prepared as follows. Monobenzone (6) is acylated with benzoyl chloride to give phenylbenzoate 7. Removal of the benzyl grouping by hydrogenation using Pd/C catalyst gives the phenol 8. Nitration of 8 is accomplished with the sodium nitrate/lanthanum nitrate reagent, affording o-nitrophenol 9, which is then coupled with R 2 OH to give the ether 10 using the stereospecific Mitsunobu reaction. The Mitsunobu coupling proceeds with inversion of configuration at the stereocenter of alcohol R 2 OH in the case where R 2 is a chiral nonracemic group. Deprotection of the phenolic hydroxyl grouping by treatment of 10 with hydroxide affords phenol 11.
Coupling of acid chloride 5 with phenol 11 then gives the compounds of formula I, wherein X 1 is NO 2 , n=1, and m=0. Alternatively, coupling of a p-alkyloxy benzoic acid chloride 12 with phenol 11 gives the compounds of formula I, wherein X 1 is NO 2 , n=0, and m=0.
The general synthesis of chiral and achiral compounds of formula I having R 1 and R 2 alkoxy, and where X 1 =NO 2 , n=0 or 1, and m=1, is illustrated in Scheme II. Biphenol (13) is protected as the mono-benzoyl ester 14 by treatment with benzoyl chloride in pyridine. The phenol ring of compound 14 is then selectively nitrated using either lanthanum nitrate with nitric acid and HCl, or with nitric acid in acetic acid. The sodium nitrate-lanthanum nitrate conditions are less preferred. Nitrophenol 14 is then coupled with R 2 OH using the stereospecific Mitsunobu coupling procedure to give 16 wherein the stereocenter of R 2 OH is inverted. Deprotection of the phenol by hydrolysis of the benzoate ester with hydroxide ion then gives 17. Coupling of phenol 17 with ether acid chloride 5 or acid chloride 12 then gives the compounds of formula I wherein n=0 or 1, m=1, and X 1 is NO 2 .
The general synthesis of chiral and achiral compounds of formula I having R 1 and R 2 alkoxy, and where X 3 =NO 2 , n=0 or 1, and m=0, is illustrated in Scheme III. Coupling of R 2 OH with monobenzone (6) gives ether 18 with inversion of configuration at the stereocenter of R 2 OH. Deprotection of the phenolic hydroxyl grouping of 18 is accomplished using hydrogenation, which gives phenol 19. Nitration of 19 using the sodium nitrate-lanthanum nitrate conditions then gives phenol 20, which is coupled with either acid chloride 12 or acid chloride 5 to give the compounds of formula I wherein X 3 is NO 2 , m=0, and n=0 or 1.
The general synthesis of chiral and achiral compounds of formula I having R 2 alkoxy and R 1 alkoxy or (OCH(CH 3 )CO 2 R), and where X 2 is NO 2 , n=0, and m=0 or 1, is illustrated in Scheme IV. The carboxyl grouping of 4-hyrdroxy-3-nitrobenzoic acid (21) is protected as the methyl ester to give 22. The alcohol R 1 OH is then coupled stereospecifically to the phenolic hydroxyl of 22 to give the ether 23 using the Mitsunobu coupling. The Mitsunobu coupling proceeds with inversion of configuration at the stereocenter of alcohol R 1 OH in the case where R 2 is a chiral nonracemic group wherein the stereocenter is on the carbon bearing the OH group. Hydrolysis of ester 23 with hydroxide ion then gives the acid 24 which is converted to acid chloride 25 by treatment with thionyl chloride. Alternatively, the ester deprotection step can involve treatment of methyl ester 23 with trimethylsilyl iodide. The latter method is preferred with R 1 is (OCH(CH 3 )CO 2 R).
Coupling of the acid chloride 25 with either the alkoxy phenol 26 or 27, prepared by mono-etherification of diphenol 13, or from monobenzone (6) by alkylation then debenzylation, respectively, then affords the compounds of formula I where X 2 is NO 2 , n=0, and m=0 or 1.
The general synthesis of chiral and achiral compounds of formula I having R 2 alkoxy and R 1 alkoxy or (OCH(CH 3 )CO 2 R), and where X 2 is NO 2 , n=1, and m=0 or 1, is illustrated in Scheme V. Protection of the carboxyl grouping of p'-hydroxy-biphenylbenzoic acid (3) as the methyl ester gives phenol 28. Nitration of phenol 28 with sodium nitrate-lanthanum nitrate and HCl gives the nitro phenol 29, which is coupled with R 1 OH using the stereospecific Mitsunobu coupling reaction. Deprotection of the resulting ester 30 using hydroxide or trimethylsilyl iodide, which is preferred when R 2 is (CH(CH 3 )CO 2 R), gives acid 31. Coupling of acid 31 with either phenol 26 or phenol 27 then gives the compounds of formula I where X 2 is NO 2 , n=1, and m=0 or 1.
The general synthesis of chiral and achiral compounds of formula I having R 1 and R 2 are alkoxy, and where X 4 is NO 2 , n=0, and m=0 or 1, is illustrated in Scheme VI. Coupling of R 1 OH with 4-hydroxy-2-nitrotoluene (33) using the Mitsunobu coupling reaction gives ether 34 with inversion of configuration at the stereocenter of R 1 OH if the stereocenter is the carbon bearing the OH group or R 1 OH. Bromination of the methyl group of 34 then gives bromide 35, which is converted to aldehyde 36 by treatment of with silver nitrate, then treatment of the resulting nitrate ester with hydroxide. Oxidation of aldehyde 36 gives acid 37, which is converted to acid chloride 38 with oxalyl chloride in benzene/DMF. Coupling of acid chloride 38 with either phenol 26 or phenol 27 then gives the compounds of formula I wherein n=0, m=0 or 1, and X 4 is NO 2 .
The general synthesis of chiral and achiral compounds of formula I having R 1 =R 2 ' and R 2 and R 2 ' are alkoxy, and where X 1 and X 2 are NO 2 , n=0 or 1, and m=0 or 1, is illustrated in Scheme VII. Coupling of either phenol 11 or phenol 17 with either acid chloride 25 or acid chloride 32 using NaH in THF solvent gives the compounds of formula I wherein n is 0 or 1, m is 0 or 1, X 1 and X 2 are NO 2 , and R 2 and R 2 ' are both chiral tails, not necessarily the same, but both affording the same sign of P when used individually.
Compounds of formula V can be employed as LC or FLC host materials. ##STR17##
The general synthesis of chiral and achiral compounds of formula V having R 1 and R 2 alkyl, is illustrated in Scheme VIII. Coupling of R 2 OH with phenol 14 using the Mitsunobu coupling reaction gives ester 39. When R 2 is a chiral group with the hydroxyl-bearing carbon a stereocenter, the product is produced with inversion of configuration at the stereocenter of R 2 . Treatment of ester 39 with hydroxide ion gives phenol 40, which is nitrated using the sodium nitrate-lanthanum nitrate-HCl conditions to give nitrophenol 41. Coupling of this phenol with acid chloride 12 using NaH then gives the compounds of formula V.
The general synthesis of chiral and achiral compounds of formula I having R 1 and R 2 alkoxy, and where X 1 and X 3 are not H, and n=0 or 1, and m=0, and where X 2 and X 4 are not H, and n=0, and m=0 or 1, proceed through the common aldehyde intermediates 49. The general synthesis of aldehyde intermediates 49 is shown in Scheme IX. Nitration of p-methylacetophenone (42) gives the nitrotoluene derivative 43. Reduction of the nitro group to an amino group with stannous chloride followed by acylation with acetyl chloride/pyridine then gives the amide 44. Baeyer-Villiger oxidation of 44 with mCPBA gives the acetate 45. The ester grouping of 45 is selectively hydrolyzed with hydroxide ion to give phenol 46, which is nitrated to nitrophenol 47 using nitric acid with acetic acid/acetic anhydride. Coupling of 47 with R 1 OH or R 2 OH using the Mitsunobu coupling reaction then gives the toluene derivative 48. When this ROH is chiral, with a stereocenter at the carbon bearing the hydroxyl grouping, then 48 is formed with inversion of configuration at the stereocenter. Oxidation of the methyl group of 48 to give aldehdye 49 is accomplished by treatment of 48 with ceric ammonium nitrate in acetic acid/water.
The general synthesis of chiral and achiral compounds of formula I having R 1 and R 2 alkoxy, and where X 1 and X 3 are not H, and n=0 or 1, and m=0, is shown in Scheme X. Baeyer-Villiger oxidation of aldehyde 49 (where the R group is R 2 ) using mCPBA gives the phenol 50 via an intermediate formate ester which is not isolated. Phenol 50 is coupled with either acid 51 or acid 4 using dicyclohexylcarbodiimide and p-dimethylaminopyridine to give the compounds of formula I where X 1 is NO 2 , X 3 is NHAc, n=0 or 1, and m=0. Selective hydrolysis of the amide grouping of I where X 3 is NHAc using HCl in acetone then gives the compounds of formula I where X 1 is NO 2 , X 3 is NH 2 , n=0 or 1, and m=0.
The general synthesis of chiral and achiral compounds of formula I having R 1 and R 2 alkoxy, and where X 2 and X 4 are not H, and n=0, and m=0 or 1, is shown in Scheme XI. Oxidation of aldehyde 49 (where the R group is R 1 ) with permanganate gives the acid 52, which is coupled with either phenol 26 or phenol 27 to give compounds 53 with m=0 or 1. The spectral properties of compounds 53 (specifically the fact that these compounds are not absorbing in the visible part of the spectrum and are white) show that in this particular functional group array, the acetamide group (NHAc) is not a donor group. Reduction of the nitro group of 53 gives the amines I, X 2 =NH 2 , X 4 =NHAc, m=0 or 1. The fact that these amines are absorbing in the visible part of the spectrum and are yellow shows that in this particular functional array the NHAc group is acting as an acceptor and the NH 2 group is acting as a donor.
Selective hydrolysis of the amide group of 53 using HCl in aqueous acetone gives compounds of formula I where X 2 =NO 2 , X 4 =NH 2 , m=0 or 1 and n=0. In this case the nitro group is acting as an acceptor and the amino group is acting as a donor.
The general synthesis of chiral and achiral compounds of formula II having R 1 alkoxy or (OCH(CH 3 )CO 2 R) and R 2 alkoxy or (OCH(CH 3 )CO 2 R), and where X 1 is NO 2 , and n=1 is shown in Scheme XII. Coupling of p-iodophenol (54) with R 1 OH using the Mitsunobu coupling reaction gives iodo ether 56. Metal catalyzed coupling of iodide 56 with the acetone adduct of acetylene, followed by deprotection of the terminal acetylene with acid then gives acetylenic ether 59.
Coupling of 54 with R 2 OH using the Mitsunobu conditions gives ether 58, while nitration of 54 gives the nitrophenol 55. Coupling of 55 with R 2 OH under Mitsunobu conditions gives nitro ether 57. Coupling of either 57 or 58 with acetylene 59 using a metal catalyst gives the compounds of formula II where X 1 is NO 2 or H, and n=1.
The general synthesis of chiral and achiral compounds of formula II having R 1 alkoxy or (OCH(CH 3 )CO 2 R) and R 2 alkoxy or (OCH(CH 3 )CO 2 R), and where X 1 and X 2 are NO 2 , and n=2 is shown in Scheme XIII. Coupling of iodoether 57 with the acetone adduct of acetylene using a metal catalyst, followed by deprotection of the terminal acetylene with acid gives acetylene 60. Dimerization of 60 using a copper catalyst in the presence of oxygen then gives the compounds of formula II where X 1 and X 2 are NO 2 , and n=2.
The general synthesis of chiral and achiral compounds of formula III and IV is outlined in Scheme XIV. Coupling of the p-iodophenol (54) with TMS-acetylene gives the phenol-substituted acetylene (61). Acid chloride 12 (Scheme 11) or 25 (Scheme IV) is reacted 61 to give a phenylbenzoate acetylene 62. Finally, coupling of iodoethers like 57 or 58 to 62 gives the benzoate tolane IV where Q' and Z' are H or NO 2 .
The starting materials for synthesis of compounds of formulas I-V by the procedures of Schemes I-XIV are readily available either as commercial products or by synthetic routes that are well known in the art. For example, alkoxy substituted phenols are either available from commercial sources or are readily prepared by known methods (see Neubert et al. (1978) Mol. Cryst. Liq. Cryst. 44:197-210). Introduction of achiral tails wherein non-alternate carbon atoms are replaced by heteroatoms, including oxygen or silicon, is generally discussed in: Hemmerling, W. et al., (1989) European Patent 0355,008. ##STR18##
TABLE 2__________________________________________________________________________Compound of formula I where R.sub.1 = OC.sub.10 H.sub.21, R.sub.2 =(S)-(OCH(CH.sub.3)C.sub.6 H.sub.11, X.sub.1 =NO.sub.2, X.sub.2 = X.sub.3 = X.sub.4 = H, k =1, m = 0 and n = 1 (W__________________________________________________________________________134)X ← 33.6°--C*--93.7°--A--119.1°--IX--80°→C*P/sinθ = -611@ T-Tc = -10°__________________________________________________________________________Compound of formula I where R.sub.2 = OC.sub.10 H.sub.21, R.sub.1 =(S)-(OCH(CH.sub.3)C.sub.6 H.sub.11, X.sub.2 =NO.sub.2, X.sub.1, X.sub.3 and X.sub.4 = H, k =1, m = 1 and n = 0 (W__________________________________________________________________________313)X ← 55°--E-- 64.8°--C*←94.2°→A.fwdarw.90.5°→IX--65°→E--84°→C*P/sinθ = -494@ T-Tc = -10°__________________________________________________________________________Compound of formula I where R.sub.1 = (S)-(OCH(CH.sub.3)C.sub.6 H.sub.11,R.sub.2 = (S)-(OCH(CH.sub.3)C.sub.6 H.sub.11, X.sub.1 = X.sub.2 = NO.sub.2, X.sub.3 =X.sub.4 = H, n = 0, k =1, and m = 1 (W319)__________________________________________________________________________For a 20% mixture in W 82X←15.5°--C*←57.5°--IP.sub.ext @ T-Tc = -10° = -119P.sub.ext @ T-Tc = -42° = -402P.sub.ext /sinθ = -273@ T-Tc = -10°__________________________________________________________________________Compound of formula I where R.sub.1 = OC.sub.10 H.sub.21, R.sub.2 =(S)-(OCH(CH.sub.3)C.sub.6 H.sub.11, X.sub.3 =NO.sub.2, X.sub.1, X.sub.2 and X.sub.4 = H, k = 1, m = 0 and n = 1 (W__________________________________________________________________________320)X ← 50°--C*--62.9°--N*--67.4°--IP.sub.ext /sinθ = -130@ T-Tc = -10°__________________________________________________________________________Compound of formula I where R.sub.2 = OC.sub.10 H.sub.21, R.sub.1 =(S)-(OCH(CH.sub.3)C.sub.6 H.sub.11, X.sub.2 =NO.sub.2, X.sub.1 = X.sub.3 = X.sub.4 = H, n = 1, k = 1, and m = 0 (W__________________________________________________________________________316)X ← 17.5°--C*←60.5°--A--89.1°--IP.sub.ext /sinθ = -330@ T-Tc = -10°__________________________________________________________________________Compound of formula I where R.sub.2 = (S)-(OCH(CH.sub.3)C.sub.6 H.sub.11,R.sub.1 = OC.sub.10 H.sub.21, X.sub.1 =NO.sub.2, X.sub.2 = X.sub.3 = X.sub.4 = H, k = 1, n = 0 and m = 1 (W__________________________________________________________________________317)X ←23.5°--A←76.5°--IX --41°→A--76.5°→I__________________________________________________________________________Compound of formula II where R.sub.1 = OC.sub.10 H.sub.21, R.sub.2 =(R)-(OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5,X.sub.1 = NO.sub.2, X.sub.2 = X.sub.3 = H, and n = 1 (W__________________________________________________________________________334)For a 10% mixture in MDW 158X←23°--C*--60.5°--A--67.5°--IP.sub.ext @ T-Tc = -10° = +79.4P.sub.ext @ T-Tc = -35.5° = +199P.sub.ext /sinθ = +238@ T-Tc = -10°__________________________________________________________________________Compound of formula II where R.sub.1 = OC.sub.10 H.sub.21, R.sub.2 =(R)-(OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5,X.sub.1 = X.sub.2 = X.sub.3 = H, and n = 1 (W 336)__________________________________________________________________________For a 10% mixture in MDW 158X←20°--C*--56.6°--A*←64.3°--N*←66.8.degree.--IP.sub.ext @ T-Tc = -10° = +63P.sub.ext @ T-Tc = -31.6° = +100P.sub.ext /sinθ = +164@ T-Tc = -10°__________________________________________________________________________The 1:1 mixture of W 316 and W 317__________________________________________________________________________X← <rt--C*←45°--A*←79°--IX← <rt→C*P.sub.ext @ T-Tc = -23° = -222P.sub.ext /sinθ = -545@ T-Tc = -23°__________________________________________________________________________Compound of formula II where R.sub.1 = OC.sub.10 H.sub.21, R.sub.2 =(R)-(OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5,X.sub.1 = NO.sub.2, X.sub.2 = X.sub.3 = H, and n = 1 (W__________________________________________________________________________334)For a 10% mixture in ZLI 3234BX← <10°--C*←53.7°--A*←68.8°--N*←85°--IP.sub.ext @ T-Tc = -10° = +112P.sub.ext @ T-Tc = -43.7° = +203P.sub.ext /sinθ = +362@ T-Tc = -10°__________________________________________________________________________Compound of formula I where R.sub.2 = OC.sub.10 H.sub.21, R.sub.1 =(S)-(OCH(CH.sub.3)C.sub.6 H.sub.11, X.sub.2 =NO.sub.2, X.sub.4 = NH.sub.2, X.sub.1 = X.sub.3 = H, k = 1, m = 1 and n =0 (W 341)__________________________________________________________________________For a 10% mixture in MDW 158X← <6°--C*←70.5°--N*←75°--IP.sub.ext @ T-Tc = -10° = -141P.sub.ext @ T-Tc = -40.5° = -202P.sub.ext /sinθ = -310@ T-Tc = -10°__________________________________________________________________________The 1:1 mixture of W 314 and W 317__________________________________________________________________________X← <rt--C*←51°--A*←97°--IP.sub.ext @ T-Tc = -29° = -272P.sub.ext /sinθ = -610@ T-Tc = -29°__________________________________________________________________________
Table 2 summarizes phase sequences, polarization densities and tilt angles of some exemplary FLC compounds of formula I, and phase sequences, polarization densities and tilt angles of some exemplary FLC mixtures containing exemplary compounds of formulas I and II. In Table 2, the phases are noted as X=crystal, I=isotropic liquid, A=smectic A, C*=chiral smectic C, and phase transition temperatures are given in °C. Also, names such as W 314 are given to the compounds in Table 2 for easier reference.
Polarization densities (P) are given in nC/cm 2 and the magnitude of P was measured by integration of the dynamic current response to a surface stabilized ferroelectric liquid crystal cell on reversing the applied electric field using a slight modification of the standard methods of Martinot-Lagarde (1976) J. Phys. Colloq. (Orsay, Fr.) 37:129 and Martinot-Lagarde (1977) J. Phys. Lett. (Orsay, Fr.) 38:L-17. The polarization reversal current was measured after applying a triangular wave form (±15 volts) across a 2.5 μm (using polyimide spacers) polymer aligned (DuPont Elvamide 8061) SSFLC cell (Patel, J. S. et al. (1986) J. Appl. Phys. 59:2355; Flatischler, K. et al., (1985) Mol. Cryst. Liq. Cryst. 131:21; Patel, J. S. et al. (1984) Ferroelectrics 57:137) with indium-tin oxide (ITO) conducting glass electrodes. The signal (current v. time) was digitized using a Sony-Tektronix 390AD programmable digitizer. The current waveform showed a peak characteristic of the polarization reversal; this current peak was integrated. Division of the value of this integration (charge) by the active area of the cell afforded the magnitude of the ferroelectric polarization. For all measurements, the diameter of the ITO coated area of the cell was 0.50 inch. The sign of the polarization was determined directly from observation of molecular orientation in SSFLC cells upon application of electric fields.
The optical tilt angle was determined by rotating the shear or polymer aligned cell until extinction was obtained. The polarity of the cell was reversed and the cell was rotated by a measured angle to obtain extinction again. The angle by which the cell was rotated is equal to 2Θ. The tilt angle was obtained by dividing this angle by two. Tilt angles and polarizations were measured as a function of temperature, and the data are shown in graphical form in PCT application U.S. 92/03427 published Nov. 12, 1992. For comparison purposes, the values of the normalized polarization (P/sinΘ at T-T c =-10° C., where T c is the temperature of the transition into the C* phase from a higher temperature) or the normalized extrapolated polarization (P ext /sinΘ where P ext is the extrapolated polarization of the compound obtained by measuring the polarization of a mixture with a known C or C* host, and assuming that the polarization is linear with concentration of the components) are also given in Table 2.
In some of the measurements on mixtures, the smectic C materials W82=4'-(n-decyloxy)phenyl-4-(4(S)-methylhexyloxy) benzote, MDW 158=racemic W 82, and ZLI 3234B (an achiral smectic C host material obtained from E. Merk, Darmstadt (see Geelhaar, T. (1988) Ferroelectrics 85:329-349) were used as hosts. W 82 is known to possess an enantiotropic ferroelectric C* phase with a very low polarization density of the order of -1 nC/cm 2 . MDW158 and ZLI 3234B are racemic and achiral C phases, respectively, and therefore possess zero polarization. Mixtures of the compounds of the present invention (guests) with these hosts possess polarization density deriving primarily or exclusively from the guest component. Extrapolated polarizations were calculated assuming a linear relationship between polarization and concentration of the components. It is understood that this extrapolation is not rigorous, and that the extrapolated values are only approximate.
Finally, the X.sup.(2) of two of the compounds of formula I as measured by the SHG method are also given in Table 2. The data were obtained using the method of type 1 eeo angle phase matched second harmonic generation from 1,064 nm Nd:YAG laser light, combined with Maker fringe experiments and a computational curve-fitting technique to extract the individual components of the d tensor. The application of type 1 eeo angle phase matched SHG to ferroelectric liquid crystals (including ZLI 3654; see Table 1) is reported in: Taguchi (1989) supra. The determination of the individual d-tensor coefficients for a ferroelectric liquid crystal (SCE 9; see Table 1) by this method is described in: Liu (1990) supra.
Referring to the data in Table 2, it should be noted that several of the compounds of formula I possess broad monotropic and in some cases enantiotropic smectic C* liquid crystal phases. Thus achiral or racemic materials of this type are useful as FLC host materials.
It is an important feature of the present invention that the compounds of formulas I and II where X 1 and/or X 2 are NO 2 , and R 2 and/or R 1 , respectively, are chiral nonracemic core-coupling tails, possess large ferroelectric polarization density. For example, the compound of formula I wherein X 1 =NO 2 , X 2 =X 3 =X 4 =H, R 1 =OC 10 H 21 , R 2 =((S)-OCH(CH 3 )C 6 H 13 , k=1, m=0, and n=1, also known as W 314, shows a polarization density of -556 nC/cm 2 at 34° C. To our knowledge this is the highest polarization density reported to date for an FLC with one chiral tail. This is important in the present invention since the functional group array for this compound providing the large β axis oriented along the polar axis also possesses a large nearly colinear permanent molecular dipole moment. Specifically, this functional group array is the o-nitroalkoxy unit, similar to that present in the parent o-nitroanisole as illustrated below. ##STR19##
The dipole moment of o-nitroanisole is reported to be 4.8 D (McClellan, A. L. (1963) Tables of Experimental Dipole Moments; W. H. Freeman and Company: San Francisco). The observed ferroelectric polarization density of W 314, expressed in units of D/molecule, and assuming a density of about 0.8 gms/cm 3 , is P W314 =-2.1 D/molecule. Thus, making the reasonable assumption that the nitroalkoxy unit is responsible for the observed polarization, we can see that about 40% of the dipole of the molecules is actually oriented along the polar axis in the FLC phase of W 314. It should be noted that this is much better (by at least a factor of 2) than could be achieved for the same functional array and the same number density of nitroalkoxy units using the poled polymer method.
The large observed polarization density of the FLC phase of W 314, coupled with the fact that the NLO active unit has a large molecular dipole moment, leads to the conclusion that the NLO active units of W 314 are indeed well aligned along the polar axis in the FLC phase. This is consistent with the NLO results obtained for W 314 as shown in Table 3. Note that the second harmonic intensity at the top of the angle phase-matched peak is 8×10 4 times that of DOBAMBC, and that the magnitudes of the largest coefficients of the d tensor are in fact larger than that for KDP (see Table 1), even though the data were taken at an elevated temperature of 60° C., where the polar order (as evidenced by the ferroelectric polarization density) is considerable smaller than at 34° C. To our knowledge this compound possesses the largest X.sup.(2) measured for any ferroelectric liquid crystal.
TABLE 3______________________________________Values of the ferroelectric polarization, SHG efficiency, andχ.sup.(2) (d.sub.eff and dcoefficients), for FLCs of the present invention.Entry P SHG dnum- (nC/ arb d.sub.eff coefficientsber compound cm.sup.2) units* (pm/V) (pm/V)______________________________________1 W 314 -420.sup.↑ 8 × 10.sup.4 0.23 d.sub.2,3 =0.63 ±The compound of 0.03formula I where d.sub.2,2 = 0.6 ±R.sub.1 = n-C.sub.10 H.sub.21, R.sub.2 = 0.3(S)--(CH(CH.sub.3)C.sub.6 H.sub.11, d.sub.2,1 = 0.08 ±X.sub.1 = NO.sub.2, X.sub.2 = X.sub.3 = 0.02X.sub.4 = H, m = 0 and n = d.sub.2,5 = 0.16 ±1 0.052 W 316 -246.sup. 2 × 10.sup.4 0.1Compound of formulaI where R.sub.2 =n-C.sub.10 H.sub.21, R.sub.1 =(S)--(CH(CH.sub.3)C.sub.6 H.sub.11,X.sub.2 = NO.sub.2, X.sub.1 = X.sub.3 =X.sub.4 = H, n = 1 and m =0______________________________________ *Intensity of the second harmonic light at the top of the type 1 eeo angl phasematched peak. .sup.↑ The SHG measurements with W 314 were performed at 60° C., where P ≅ -420 nC/cm.sup.2.
TABLE 4__________________________________________________________________________ ##STR20##__________________________________________________________________________W335, X.sub.1 = H, X.sub.2 = H, R.sub.1 = n-C.sub.10 H.sub.21 W333, X.sub.1 = NO.sub.2, X.sub.2 = H, R.sub.1 = n-C.sub.10 H.sub.21MX511, 10% (wt) W335 in MDW158 MX542, 10% (wt) W333 in W346X←-21.2--C*.sup.← -64.2--A*←-68--N*←-70--I X←- <31--C*←-67--A*←-107--IX-→C*--74-→N*--77-→I X-- -→C*--68-→A*--107-→IP.sub.ext = -46 nC/cm.sup.2 @ 25° C., T-Tc = -39° C.,θ = 23.5° P.sub.ext = -290 nC/cm.sup.2 @ 25° C., T-Tc = -43° C., θ = 28°P.sub.ext = -37 nC/cm.sup.2 @ 55° C., T-Tc = -10° C.,θ = 18.5° P.sub.ext = -180 nC/cm.sup.2 @ 55° C., T-Tc = -10° C., θ = 18.3°MX545, 10% (wt) W335 in W346 X←- --SB←-7--C*←-75.5--A*.rarw.-112--I P.sub.ext = -150 nC/cm.sup.2 @ 30° C., T-Tc= -45.5° C., θ = 29° ##STR21##P.sub.ext = -120 nC/cm.sup.2 @ 65° C., T-Tc = -10° C.,θ = 24.5° MX547, 10% (wt) W340 in W346MX546, 16% (wt) W355 in W346 X←- <32--C*←-55.5--A*←-113--IX←-23--C*←-69--A*←-105.8--1 X--57-→A*--114-→IP.sub.ext = -160 nC/cm.sup.2 @ 24° C., T-Tc = -45° C.,θ = 29° P.sub.ext = -250 nC/cm.sup.2 @ 25° C., T-Tc = -30.5° C., θ = 27.5°P.sub.ext = -94 nC/cm.sup.2 @ 60° C., T-Tc = -10° C.,θ = 22.5° P.sub.ext = -200 nC/cm.sup.2 @ 45° C., T-Tc = -10° C., θ = 26°__________________________________________________________________________
TABLE 5__________________________________________________________________________ ##STR22##__________________________________________________________________________W355, Z' = H, Q' = H, R.sub.1 = n-C.sub.10 H.sub.21 MX549, 50% (wt) W349 in W346X←-S.sub.7 ←-61--C*←-79--N*←-114--I X←-25--C*←-45.7--A*←-105.5--IX--61-→C*--75-→N*--114--I X--36-→C*P = -27 nC/cm.sup.2 @ 65° C., T-Tc = -14° C., θ =26.5° P.sub.ext = -95 nC/cm.sup.2 @ 10° C., T-Tc = -35.7° C., θ = 14°P = -27 nC/cm.sup.2 @ 69° C., T-Tc = -10° C., θ =26.5° P.sub.ext = -57 nC/cm.sup.2 @ 35° C., T-Tc = -10° C., θ = 11°W349, Z' = NO.sub.2, Q' = H, R.sub.1 = n-C.sub.10 H.sub.21 MX556, 20% (wt) W349 in [75% W346/25% MDW158]X--36-→A*--80-→1 X←-<14--C*←-62--A*←-105--IX←-SB←-5--A*←-80--I X--<14-→C*--62-→A*--107-→IMX541, 10% (wt) W349 in W346 P.sub.ext = -200 nC/cm.sup.2 @ 15° C., T-Tc = -47° C., θ = 25°X←-29--C*←-80.5--A*←-120--I P.sub.ext = -133 nC/cm.sup.2 @ 50° C., T-Tc = -10° C., θ = 16.5°X--36-→C*P.sub.ext = -350 nC/cm.sup.2 @ 30° C., T-Tc = -50.5° C.,θ = 30.5° P.sub.ext = -170 nC/cm.sup.2 @ 70° C., T-Tc= -10° C., θ = 26° ##STR23## Liquid at room temperature, no apparent LC phases down to -20° C.MX548, 25% (wt) W349 in W346 MX550, 10% (wt) W349 in W346X←-<25--C*←-74.9--A*←-115--I X←-23--C*←-69--A*←-106--IX--36-→C* X-→30-→C*P.sub.ext = -280 nC/cm.sup.2 @ 20° C., T-Tc = -54.9° C.,θ = 28° P.sub.ext = -720 nC/cm.sup.2 @ 25° C., T-Tc = -44° C., θ = 30.5°P.sub.ext = -190 nC/cm.sup.2 @ 65° C., T-Tc = -10° C.,θ = 23.5° P.sub.ext = -460 nC/cm.sup.2 @ 60° C., T-Tc = -10° C., θ = 24.5°__________________________________________________________________________
While the individual components of the d tensor have not yet been measured, angle phase-matched SHG from the compound of formula I wherein X 2 =NO 2 , X 1 =X 3 =X 4 =H, R 1 =((S)-CH(CH 3 )C 6 H 13 , R 2 =C 10 H 21 , n=1 and m=0, also known as W 316, is also large relative to previously known FLC materials as shown in Table 3.
The polarization density observed for the compound of formula I where X 1 =H, X 3 =NO 2 , X 2 and X 4 =H, R 1 =OC 10 H 21 , and R 2 =(S)-(O(CH(CH 3 )C 6 H 13 , k=1, m=0, and n=1 (W 320) exhibits the same polarization expected for the compound where all the X groups are H (Furukawa (1988) supra, Walba (1991) supra). Similarly, the compound of formula II where where R 1 =OC 10 H 21 , R 2 =((R)-(OCH(CH 3 )CO 2 C 2 H 5 ), X 1 =NO 2 , X 2 =X 3 =H, and n=1 (W 334) shows a considerably larger extrapolated polarization in two hosts than the compound of formula II where R 1 =OC 10 H 21 , R 2 =((R)-(OCH(CH 3 )CO 2 C 2 H 5 ), X 1 =X 2 =X 3 =H, and n=1 (W 336).
Also provided is the compound of formula I where R 2 =(S)-(OCH(CH 3 )C 6 H 11 ), R 1 =OC 10 H 21 , X 1 =NO 2 , X 2 =X 3 =X 4 =H, k=1, n=0 and m=1 (W 317). This compound possesses a broad temperature smectic A phase, but no smectic C* phase. It is known that chiral smectic A LC materials exhibit the electroclinic effect (Garoff, S., et al., (1977) Phys. Rev. Lett. 38:848) and that the electroclinic effect can be useful for electrooptic device applications of the type involving nuclear motions (Andersson, G., et al., (1987) Appl. Phys. Lett. 51:640). The compound of the present invention (W 317) exhibits a surprisingly large, relatively temperature independent electroclinic effect far from the virtual smectic C*-smectic A transition. When R 1 =ω-decenyloxy, the electroclinic effect of the W 317 alkene is approximately half as large.
Finally, two mixtures containing only components of formula I, and possessing room temperature C* phases, including one mixture with an enantiotropic room temperature C* phase (1:1 W316 and W 317) are provided. This illustrates the general fact that when LC components with immiscible crystal phases but miscible LC phases are mixed, then the temperature range of the LC phases are broadened. This technique can produce stable room temperature FLC mixtures composed entirely of the compounds of the present invention. The mixtures wherein W317 is a component, in particular the 1:1 mixture of W316 and W317, also exhibits a large electroclinic effect in the smectic A phase.
The FLC properties of the compounds of formula II are illustrated by the properties of the compounds and mixtures listed in Table 4.
The FLC properties of the compounds of formula IV are illustrated by the properties of the compounds and mixtures listed in Table 5. Of particular interest is the high polarization room temperature smectic C* mixture MX556 of W349 in a 3:1 (by weight) mixture of W346 with MDW158. W346 is racemic W314. Also of interest is W350 which has a very high extrapolated polarization density.
Although not wishing to be bound by any theory, it is believed that the properties of the compounds of the present invention may be qualitatively understood and interpreted in terms of the diagrams shown in Schemes XV-XVIII. These diagrams assume that in the smectic C phase the "crystal packing" forces exerted on an individual molecule by the rest of the molecules in the phase may be approximated by a binding site taking the shape of a bent cylinder (see Walba, D. M., et al., (1986) J. Am. Chem. Soc. 108:5210-5221 and Walba (1991) supra). The functional group orientation occurring in the phase may be considered to result from the way the molecules "dock" into this binding site. The diagrams afford a qualitative estimate of how the molecules are oriented relative to the C* phase tilt plane when docked in a preferred way in the binding site. In order to make this estimate, a judgment concerning the preferred conformations present in the phase, and how these conformations dock into the binding site must be made. For many FLC structural types, it is possible to make educated guesses as to these preferred conformations and their docking mode. Such educated guesses were used to construct the diagrams shown in the schemes.
Scheme XV illustrates the suggested origins of the ferroelectric polarization of compounds of formula I wherein X 1 -X 4 are H, R 2 is (S)-OCH(CH 3 )C 6 H 13 , k=1 and m=0. That is, the polarization derives from an excess of molecules occurring in orientation A relative to orientations B or C. In orientation A, the molecular dipole moment from the Ar--O--C.sub.α functional group is oriented along the polar axis (normal to the tilt plane) in such a way that negative P is predicted (P is opposed to z×n). If orientation C were favored, the positive P would be expected. If orientation B were favored, then small P would be expected since the dipole component oriented normal to the tilt plane is small. Conformation A should be favored by simple conformational analysis arguments (i.e., the methyl group should prefer to be anti to the methylene group at C.sub.γ of the tail and the orientation shown relative to the tilt plane comes from the preferred mode of docking in the binding site.
Scheme XVI illustrates the suggested origins of the ferroelectric polarization and X.sup.(2) of compounds of formula I wherein X 1 =NO 2 , X 2 -X 4 are H, R 2 is (S)-OCH(CH 3 )C 6 H 13 , k=1 and m=0. When one position ortho to the alkoxy tail is occupied by a nitro grouping and the other ortho position bears a hydrogen atom, the preferred conformation A now has two different possible orientations of the nitro group relative to the tilt plane. Due to a clear excess steric hindrance present in conformation A", it is suggested that conformation A' is preferred. In this conformation and orientation, the molecular dipole moment and the molecular β from the nitro alkoxy unit are oriented along the polar axis of the phase. An enhanced ferroelectric polarization relative to the compounds without the ortho nitro grouping is expected, as well as enhanced X.sup.(2).
In the case where the nitro grouping is mete to the alkoxy tail, as for example in the compound of formula I W320, no enhancement in the polarization or X.sup.(2) relative to compounds without a nitro substituent is expected. This can be seen by inspection of the diagrams in Scheme XVII. In this case the conformations A' and A" are expected to be close in energy, and to have almost equal number densities in the phase. Therefore, the nitroalkoxy grouping of this molecule is not expected to be oriented in a polar fashion relative to the tilt plane, and most or all of the polarization and X.sup.(2) of the molecule derives simply from the alkoxy grouping in the chiral tail.
Scheme XVIII illustrates the binding site model for orientation of the prototypical "large β" functional array, the p-nitroaniline unit, along the polar axis in FLC phases of compounds of formula I where X 1 =NO 2 , X 3 =NH 2 , X 2 and X 4 are H, R 2 is (S)-OCH(CH 3 )C 6 H 13 , k=1 and m=0 (diagram on the left), and where X 2 =NO 2 , X 4 =NH 2 , X 1 and X 3 are H, R 1 is (S)-OCH(CH 3 )C 6 H 13 , k=1 and n=0 (diagram on the right). In the latter case, it is possible that the indicated intramolecular hydrogen bonding is also occurring between the carbonyl oxygen of the group (B)=COO, and one of the hydrogens on the nitrogen atom, leading to additional polar orientation of the carbonyl grouping as indicated.
These same arguments can be made for other core coupling chiral tails. Variation in the structure, length and degree of branching of the R 1 and R 2 groups of compound encompassed in formulas I and II can affect the liquid crystal properties of the pure material or mixtures containing them. For example, some of the chiral nonracemic compound of the present invention may possess smectic C* phases while others do not and the characteristics of any such smectic C* phases (i.e., stability, temperature range) may vary. ##STR24##
The following examples illustrate the invention and are in no way intended to limit the scope of the invention. In particular, it will be apparent to those of ordinary skill in the art that when attached to a polymeric backbone to give side-chain LC homopolymers or copolymers, the mesogenic units of the present invention may give FLC polymers with LC properties similar to the low molar mass mesogens of the present invention. In addition, such FLC polymers will, upon cooling, give crystalline, microcrystalline, or glassy polymer solids (Walba (1989) supra) with stable polar order which are of particular utility in certain NLO applications requiring a solid thin film material. It is within the skill of an ordinary artisan to prepare FLC polymers, such polysiloxanes, employing the compounds of the present invention, in particular the compounds wherein the achiral tail is an ω-alkenyl tail. It will be understood by those in the art that enantiomers will have equal magnitude but opposite sign of the ferroelectric polarization, and that such enantiomers are of similar utility for NLO applications and are encompased by this invention. This invention also encompasses mixtures of the compounds of the present invention with themselves or with any compatible hosts.
All references cited in this specification are hereby incorporated by reference in their entirety.
EXAMPLES
Example 1: Synthesis of (S)-4-(1-methylheptyloxy)-3-nitrophenol (compound 11 of Scheme I, R 2 =(S)-OCH(CH 3 )C 6 H 13 )
(S)-[4-(1-methylheptyloxy)-3-nitrophenyl]-benzoate
To an argon-flushed flask containing 8 mmol of nitro-phenol 9 (Scheme I) (literature: Rajamohan, K. et al., (1973) Indian J. Chem. 11:1076) and 1.25 eq. of triphenylphosphine dissolved 150 ml of dry THF, a solution of 8.08 mmol of (R)-2-octanol in 20 ml of dry THF was added via syringe. Then 1.25 eq. of diethyl azodicarboxylate dissolved in 40 ml of dry THF was added dropwise over 30 min. The reaction mixture was heated to 60° C. and stirred at this temperature for 19-22 h. Water (5 drops) was added and stirring was continued for another hour. The reaction mixture was evaporated and the crude product was extracted with a hexanes/ethyl acetate (70/30) and filtered through a short pad of silica gel. The filtrate was evaporated and the ether-derivative was purified by flash chromatography on silica gel to give (S)-[4-(1-methylheptyloxy)-3-nitrophenyl]-benzoate (Compound 10, Scheme I, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) in 80-90% yield as a yellow liquid: R f [hexanes/ethyl acetate 85/15]: 0.52; 1 H-NMR (300 MHz, CDCl 3 ): δ 0.82 (t, 3H, J=6.8 Hz); 1.15-1.52(m, 8H); 1.35(d, 1H, J=6.1 Hz); 1.62(m, 1H); 1.78(m, 1H); 4.48(m, 1H); 7.09(d, 1H, J=9 Hz); 7.37(dd, 1H, J=2.8 Hz, J=9 Hz); 7.46-7.67(m, 3H); 7.70(d, 1H, J=2.8 Hz); 8.16(dd, 2H, J=2.1 Hz, J=7.2 Hz); 13 C-NMR (300 MHz, CDCl 3 ): δ 14.00, 19.45, 22.50, 25.18, 29.10, 31.66, 36.16, 76.94, 116.44, 119.12, 127.25, 128.71, 128.77, 130.24, 134.02, 140.44, 142.79, 149.57, 164.96; IR (CHCl 3 ): 3040, 2940, 2850, 1740, 1600, 1525, 1490, 1305, 1260, 1190, 1060, 1025, 900, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 371 (M + 0.2), 259(3), 213(4), 184(14), 105(100), 77(15), 55(10), 43(19), 41(11).
Anal. Calcd. for C 21 H 25 NO 5 : C 67.91, H 6.78, N 3.77. Found: C68.22, H 6.90, N3.99.
(S)-4-(1-methylheptyloxy)-3-nitro-phenol
To a solution of 5.3 mmol of ester 10 in 40 ml of methanol and 15 ml of water, 22 mmol of LiOH·H 2 O was added. The reaction mixture was stirred vigorously at room temperature for 14-22 h until no starting material was detected by TLC. The solution was diluted with 65 ml of 3.5% (wt/wt) NaOH solution, acidified by adding concentrated HCl with ice and extracted several times with ethyl ether. The combined organic layers were dried over anhydrous MgSO 4 and the solvent removed. The phenol were purified by flash chromatography with hexanes/ethyl acetate [90:10] to give (S)-4-(1-methyl-heptyloxy)-3-nitro-phenol (Compound 11, Scheme I, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) in 89-98% yield as an orange liquid: R f [hexanes/ethyl acetate 85/15]: 0.24; 1 H NMR (300 MHz, CDCl 3 ): δ 0.84(t, 3H, J=6.8 Hz), 1.16-1.48(m, 8H), 1.27(d, 3H, J=6.1 Hz), 1.56(m, 1H), 1.72(m, 1H), 4.35(m, 1H), 5.44(broad s, 1H), 6.94(d, 1H, J=9 Hz), 7.01(dd, 1H, J=2.8 Hz, J=9 Hz), 7.28(d, 1H, J=2.8 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.98, 19.49, 22.50, 25.19, 29.15, 31.66, 36.19, 77.57, 112.03, 118.50, 121.44, 140.98, 145.81, 148.84; Mass spectrum, m/z(rel.intensity): 267(M + 0.3), 156(8), 155(100), 71(9) 57(20), 55(16), 43(29).
Anal. Calcd. for C 14 H 21 NO 4 : C 62.90, H 7.92, N 5.24. Found: C 62.82, H 8.05, N 5.24.
Example 2. Synthesis of (S)-4'-(1-methylheptyloxy)-3'-nitro-4-hydroxybiphenyl (Compound 17, Scheme II, R 2 =(S)-OCH(CH 3 )C 6 H 13 )
4'-Hydroxy-4-biphenylyl-benzoate
To a solution of 100 mmol of biphenol in 120 ml of dry pyridine was added 1.5 eq. of benzoyl chloride dropwise over 45 min. The reaction mixture was stirred for another 45 min at room temperature and then 20 ml of ethanol was added and stirring was continued for 30 min. The mixture was poured into water-ice and stirred for 30 min. The precipitate was filtered and washed several times with water. The product phenol was purified by flash chromatography on silica gel with dichloromethane as eluent. Recrystallization from toluene afforded 4'-hydroxy-4-biphenylyl-benzoate (Compound 14, Scheme II, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a white solid in 22% yield: R f [dichloromethane]: 0.25; 1 H NMR (300 MHz, Acetone-d 6 ): δ 7.95(d, 2H, J=8.8 Hz), 7.34(d, 2H, J=8.5 Hz), 7.50-7.80(m, 7H), 8.21(dd, 2H, J=1.2 Hz J=8.3 Hz), 8.64(broad s, 1H); 13 C NMR (300 MHz, Acetone-d 6 ): δ 116.60, 123.02, 128.12, 128.90, 129.69, 130.62, 130.78, 132.33, 134.61, 139.65, 150.94, 158.14, 165.64; Mass spectrum, m/z(rel.intensity): 290(M + 16), 105(100), 77(29).
Anal. Calcd. for C 19 H 14 O 3 : C 78.61, H 4.86. Found: C 79.02, H 4.80.
4'-Hydroxy-3'-nitro-4-biphenylyl benzoate
To an argon-flushed flask containing a suspension 0.486 g (1.68 mmol) of 4'-hydroxy-4-biphenylyl benzoate in 10 ml of acetic acid at 10°-15° C., 0.345 ml of HNO 3 (d: 1.41) was added dropwise (about a drop per min). Then the reaction mixture was vigorously stirred at the same temperature for 30 min. Water (40 ml) was added and the mixture was again stirred for 30 min. The yellow precipitate was filtered, washed several times with water, dried and purified by flash chromatography on silica gel using dichloromethane/hexanes [65/35] as eluent to give 4'-hydroxy-3'-nitro-4-biphenylyl benzoate (compound 15, Scheme II) as a yellow solid (0.539 g, 96%). This material was recrystallized from ethanol to give product of mp. 163° C.; . R f [hexanes/dichloromethane 40/60]: 0.42; 1 H NMR (300 MHz, CDCl 3 ): δ 7.25(d, 1H, J=8.7 Hz), 7.33(d, 2H, J=8.7 Hz), 7.50-7.70(m, 5H), 7.84(dd, 1H, J=2.7 Hz, J=8.7 Hz), 8.23(d, 2H, J=7.2 Hz), 8.32(d, 1H, J=2.7 Hz), 10.60(s, 1H); 13 C NMR (300 MHz, CDCL 3 ): δ 120.54, 122.45, 122.81, 127.85,, 128.65, 129.33, 130.23, 133.04, 133.78, 136.04, 136.22, 150.91, 154.44, 165.15; IR (CHCL 3 ): 3250(broad), 3020, 1740, 1620, 1540, 1510, 1490, 1325, 1270, 1225, 1220, 1170, 1080, 1065, 1025, 1000, 850 cm -1 ; Mass spectrum, m/z(rel.intensity): 335(M + 7), 105(100), 77(16) .
Anal. Calcd. for C 19 H 13 NO 5 : C 68.06, H 3.91, N 4.18. Found: C 68.11, H 3.84, N 4.03.
(S)-4'-(1-methylheptyloxy)-3'-nitro-4-biphenylylbenzoate
4'-Hydroxy-3'-nitro-4-biphenylyl benzoate was alkylated using the same procedure as that used to prepare (S)-[4-(1-methylheptyloxy)-3-nitrophenyl]-benzoate to give (S)-4'-(1-methyl-heptyloxy)-3'-nitro-4-biphenylylbenzoate (Compound 16, Scheme II, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a slightly yellow solid; (mp. 39° C.). R f [toluene/hexanes 70/30]: 0.27; 1 H NMR(300 MHz, CDCl 3 ); δ 0.87(t, 3H, J=6.7 Hz), 1.20-1.55(m, 8H), 1.36(d, 3H, J=6.1 Hz), 1.65(m, 1H), 1.80(m, 1H), 4.53(m, 1H), 7.11(d, 1H, J=8.8 Hz), 7.28(d, 2H, J=8.7 Hz), 7.46-7.65(m, 5H), 7.68(dd, 1H, J=2.4 Hz, J==8.8 Hz), 7.98(d, 1H, J=2.4 Hz), 8.21(dd, 2H, J=1.5 Hz, J=7.2 Hz); 13 C NMR (300 MHz, CDCl 3 ); δ 13.99, 19.48, 22.50, 25.16, 29.11, 31.66, 36.17, 76.51, 116.10, 122.34, 123.77, 127.81, 128.63, 129.33, 130.21, 131.95, 132.46, 133.75, 136.35, 141.07, 150.69, 165.18; Mass spectrum, m/z(rel.intensity): 447(M + 5), 417(12), 416(9), 335(16), 305(13), 105(100), 77(8), 71(12), 57(18), 55(10), 43(30).
Anal. Calcd. for C 27 H 29 NO 5 : C 72.46, H 6.53, N 3.13. Found: C 72.46, H 6.55, N 3.10.
(S)-4'-(1-methylheptyloxy)-3'-nitro-4-hydroxybiphenyl
The benzoyl ester of (S)-4'-(1-methylheptyloxy)-3'-nitro-4-biphenylylbenzoate was saponified using the same procedure as that used for saponification of (S)-[4-(1-methylheptyloxy)-3-nitrophenyl]-benzoate except that the reaction was carried out at 60° C. to give (S)-4'-(1-methylheptyloxy)-3'-nitro-4-hydroxybiphenyl (Compound 17, Scheme II, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a very viscous orange liquid after flash chromatography with hexanes/ethyl acetate [88/12]; R f [hexanes/ethyl acetate 85/15]: 0.17; 1 H NMR (300 MHz, CDCl 3 ): δ 0.86(t, 3H, J=6.6 Hz), 1.18-1.52(m, 8H), 1.35(d, 3H, J=6.1 Hz), 1.62(m, 1H), 1.78(m, 1H), 4.50(m, 1H), 5.22(broad s, 1H), 6.89(d, 2H, J=8.5 Hz), 7.07(d, 1H, J=8.8 Hz), 7.39(d, 2H, J=8.5 Hz), 7.62(dd, 1H, J=2.4 Hz, J=8.8 Hz), 7.92(d, 1H, J=2.4 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.99, 19.49, 22.50, 25.19, 29.10, 31.65, 36.17, 76.57, 115.94, 116.17, 123.30, 127.99, 131.21, 131.64, 133.09, 141.00, 15.42, 155.52; IR (CHCl 2 ); 350, 3300(broad), 3020, 2920, 2840, 1610, 1540, 1510, 1485, 1350, 1260, 1220, 1160, 1110, 1040, 925, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 343(M + 5), 231(100), 185(6), 57(6), 43(12).
Anal. Calcd. for C 20 H 25 NO 4 : C 69.95, H 7.34, N 4.08. Found: C 69.84, H 7.44, N 4.08.
Example 3. Synthesis of (S)-4(1-methyl-heptyloxy)-2-nitro-phenol Compound 20, Scheme III, R 2 =(S)-OCH(CH 3 )C 6 H 13 )
(S)-p-Benzyloxy-(1-methylheptyloxy)benzene
To an argon-flushed flask containing a solution of 3.01 g (15 mmol) of p-benzyloxy-phenol and 1.25 eq of triphenylphosphine in 220 ml in dry dichloromethane, was added a solution of 4.91 g (15.14 mmol) of (R)-2-octanol in 30 ml of dry dichloromethane via syringe. Then 1.20 eq of diethyl azodicarboxylate dissolved in 60 ml of dry dichloromethane was added dropwise for 30 min. The reaction mixture was stirred at room temperature for 19 h, Then 5 drops of water were added and the mixture was stirred for 1 h. The solvent was then evaporated and the residual crude product was triturated in a mixture of hexanes/ethyl acetate [70/30] for 1 h and filtered through a short silica gel pad. The filtrate was evaporated and the product was purified by flash chromatography on silica gel using dichloromethane/hexanes [10/90] as eluent, affording 3.32 g (71%) of (S)-p-Benzyloxy-(1-methylheptyloxy)benzene (Compound 18, Scheme III, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a colorless liquid: R f [dichloromethane/hexanes 10/90]: 0.13; 1 H NMR (300 MHz, CDCl 3 ): δ 0.87(t, 3H, J=6.6 Hz), 1.20-1.60(m, 12H), 1.70(m, 1H), 4.21(m, 1H), 5.00(s, 2H), Distorted AA'BB' System [6.82(d, 2H) 6.88(d, 2H)], 7.30-7.46(m, 5H); 13 C NMR (300 MHz, CDCl 3 ): δ 14.02, 19.77, 22.55, 25.52, 29.26, 31.77, 36.51, 70.63, 74.95, 115.77, 117.35, 127.49, 127.87, 128.55, 137.39, 152.53, 153.01; IR (CHCl 3 ): 3010, 2940, 2850, 1600, 1500, 1475, 1450, 1375, 1230, 1200, 1125, 1025, 925, 825 cm -1 ; Mass spectrum, m/z (rel.Intensity): 312(M + 7), 212(15), 91(100), 71(5), 57(8), 43(10).
(S)-p-(1-methylheptyloxy)phenol
A flask fitted with a gas inlet tube was charged with a suspension of 10% Pd/C (6 g) in 100 ml of dry dichloromethane. The flask was evacuated and filled with argon, then evacuated again and filled with hydrogen, which was then allowing to bubble through the stirred suspension for 30 min before a solution of 30 mmol of benzyl ether in 70 ml of dry dichloromethane was added via syringe. After the reaction was judged complete by TLC (about 4 h) hydrogen ebullition was stopped, and the resulting suspension was filtered through a Celite pad. The solvent was evaporated and the resulting crude product was purified by flash chromatography on silica gel (hexanes/ethyl acetate [99/1]) to give (S)-p-(1-methylheptyloxy)phenol (Compound 19, Scheme III, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a colorless liquid in 85-97% yield: R f [hexanes/ethyl acetate 95/5]: 0.15. [α] D 25 : +11.5° (c 3.31, CHCl 3 ) (Literature value=+11.4° (c 10.1, CHCl 3 ): Inukai, T. et. al., (1986) Mol. Cryst. Liq. Cryst. 141:251); 1 H NMR (300 MHz, CDCl 3 ): δ 0.87(t, 3H, J=6.3 Hz), 1.15-1.56(m, 9H), 1.23(d, 3H, J=6.1 Hz), 1.70(m, 1H), 4.17(m, 1H), 5.28(s, 1H), Distorted AA'BB' System [6.72(d,2H) 6.76(d, 2H)]; 13 C NMR (300 MHz, CDCl 3 ): δ 14.00, 19.72, 22.52, 25.49, 29.22, 31.74, 36.43, 75.55, 116.08, 117.85, 149.64, 152.12; IR (CHCl 3 ): 3600, 3480(broad), 3010, 2940, 2850, 1600, 1500, 1450, 1375, 1225, 1170, 1120, 1030, 925, 825 cm -1 ; Mass spectrum, m/z (rel.intensity): 222(M + 5), 110(100), 43(7).
(S)-4(1-methylheptyloxy)-2-nitro-phenol
To an argon-flushed flask containing 85 mg (1 mmol) of NaNO 3 , 4.3 mg (0.01 mmol) of La(NO 3 ) 3 ·6 H 2 O, 1.2 ml of water and 0.8 ml of HCl, was added a solution of 222 mg (1 mmol) of (S)-4-(1-methylheptyloxy)-phenol in 6 ml of ethyl ether. After 4 h 30 min of vigorous stirring at room temperature the reaction mixture took on a yellow color that changed very fast to orange. After turning orange, the mixture was stirred for another 15-20 min and then water was added. The organic layer was separated and the aqueous layer was extracted several times with water. The combined organic layers were washed with water until the washes were pH-6 and then with brine. The resulting organic solution was dried and the solvent evaporated. Flash chromatography on silica gel with hexanes/ethyl acetate [99/1] (other eluents were used with the same results) afforded a mixture of two compounds that could be purified by flash chromatography on alumina [activity grade III, 6% of water] using Cl 4 C→Cl 4 C/Cl 2 CH 2 [80/20] as eluent. The first fractions afforded 130 mg (50% ) of (S)-4-(1-methyl-heptyloxy)-2-nitrophenol (Compound 20, Scheme III, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as an orange liquid; R f [toluene/hexanes 45/55]: 0.45; 1 H NMR (300 MHz, CDCl 3 ): δ 0.86(t, 3H, J=6.7 Hz), 1.15-1.46(m, 11H), 1.56(m, 1H), 1.67(m, 1H), 4.28(m, 1H), 7.03(d, 1H, J=9.2 Hz), 7.17(dd, 1H, J=2.9 Hz, J=9.2 Hz), 7.47(d, 1H, J=2.9 Hz), 10.27(s, 1H); 13 C NMR (300 MHz, CDCl 3 ): δ 13.97, 19.34, 22.50, 25.32, 29.14, 31.69, 36.16, 75.32, 108.53, 120.72, 128.71, 133.11, 149.78, 151.16; IR (CHCl 3 ): 3250(broad), 3010, 2930, 2840, 1600, 1570, 1480, 1425, 1375, 1325, 1250, 1125, 1075, 975, 825 cm -1 ; Mass spectrum, m/z (rel.intensity): 267(M + 5), 155(100), 71(21), 57(21), 55(10), 43(27);
Anal. Calcd. for C 14 H 21 NO 4 : C 62.90, H 7.92, N 5.24. Found: C 62.16, H 7.82, N 5.06.
Example 4. Synthesis of (S)-4'-(1-methyl-heptyloxy)-4-hydroxy-3 -nitro-biphenyl (Compound 41, Scheme VIII, R 2 =(S)-OCH(CH 3 )C 6 H 13 )
(S)-4'-(1-Methylheptyloxy)-4-biphenyl benzoate
To an argon-flushed flask containing 2.32 g (8 mmol) of 4'-hydroxy-4-biphenylyl benzoate and 1.25 eq of triphenylphosphine in 200 ml of dry THF was added a solution of 1.052 g (8.08 mmol) of (R)-2-octanol dissolved in 15 ml of dry THF via syringe. Then 1.2 eq of diethyl azodicarboxylate in 30 ml of dry THF was added dropwise over 30 min. The reaction mixture was stirred at room temperature for 20 h and then 5 drops of water was added and stirring was continued for an additional 1 h. The solvent was evaporated and the crude product was triturated for 1 h in a mixture of hexanes/ethyl acetate [70/30]. The solution was filtered through a short silica gel pad and the solvent evaporated. Flash chromatography on silica gel using hexanes/ethyl acetate [98/2] as eluent afforded 2.42 g (75%) of (S)-4'-(1-methylheptyloxy)-4-biphenylyl benzoate (Compound 39, Scheme VIII, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a white solid (mp. 84° C.); R f [hexanes/ethyl acetate 95/5]: 0.34; 1 H NMR (300 MHz, CDCl 3 ): δ 0.89(t, 3H, J=6.8 Hz), 1.14-1.68(m, 9H), 1.32(d, 3H, J=6.1 Hz), 1.75(m, 1H), 4.39(m, 1H), 6.95(d, 2H, J=9 Hz), 7.25(d,2H, J=8.4 Hz), 7.46-7.68(m, 7H), 8.22(dd, 2H, J=1.2 Hz J=6.9 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 14.02, 19.73, 22.55, 25.50, 29.24, 31.75, 36.48, 73.96, 116.10, 121.88, 127.72, 128.58, 129.61, 130.21, 132.64, 133.59, 138.79, 149.87, 157.94, 165.30; IR (CHCl 3 ): 3020, 2930, 2850, 1745, 1600, 1500, 1260, 1240, 1170, 1190, 1070, 1000, 840, 820 cm -1 ; Mass spectrum, m/z(rel.intensity): 402(M + 16), 290(14), 105(100), 77(16), 43(6).
(S)-4'-(1-methylheptyloxy)-4-hydroxybiphenyl
The same procedure as that used for saponification of (S)-4-(1-methylheptyloxy)-3-nitro-phenol was used except the reaction was carried out in a methanol/dichloromethane [4:1] mixture at 60° C. Flash chromatography with hexanes/ethyl acetate [93/7] afforded (S)-4'-(1-methylheptyloxy)-4-hydroxybiphenyl (Compound 40, Scheme VIII, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a white solid (mp 100.5° C.); R f [hexanes/ethyl acetate 90/10]: 0.2; 1 H NMR (300 MHz, CDCl 3 ): δ 0.88(t, 3H, J=6.6 Hz), 1.20-1.64(m, 9H), 1.33(d, 3H, J=6.1 Hz), 1.74(m, 1H), 4.38(m, 1H), 5.07(s, 1H), 6.87(d,2H, J=8.5 Hz), 6.93(d, 2H, J=8.5 Hz), 7.42(d, 2H, J=8.5 Hz), 7.44(d, 2H, J=8.5 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 14.02, 19.73, 22.54, 25.51, 29.22, 31.74, 36.45, 74.17, 115.59, 116.16, 127.74, 127.94, 133.22, 133.77, 154.55, 157.31; IR (CHCl 3 ): 3560, 3350(broad), 3020, 2920, 2840, 1610, 1500, 1250, 1220, 1175, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 298(M + 11), 186(100), 185(4), 157(4).
Anal. Calcd. for C 20 H 26 O 2 : C 80.50, H 8.78. Found: C 80.41, H 8.77
(S)-4'-(1-methylheptyloxy)-4-hydroxy-3-nitro-biphenyl
To an argon-flushed flask containing 0.127 g (1.5 mmol) of NaNO 3 , 6.5 mg (0.015 mmol) of La(NO 3 ) 3 ·6 H 2 O, 1.2 ml of HCl and 1.5 ml of water was added a solution of 0.447 g (1.5 mmol) of (S)-4'-(1-methylheptyloxy)-4-hydroxy-biphenyl in 10 ml of ethyl ether. The reaction mixture was vigorously stirred at room temperature for 2 h and 30 min. Then water was added and the orange organic layer was removed. The aqueous layer was extracted several times with ethyl acetate and the combined organic layers were washed with water until the washes were pH-6, and then with brine. The organic solution was dried and the solvent evaporated. The crude product was purified by flash chromatography using hexanes/ethyl acetate [97/3] as eluent, affording 0.412 g (80%) of (S)-4'-(1-methylheptyloxy)-4-hydroxy-3-nitro-biphenyl (Compound 41, Scheme VIII, R 2 =(S)-OCH(CH 3 )C 6 H 13 ) as a yellow solid (mp. 40° C.); R f [hexanes/ethyl acetate [95/5]: 0.5; 1 H NMR (300 MHz, CDCl 3 ): δ 0.88(t, 3H, J=6.6 Hz), 1.17-1.69(m, 9H), 1.32(d, 3H, J=6.1 Hz), 1.77(m, 1H), 4.39(m, 1H), 6.95(d, 2H, J=8.4 Hz), 7.20(d, 1H, J=8.7 Hz), 7.47(d, 2H J=8.4 Hz), 7.78(dd, 1H J=2.4 Hz, J=8.7 Hz), 8.25(d, 1H, J=2.4 Hz), 10.55(s, 1H); 13 C NMR (300 MHz, CDCl 3 ): δ 14.00, 19.65, 22.53, 25.45, 29.21, 31.74, 36.40, 74.03, 116.29, 120.25, 122.03, 127.77, 130.35, 133.68, 133.75, 135.92, 153.86, 158.37; IR (CHCl 3 ): 3240(broad), 3020, 2950, 2850, 1625, 1600, 1510, 1485, 1425, 1325, 1240, 1225, 1175, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 343(M + 6), 231(100), 230(1), 214(2), 201(5), 185(5), 57(10), 34(15).
Anal. Calcd. for C 20 H 25 NO 4 : C 69.95, H 7.34, N 4.08. Found: C 70.24, H 7.44, N 4.07.
Example 5. Synthesis of (S)-4-(1-methylheptyloxy)-3-nitro-benzoyl chloride (Compound 25, Scheme IV, R 1 =(S)-OCH(CH 3 )C 6 H 13 )
(S)-Methyl-4-(1-methyheptyloxy)-3-nitrobenzoate
Methyl 4-hydroxy-3-nitrobenzoate was coupled with (R)-2-octanol using the same procedure as that given for alkylation of phenol 9, Scheme I, to give (S)-methyl-4-(1-methyheptyloxy)-3-nitrobenzoate (Compound 23, Scheme IV, R 1 =(S)-OCH(CH 3 )C 6 H 13 ). The product was purified by flash chromatography with hexanes/ethyl acetate (95/5) as eluent affording a yellow liquid, R f [hexanes/ethyl acetate 95/5]:0.25; 1 H-NMR (300 MHz, CDCl 3 ): δ 0.82 (t, 3H, J=7.1 Hz); 1.14-1.50 (m, 8H); 1.34(d, 3H, J=6.1 Hz); 1.60(m, 1H); 1.75(m, 1H); 3.87(s, 3H); 4.57(m, 1H); 7.06(d, 1H, J=8.9 Hz); 8.11(dd, 1H, J=2.2 Hz, J=8.9 Hz); 8.39(d, 1H, J=2.2 Hz); 13 C-NMR (300 MHz, CDCl 3 ): δ 13.96, 19.31, 22.47, 25.06, 29.02, 31.60, 36.00, 52.35, 76.80, 114.63, 121.80, 127.17, 134.80, 140.27, 154.91, 165.08; Mass spectrum, m/z(rel.intensity): 309 (M + 1), 197(32), 166(46), 112(48), 71(63), 57(100), 55(46).
Anal. Calcd. for C 16 H 23 NO 5 : C 62.12, H 7.49, N 4.53. Found: C 62.11, H 7.36, N 4.86.
(S)-4-(1-Methyl-heptyloxy)-3-nitro-benzoic acid
The same procedure as that used for saponification of (S)-4-(1-methylheptyloxy)-3-nitro-phenyl was used, affording (S)-4-(1-methyl-heptyloxy)-3-nitro-benzoic acid (Compound 24, Scheme IV, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) as a white solid after recrystallization from hexanes; R f [hexanes/ethyl acetate 1:1+a drop of acetic acid]: 0.28; 1 H NMR (300 MHz, CDCl 3 ): δ 0.83(t, 3H, J=6.8 Hz), 1.14-1.50(m, 8H), 1.37(d, 3H, J=6.1 Hz), 1.64(m, 1H), 1.79(m, 1H), 4.63(m, 1H), 7.10(d, 1H, J=8.9 Hz), 8.20(dd, 1H, J=2.2 Hz, J=8.9 Hz), 8.48(d, 1H, J=2.2 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.91, 19.34, 22.47, 25.07, 29.04, 31.62, 36.04, 77.15, 114.81, 120.89, 127.87, 135.35, 140.61, 155.71, 170.20; IR (CHCl 3 ): 3400-2500, 2940, 2850, 1680, 1610, 1530, 1400, 1350, 1280, 1125, 1075, 925 cm -1 ; Mass spectrum, m/z(rel.intensity): 295(M + 17), 184(100), 112(47, 71(53), 57(70), 55(35), 43(80), 41(79).
(S)-4-(1-methylheptyloxy)-3-nitro-benzoyl chloride
Acid 24 (Scheme IV, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) was converted to the acid chloride using oxalyl chloride in benzene. After removal of solvent, the crude acid chloride 25 (Scheme IV, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) was used directly in the coupling reactions without further purification or characterization.
Example 6. Synthesis of (S)-4'-(1-methylheptyloxy)-3'-nitro-4-biphenylcarboxylic acid chloride (Compound 32, Scheme V, R 1 =(S)-OCH(CH 3 )C 6 H 13 )
Methyl 4'-hydroxy-3'-nitro-4-biphenylcarboxylate
To an argon-flushed flask charged with 0.544 g (6.4 mmol) of NaNO 3 , 27.7 mg (0.064 mmol) of La(NO 3 ) 3 ·6 H 2 O, 9 ml of water and 5.1 ml of HCl, was added a solution of 1.46 g (6.4 mmol) of methyl 4'-hydroxy-biphenylcarboxylate (28, Scheme V, Literature: Otterholm, B., (1987), Ph.D. Thesis, Chalmers Technical University, Goteborg, Sweden) dissolved in 25 ml of THF/ethyl ether (55:45). The reaction mixture was vigorously stirred at 55° C. for 7 h. After cooling, water was added and the organic layer removed. The aqueous layer was extracted several times with ethyl ether and the combined organic layers were washed with water until the washes were pH-6. The organic solution was dried and the solvent evaporated. Flash chromatography on silica gel with hexanes/ethyl acetate [90/10] as eluent afforded 1.5 g (85%) of methyl 4'-hydroxy-3'-nitro-4-biphenylcarboxylate (Compound 29, Scheme V, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) as a yellow solid. Recrystallization from cychlohexane gave material with mp. 1.43° C.; R f [hexanes/ethyl acetate 90/10]: 0.26; 1 H NMR (300 MHz, CDCl 3 ): δ 3.92(s, 3H), 7.24(d, 1H, J=8.8 Hz), 7.59(d, 2H, J=8.5 Hz), 7.84(dd, 1H, J=2.2 Hz, J=8.8 Hz), 8.09(d, 2H, J=8.5 Hz), 8.20(d, 1H, J=2.2 Hz), 10.60(s, 1H); 13 C NMR (300 MHz, CDCl 3 ): δ 52.19, 120.71, 123.77, 126.57, 129.58, 130.40, 132.55, 133.82, 136.18, 142.46, 154.90, 166.66; IR (CHCl 3 ): 3240(broad), 1040, 2950, 1720, 1625, 1600, 1540, 1490, 1425, 1320, 1290, 1210, 1190, 980, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 273(M + 85), 242(100), 196(11), 168(14), 139(41), 59(9).
Anal. Calcd. for C 14 H 11 NO 5 : C 61.54, H 4.06, N 5.13. Found: C 62.10, H 4.00, N 4.92.
(S)-Methyl-4'-(1-methylheptyloxy)-3'-nitro-4-biphenylcarboxylate
Methyl 4'-hydroxy-3'-nitro-4-biphenylcarboxylate was coupled with (R)-2-octanol using the same procedure as that given for alkylation of phenol 9, Scheme I, to give (S)-methyl 4'-(1-methylheptyloxy)-3'-nitro-4-biphenylcarboxylate (Compound 30, Scheme V, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) as a slightly yellow solid after flash chromatography with hexanes/ethyl acetate [93/7]. Recrystallization from hexanes gave material with mp 69° C.; R f [hexanes/ethyl acetate 90/10]: 0.23; 1 H-NMR (300 MHz, CDCl 3 ): δ 0.85(t, 3H, J=6.8 Mz), 1.20-1.52(m, 8H), 1.36(d, 3H, J=6.1 Hz), 1.62(m, 1H), 1.80(m, 1H), 3.92(s, 3H), 4.53(m, 1H), 7.12(d, 1H, J=8.7 Hz), 7.59(d, 2H, J=8.4 Hz), 7.72(dd, 1H, J=2.4 Hz, J=8.7 Hz), 8.02(d, 1H, J=2.4 Hz), 8.08(d, 2H, J=8.4 Hz); 13 C NMR (300 Mz, CDCl 3 ): δ 13.99, 19.46, 22.50, 25.19, 29.09, 31.65, 36.13, 52.17, 76.58, 116.07, 124.04, 126.53, 129.31, 130.35, 131.90, 132.06, 141.11, 142.81, 151.49, 166.75; IR (CHCl 3 ): 3020, 2920, 2850, 1725, 1625, 1620, 1540, 1490, 1360, 1280, 1180, 1120, 1020, 820 cm -1 ; Mass spectrum m/z(rel.intensity): 385(M + 47), 354(27), 273(100), 242(34), 139(17), 71(10) 57(20), 43(45), 41(38).
Anal. Calcd. for C 22 H 27 NO 5 : C 68.55, H 7.06, N 3.63. Found: C 68.65, H 7.06, N 3.59.
(S)-4'-(1-methyl-heptyloxy)-3'-nitro-4-biphenylcarboxylic acid
The same procedure as that used for saponification of (S)-4-(1-methylheptyloxy)-3-nitro-phenol was used except that the reaction was carried out at 60° C., affording (S)-4'-(1-methyl-heptyloxy)-3'-nitro-4-biphenylcarboxylic acid (Compound 31, Scheme V, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) as a yellow solid; R f [hexanes/ethyl acetate 50%+a drop of acetic acid]: 0.36; 1 H NMR (300 MHz, CDCl 3 ): δ 0.86(t, 3H, J=6.7 Hz), 1.20-1.55(m, 8H), 1.37(d, 3H, J=6.1 Hz), 1.65(m, 1H), 1.80(m, 1H), 4.55(m, 1H), 7.14(d, 1H, J=8.7 Hz), 7.64(d, 2H, J=8.4 Hz), 7.74(dd, 1H, J=2.4 Hz, J=8.7 Hz), 8.05(d, 1H, J=2.4 Hz), 8.17(d, 2H, J=8.4 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.99, 19.47, 22.51, 25.17, 29.11, 31.64, 36.15, 76.65, 116.13, 124.13, 128.42, 131.04, 132.12, 141.16, 143.78, 151.66, 171.93; Mass spectrum, m/z(rel.intensity): 371(M + 0.38), 259(100), 139(11), 71(7), 57(16), 55(11), 43(27), 41(23).
(S)-4'-(1-methyl-heptyloxy)-3'-nitro-4-biphenylcarboxylic acid chloride
Acid 31 (Scheme V, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) was converted to the acid chloride using oxalyl chloride in benzene. After removal of solvent, the crude acid chloride 32 (Scheme V, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) was used directly in the coupling reactions without further purification or characterization.
Example 7. Synthesis of (S)-4-(1-methylheptyloxy)-2-nitro-benzoyl chloride (Compound 38, Scheme VI, R 1 =(S)-OCH(CH 3 )C 6 H 13 )
(S)-4-(1-Methylheptyloxy)-2-nitro-toluene
4-Methyl-3-nitrophenol (Compound 33, Scheme VI) was coupled with (R)-2-octanol using the same procedure as that given for alkylation of phenol 9, Scheme I, to give (S)-4-(1-methylheptyloxy)-2-nitro-toluene (Compound 34, Scheme VI, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) as a yellow liquid; R f [Hexanes/ethyl acetate 99/1]: 0.26; 1 H NMR (300 MHz, CDCl 3 ): δ 0.87(t, 3H, J=6.6 Hz), 1.16-1.65(m, 12H), 1.70(m, 1H), 2.50(s, 3H), 4.37(m, 1H), 7.02(dd, 1H ,J=2.7 Hz, J=8.5 Hz), 7.19(d, 1H, J=8.5 Hz), 7.47(d, 1H, J=2.7 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.97, 19.41, 19.63, 22.51, 25.32, 29.14, 31.69, 36.20, 74.72, 111.05, 121.44, 125.12, 133.44, 149.5, 156.77; IR (CHCl 3 ): 3020, 2940, 2850, 1620, 1550, 1525, 1490, 1375, 1300, 1240, 1220, 1110, 1050, 975, 860, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 265(M + 11), 153(33), 136(100), 112(21), 71(40), 57(70), 51(11), 43(78), 41(66).
Anal. Calcd. for C 15 H 23 NO 3 : C 67.90, H 8.74, 5.28. Found:C 67.42, H 8.49, N 5.51.
(S)-α-Bromo-4-(1-methylheptyloxy)-2-nitrotoluene
A suspension of 6.1 g (34.4 mmol) of NBS and 4 g of silica gel in 125 ml of dry dichloromethane was stirred under argon for 30 min. Then a solution of 4.56 g (17.2 mmol) of (S)-4-(1-methylheptyloxy)-2-nitro-toluene in 150 ml of dichloromethane was added via syringe. The reaction mixture was stirred at room temperature for 72 h. The resulting suspension was filtered through a short silica gel pad and the pad was washed several times with dichloromethane. The solvent was evaporated and the crude product extracted with a mixture of hexanes/ethyl acetate [95/5]. The suspension was filtered, the solvent removed and the residue was purified by flash chromatography using hexanes as eluent, affording 4.6 g (78%) of (S)-α-Bromo-4-(1-methylheptyloxy)-2-nitrotoluene (Compound 35, Scheme VI, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) as a yellow liquid; R f [hexanes/ethyl acetate 98/2]: 0.26; 1 H NMR (300 MHz, CDCl 3 ): δ 0.86(t, 3H, J=6.7 Hz), 1.18-1.48(m, 8H), 1.30(d, 3H, J=6.1 Hz), 1.58(m 1H), 1.70(m, 1H), 4.40(m, 1H), 4.77(s, 2H), 7.06(dd, 1H, J=2.7 Hz, J=8.5 Hz), 7.40(d, 1H, J=8.5 Hz), 7.50(d, 1H, J=2.7 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.98, 19.36, 22.50, 25.28, 29.10, 29.25, 31.67, 36.12, 75.00, 111.93, 121.08, 124.14, 133.61, 148.69, 158.92; IR (CHCl 3 ): 3020, 2930, 2850, 1625, 1525, 1500, 1350, 1320, 1250, 1100, 975, 850, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 345(M + +1 1.38), 343(M + -1 1.35), 264(37), 152(100), 112(28), 71(59), 57(93), 55(38), 43(93), 41(70).
Anal. Calcd. for C 15 H 22 BrNO 3 : C 52.34, H 6.44, Br 23.21, N 4.07. Found: C 52.38, H 6.33, N 4.37, Br 23.10.
(S)-[4-(1-methylheptyloxy)-2-nitro-phenyl]-methyl nitrate
To a solution of 3.95 g (11.5 mmol) of (S)-α-bromo-4-(1-methyl-heptyloxy)-2-nitro-toluene in 160 ml of dioxane was added a solution of 8.03 g (47.26 mmol) of AgNO 3 in 16 ml of water. The reaction mixture was stirred at room temperature for 18 h. The precipitate was filtered and washed with ethyl acetate. The filtrate was treated with 150 ml of water and the organic layer separated. The aqueous layer was extracted with ethyl acetate and the combined organic layers evaporated. The resulting crude product was purified by flash chromatography with hexanes/ethyl acetate [100/0.2] and used in the next step without further purification (2.14 g of a yellow liquid, 57% yield); 1 H NMR (300 MHz, CDCl 3 ): δ 0.86(t, 3H, J=6.8 Hz), 1.18-1.50(m, 8H), 1.31(d, 3H, J=6.1 Hz), 1.60(m, 1H), 1.72(m, 1H), 4.42(m, 1H), 5.76(s, 2H), 7.13(dd, 1H, J=2.5 Hz J=8.6 Hz), 7.43(d, 1H, J=8.6 Hz), 7.61(d, 1H, J=2.5 Hz); IR (CHCl 3 ): 3020, 2940, 2840, 1640, 1530, 1500, 1460, 1115, 975, 900, 850, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 326(M + 2), 264(2), 151(13), 112(34), 71(70), 57(100), 55(28), 43(79), 41(47) .
(S)-4-(1-methyl-heptyloxy)-2-nitro-benzaldehyde
To a solution of 1.96 g (6 mmol) of the methyl-nitrate prepared above in 96 ml of dioxane was added a solution of KOH (5.52 g) in 20 ml of water. The reaction mixture was stirred at room temperature under argon for 20 h. Then the mixture was poured into 120 ml of water and the resulting solution was treated with brine (48 ml). This mixture was then extracted with dichloromethane, the extract dried with MgSO 4 , and solvent evaporated. Flash chromatography of the resulting crude product using hexanes/ethyl acetate [100/0.4] furnished (S)-4-(1-methylheptyloxy)-2-nitrobenzaldehyde (95%) (Compound 36, Scheme VI, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) as a yellow liquid; R f [hexanes/ethyl acetate 98/2]: 0.2; 1 H NMR (300 MHz, CDCl 3 ): δ 0.85(t, 3H, J=6.6 Hz), 1.16-1.51(m, 8H), 1.34(d, 3H, J=6.1 Hz), 1.60(m, 1H), 1.76(m, 1H), 4.50(m, 1H), 7.15(dd, 1H, J=2.4 Hz, J=8.8 Hz), 7.43(d, 1H, J=2.4 Hz), 7.93(d, 1H, J=8.8 Hz), 10.24(s, 1H); 13 C NMR (300 MHz, CDCl 3 ): δ 13.95, 19.29, 22.47, 25.21, 29.05, 31.63, 36.05, 75.63, 110.81, 120.02, 122.86, 131.50, 151.84, 162.71, 186.98; Mass spectrum, m/z(rel.intensity): 279(M + 1), 167(31), 120(11), 112(14), 92(9), 71(70), 57(100), 43(85), 41(57).
Anal. Calcd. for C 15 H 21 NO 4 : C 64.50, H 7.58, N 5.01. Found: C 64.11, H 7.46, N 5.25.
(S)-4-(1-Methylheptyloxy)-2-nitrobenzoic acid
To a solution of 1.086 g (3.89 mmol) of (S)-4-(1-methylheptyloxy)-2-nitrobenzaldehyde in 40 ml of acetone was added a solution of KMnO 4 (0.984 g, 6.23 mmol) in 47 ml of water dropwise. The reaction mixture was stirred at room temperature for 6 h and then treated with 5% Na 2 SO 3 (100 ml), acidified with conc. HCl (pH: 4-5), and the resulting solution was extracted with ethyl ether several times. The organic extract was concentrated and extracted with 10% NaOH solution. The alkaline extract was washed with ether, acidified with conc. HCl/ice, and the resulting solution extracted with ethyl ether. The organic layer was washed with water, dried, and the solvent evaporated. (S)-4-(1-Methylheptyloxy)-2-nitrobenzoic acid (Compound 37, Scheme VI, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) was obtained as a dark orange liquid (0.8 g, 70% ) which was used in the next step without further purification; R f [hexanes/ethyl acetate 70/30+1 drop of acetic acid]: 0.16; 1 H NMR (300 MHz, CDCl 3 ): δ 0.86(t, 3H, J=6.8 Hz), 1.16-1.48(m, 8H), 1.32(d, 3H, J=5.(Hz), 1.60(m, 1H), 1.72(m, 1H) 4.45(m, 1H), 7.02(dd, 1H, J=2.4 Hz J=8.8 Hz), 7.09(d, 1H, J=2.4 Hz), 7.90(d, 1H, J=8.8 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.98, 19.22, 22.51, 25.24, 29.14, 31.68, 36.14, 79.94, 110.26, 117.84, 118.98, 132.97, 150.69, 160.61, 170.81; Mass spectrum, m/z(rel.intensity): 295(M + 1), 265(9), 166(8), 135(36), 112(14), 71(66), 57(100), 55(27), 43(94), 41(69).
(S)-4-(1-Methylheptyloxy)-2-nitrobenzoyl chloride
Acid 36 (Scheme VI, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) was converted to the acid chloride using oxalyl chloride in benzene. After removal of solvent, the crude acid chloride 37 (Scheme VI, R 1 =(S)-OCH(CH 3 )C 6 H 13 ) was used directly in the coupling reactions without further purification or characterization.
Example 8. General procedure for coupling phenols with acid chlorides, and synthesis of exemplary compounds of formula I
Procedure for Coupling Phenols with Acid Chlorides
To a flame dried and argon-flushed flask containing a suspension of 2.1 mmol of NaH in 30 ml of dry THF was added a solution of 2.1 mmol of phenol in 17 ml of dry THF via syringe. After stirring for 20-45 min, a solution of 2.1 mmol of acid chloride in 12 ml of dry THF was added. The reaction mixture was then allowed to stir at room temperature. When the reaction was judged complete by TLC (19-22 h), the reaction was quenched by addition of water, and the resulting aqueous phase was extracted with ethyl ether. The combined organic extracts were washed with 10% aqueous HCl, 5% aqueous NaOH and brine, then dried and filtered. Once the filtrate was evaporated to dryness, the crude product was purified by flash chromatography to give the product ester in 70-92% yield. In order to obtain material suitable for liquid crystals studies, several flash chromatographic purifications and often recrystallizations from hexanes were required to obtain material of sufficient purity as judged by TLC and the sharpness of the LC phase transitions or melting points.
Analytical Data for Compounds of Formula I
(S)-4"-(1-Methylheptyloxy-3"-nitrophenyl-4'-n-decyloxy-4-biphenylcarboxylat
The compound of formula I where R 1 =n--C 10 H 21 O, R 2 =(S)-OCH(CH 3 )C 6 H 13 , m=0, n=1, k=1, X 1 =NO 2 , and X 2 -X 4 =H (Scheme I) was purified by flash chromatography with toluene/hexanes [80/20]; R f [hexanes/ethyl acetate 95/5]: 0.22; [α] D 25 : +12.3° (2.74, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.87(m, 6H), 1.18-1.54(m, 22H), 1.35(d, 3H, J=6.1 Hz), 1.62(m, 1H), 1.80(m, 3H), 4.00(t, 2H, J=6.6 Hz), 4.48(m, 1H), 6.99(d, 2H, J=8.7 Hz), 7.09(d, 1H, J=9.3 Hz), 7.38(dd, 1H, J=2.8 Hz, J=9.3 Hz), 7.56(d, 2H, J=8.3 Hz), 7.68(d, 2H, J=8.3 Hz), 7.71(d, 1H, J=2.8 Hz), 8.19(d, 2H, J=8.7 Hz); 13 C NMR (300 MHz, CDCl 3 : δ 13.99, 14.04, 19.47, 22.51, 22.62, 25.18, 25.99, 29.11, 29.19, 29.26, 29.34, 29.50, 29.52, 31.67, 31.84, 36.19, 68.15, 77.00, 115.04, 116.51, 119.14, 126.68, 127.26, 128.40, 130.79, 131.78, 140.55, 142.95, 146.43, 149.53, 159.75, 164.92; IR (CHCl 3 ): 3020, 2940, 2860, 1740, 1610, 1540, 1490, 1300, 1260, 1170, 1015, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 603(M + 0.03), 337(100), 197(13), 57(5), 55(3), 43(12).
Anal. Calcd. for C 37 H 49 NO 6 : C 73.60, H 8.18, N 2.32. Found: C 73.98, H 8.23, N 2.29.
(S)-4"-(1-Methylheptyloxy -3"-nitro-4"-biphenylyl-4-n-decyloxy-benzoate
The compound of formula I where R 1 =n--C 10 H 21 O, R 2 =(S)-OCH(CH 3 )C 6 H 13 , m=1, n=0, k=1, X 1 =NO 2 , and X 2 -X 4 =H (Scheme II) was purified by flash chromatography with hexanes/ethyl acetate [99/1]; R f [hexanes/ethyl acetate 95/5]: 0.16. [α] D 25 : +7.2° (c 2.57, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.88(t, 6H, J=6.6 Hz), 1.15-1.50(m, 22H), 1.36(d, 3H, J=6.1 Hz), 1.62(m, 1H), 1.80(m, 3H), 4.03(t, 2H, J=6.4 Hz), 4.52(m, 1H), 6.96(d, 2H, J=8.7 Hz), 7.11(d, 1H, J=8.7 Hz), 7.26(d, 2H, J=8.7 Hz), 7.56(d, 2H, J=8.4 Hz), 7.67(dd, 1H, J=2.1 Hz, J=8.7 Hz), 7.98(d, 1H, J=2.1 Hz), 8.13(d, 2H, J=8.4 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 14.00, 14.07, 19.51, 22.52, 22.63, 25.20, 25.92, 29.04, 29.13, 29.26, 29.31, 29.50, 31.68, 31.85, 36.20, 68.33, 76.58, 114.35, 116.14, 121.34, 122.47, 123.78, 127.78, 131.94, 132.35, 132.63, 136.16, 141.15, 150.89, 163.70, 164.95; IR (CHCl 3 ): 3020, 2940, 2850, 1740, 1600, 1540, 1490, 1350, 1270, 1210, 1175, 1075, 1025, 975, 840 cm -1 ; Mass spectrum, m/z(rel.intensity): 603(M + 0.03), 261(100), 121(66), 57(10), 55(6), 43(17).
Anal. Calcd. for C 37 H 49 NO 6 : C 73.60, H 8.18, N 2.32. Found: C 73.68, H 8.32, N 2.33.
(S)-4"-(1-Methylheptyloxy)-2"-nitrophenyl-4'-n-decyloxy-4-biphenylcarboxylate
The compound of formula I where R 1 =n--C 10 H 21 O, R 2 =(S)-OCH(CH 3 )C 6 H 13 , m=0, n=1, k=1, X 2 =NO 2 , and X 1 , X 3 and X 4 =H (Scheme III) was purified by flash chromatography with hexanes/dichloromethane [77/23]; R f [hexanes/ethyl acetate 90/10]: 0.57. [α] D 25 : +3.8° (c 3.16, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.88(m, 6H), 1.18-1.54(m, 22H), 1.34(d, 3H, J=6.1 Hz), 1.62(m, 1H), 1.80(m, 3H), 4.03(t, 2H, J=6.6 Hz), 4.40(m, 1H), 7.00(d, 2H, J=8.7 Hz), 7.18(dd, 1H, J=2.7 Hz J=9 Hz), 7.26(d, 1H, J=9 Hz), 7.59(d, 2H, J=9 Hz), 7.61(d, 1H, J=2.7 Hz), 7.70(d, 2H, J=8.7 Hz), 8.22(d, 2H, J=8.7 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 14.00, 14.05, 19.39, 22.52, 22.63, 25.34, 25.99, 29.15, 29.20, 29,28, 29.35, 29.52, 29.53, 31.71, 31.85, 36.19, 68.13, 75.28, 11.67, 115.00, 122.38, 126.06, 126.58, 126.68, 128.44, 131.04, 131.93, 137.39, 142.10, 146.45, 156.10, 159.69, 164.82; IR (CHCl 3 ): 3020, 2930, 2850, 1740, 1620, 1540, 1510, 1340, 1270, 1250, 1170, 1140, 1075, 975, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 603(M + 0.5), 337(100), 214(27), 197(18), 169(71), 155(22), 150(28), 119(11), 71(13), 69(41), 57(31), 55(18), 43(42).
(S)-[4"-n-Decyloxy-4'-biphenylyl]-4-(1-methylheptyloxy)-3-nitrobenzoate
The compound of formula I where R 2 =n--C 10 H 21 O, R 1 =(S)-OCH(CH 3 )C 6 H 13 , m=1, n=0, k=1, X 2 =NO 2 , X 1 , X 3 and X 4 =H (Scheme IV) was purified by flash chromatography with toluene/hexanes [88/12]; R f [toluene/hexanes 90/10]: 0.45. [α] D 25 : +5.8° (c 2.26, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.88(t, 6H, J=6.8 Hz), 1.15-1.55(m, 22H), 1.33(d, 3H, J=6.1 Hz) 1.67(m, 1H), 1.82(m, 1H), 3.99(t, 2H, J=6.4 Hz), 4.65(m, 1H), 6.97(d, 2H, J=8.8 Hz), 7.16(d, 1H, J=9 Hz), 7.24(d, 2H, J=8.8 Hz), 7.51(d, 2H J=8.5 Hz), 7.59(d, 2H, J=8.5 Hz), 8.32(dd, 1H, J=2.2 Hz J=9 Hz), 8.63(d, 1H, J=2.2 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 14.00, 14.07, 19.34, 22.05, 22.09, 25.09, 26.01, 29.05, 29.24, 29.28, 29.36, 29.51, 29.56, 31.64, 31.85, 36.00, 68.09, 77.00, 114.83, 121.13, 121.74, 127.76, 127.80, 128.12, 132.57, 135.42, 139.03, 140.44, 149.52, 155.43, 158.89, 163.34; IR (CHCl 3 ): 3010, 2940, 2840, 1740, 1610, 1525, 1490, 1310, 1280, 1240, 1200, 1170, 1090, 1000, 840, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 603(M + 21), 326(28), 248(37), 246(30), 186(87), 166(100), 136(70), 71(11), 57(26), 55(22), 43(43).
Anal. Calcd. for C 37 H 49 NO 6 : C 73.60, H 8.18, N 2.32. Found: C 73.97, H 8.12, N 2.34.
(S)-4"-n-Decyloxyphenyl-4'-(1-methylheptyloxy-3'-nitro-4-biphenylcarboxylate
The compound of formula I where R 2 =n--C 10 H 21 O, R 1 =(S)-OCH(CH 3 )C 6 H 13 , m=0, n=1, k=1, X 2 =NO 2 , and X 1 , X 3 and X 4 =H (Scheme V) was purified by flash chromatography with toluene/hexanes [75/25]; R f [hexanes/ethyl acetate 90/10]: 0.41. [α] D 25 : +5.0° (c 2.46, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.88(m, 6H), 1.16-1.54(m, 22H), 1.37(d, 3H, J=5.9 Hz), 1.64(m, 1H), 1.80(m, 3H), 3.94(t, 2H, J=6.6 Hz), 4.55(m , 1H), 6.92(d, 2H, J=9 Hz), 7.17(d, 2H, J=9 Hz), 7.14(d, 1H, J=8.8 Hz), 7.66(d, 2H, J=8.4 Hz), 7.76(dd, 1H, J=2.4 Hz J=8.8 Hz), 8.06(d, 1H, J=2.4 Hz), 8.24(d, 2H J=8.4 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.98, 14.04, 19.47, 22.50, 22.62, 25.17, 25.99, 29.11, 29.22, 29.26, 29.51, 29.52, 31.66, 31.84, 36.16, 68.43, 76.66, 115.14, 116.16, 122.35, 124.09, 126.68, 128.87, 130.92, 131.82, 132.09, 141.23, 143.40, 144.23, 151.61, 157.02, 165.21; IR (CHCl 3 ): 3040, 2940, 2860, 1735, 1610, 1510, 1530, 1360, 1275, 1190, 1180, 1070, 1020, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 603(M + 0.6), 573(2), 354(44), 324(30), 242(100), 212(46), 110(33), 57(19), 55(14), 43(34).
Anal. Calcd. for C 37 H 49 NO 6 : C 73.60, H 8.18, N 2.32. Found: C 73.60, H 8.34, N 2.35.
(S)-[4"-n-Decyloxy-4'-biphenylyl]-4-(1-methylheptyloxy)-2-nitrobenzoate
The compound of formula I where R 2 =n--C 10 H 21 O, R 1 =(S)-OCH(CH 3 )C 6 H 13 , m=1, n=0, k=1, X 4 =NO 2 , and X 1 , X 2 and X 3 =H (Scheme VI) was purified by flash chromatography with hexanes/dichloromethane [75/25]; R f [hexanes/ethyl acetate 95/5]: 0.19. [α] D 25 : +2.1° (c 2.72, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ) : δ 0.87(m, 6H), 1.16-1.54(m, 22), 1.34(d, 3H, J=6.1 Hz), 1.62(m, 1H), 1.72(m, 3H), 3.97(t, 2H, J=6.6 Hz), 4.48(m, 1H), 6.94(d, 2H, J=8.5 Hz), 7.12(dd, 1H, J=2.4 Hz J=8.8 Hz), 7.23(d, 2H, J=8.5 Hz), 7.29(d, 1H, J=2.4. Hz), 7.47(d, 2H, J=8.5 Hz), 7.55(d, 2H, J=8.5 Hz), 7.90(d, 1H, J=8.5 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 14.00, 14.06, 19.32, 22.52, 22.63, 25.26, 26.01, 29.09, 29.24, 29.28, 29.36, 29.52, 29.54, 31.67, 31.85, 36.05, 68.10, 75.48, 110.85, 114.84, 117.08, 118.74, 121.52, 127.80, 128.16, 132.51, 132.67, 139.18, 149.47, 151.05, 158.89, 161.63, 163.46; Mass spectrum, m/z(rel.intensity): 603(M + 0.3), 325(20), 201(64), 185(19), 166(8), 91(100), 71(17), 57(37), 43(51), 41(54).
(S,S)-4,4'-Di-(1-methylheptyloxy-3,3'-dinitrophenylbenzoate
The compound of formula I where R 2 =(S)-OCH(CH 3 )C 6 H 13 ), R 1 =(S)-OCH(CH 3 )C 6 H 13 , m=0, n=1, k=1, X 1 and X 2- NO 2 , X 3 and X 4 =H (Scheme VII) was purified by flash chromatography with hexanes/ethyl acetate [88/12]; R f [Hexanes/ethyl acetate 90/10]: 0.24. [α] D 25 : +18.9° (c 2.75, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.88(t, 6H, J=6.8 Hz), 1.20-1.55(m, 16H), 1.37(d, 3H, J=6.1 Hz), 1.41(d, 3H, J=6.1 Hz), 1.68(m, 2H), 1.82(m, 2H), 4.50(m, 1H), 4.62(m, 1H), 7.11(d, 1H, J=9 Hz), 7.17(d, 1H, J=9 Hz), 7.37(dd, 1H, J=2.7 Hz, J=9 Hz), 7.71(d, 1H, J=2.7 Hz), 8.28(dd, 1H, J=2.1 Hz J=9 Hz), 8.58(d, 1H, J=2.1 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.96, 19.28, 19.41, 22.45, 22.47, 25.03, 25.14, 29.00, 29.07, 31.57, 31.69, 35.95, 36.13, 77.00, 77.10, 114.92, 116.47, 119.00, 120.22, 127.05, 127.78, 135.44, 140.38, 142.38, 149.72, 155.72, 162.97; IR (CHCl 3 ): 3010, 2930, 2850, 1740, 1610, 1540, 1360, 1290, 1200, 1110, 1075, 880, 825 cm -1 ; Mass. spectrum; m/z(rel.intensity): 544(M + 0.7), 278(100), 166(100), 120(63), 112(18), 71(79), 57(100), 55(54), 43(100), 41(81).
Anal. Calcd. for C 29 H 40 N 2 O 8 : C 63.95, H 7.40, N 5.14. Found: C 63.53, H 7.52,, N 5.12.
(S,S)-4,4"-Di-(1-methylheptyloxy)-3,3"-dinitro-4'-biphenylylbenzoate
The compound of formula I where R 2 =(S)-OCH(CH 3 )C 6 H 13 ), R 1 =(S)-OCH(CH 3 )C 6 H 13 , m=1, n=0, k=1, X 1 and X 2= NO 2 , X 3 and X 4 =H (Scheme VII) was purified by flash chromatography with hexanes/ethyl acetate [95/5]; R f [hexanes/ethyl acetate 85/15]: 0.20. [α] D 25 : +12.0° (c 2.53, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.86(t, 6H, J=6.4 Hz), 1.16-1.54(m, 16H), 1.36(d, 3H, J=6.1 Hz), 1.40(d, 3H, J=6.1 Hz), 1.66(m, 2H), 1.80(m, 2H), 4.53(m, 1H), 4.64(m, 1H), Distorted AA'BB' System [7.14 (4H)], 7.26(d, 1H, J=8.7 Hz), 7.58(d, 1H, J=8.7 Hz), 7.68(dd, 1H, J=2.4 Hz J=8.7 Hz), 7.92(d, 1H, J=2.4 Hz), 8.30(dd, 1H, J=2.1 Hz J=8.7 Hz), 8.61(d, 1H, J=2.1 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 13.97, 19.32, 19.48, 22.47, 22.49, 25.06, 25.17, 29.02, 29.10, 31.61, 31.65, 35.98, 36.17, 76.57, 114.87, 116.14, 120.91, 122.19, 123.79, 127.76, 127.88, 131.93, 132.35, 135.43, 136.62, 140.45, 141.12, 150.36, 150.99, 155.54, 163.18; IR (CHCl 3 ): 3020, 2940, 2850, 1740, 1610, 1525, 1510, 1490, 1350, 1275, 1240, 1175, 1090, 925, 875, 820 cm -1 ; Mass. spectrum, m/z (rel.intensity); 620(M + 1), 508(7), 397(8), 278(19), 231(22), 230(10), 166(100), 120(12), 71(14), 69(6), 57(24), 55(10), 43(27).
Anal. Calcd. for C 35 H 44 N 2 O 8 : C 67.72, H 7.15, N 4.51. Found: C 67.65, H 7.26, N 4.48.
(S)-4"-(1-Methylheptyloxy)-3'-nitro-4'-biphenylyl-4-n-decyloxybenzoate
The compound of formula III where R 2 =(S)-OCH(CH 3 )C 6 H 13 ) and R 1 =C 10 H 21 O (Scheme VIII) was purified by flash chromatography with hexanes/ethyl acetate [99/1]; R f [hexanes/ethyl acetate 95/5]: 0.28. [α] D 25 : -0.88° (c 2.55, CHCl 3 ); 1 H NMR (300 MHz, CDCl 3 ): δ 0.87(t, 6H. J=6.8 Hz), 1.13-1.64(m, 23H), 1.32(d, 3H, J=6.1 Hz), 1.80(m, 3H), 4.03(t, 2H, J=6.5 Hz), 4.40(m, 1H), 6.96(d, 4H, J=8.7 Hz), 7.37(d, 1H, J=8.7 Hz), 7.51(d, 2H, J=8.7 Hz), 7.81(dd, 1H, J=2.4 Hz, J=8.7 Hz), 8.13(d, 2H, J=8.7 Hz), 8.24(d, 1H, J=2.4 Hz); 13 C NMR (300 MHz, CDCl 3 ): δ 14.03, 14.06, 19.67, 22.55, 22.63, 25.47, 25.93, 29.03, 29.22, 29.27, 29.31, 29.51, 31.76, 31.85, 36.41, 68.36, 74.06, 114.48, 116.35, 120.46, 122.44, 125.69, 128.57, 130.12, 132.28, 132.76, 139.81, 142.22, 142.93, 158.84, 164.05, 164.25; IR (CHCl 3 ): 3020, 2920, 2850, 1740, 1610, 1550, 1520, 1480, 1360, 1250, 1170, 1090, 1050, 1010, 825 cm -1 ; Mass spectrum, m/z(rel.intensity): 603(M + 0.23), 261(100), 121(70), 71(5), 69(5), 57(15), 55(10), 43(27).
Anal. Calcd. for C 37 H 49 NO 6 : C 73.60, H 8.18, N 2.32. Found: C 73.48, H 8.31, N 2.32. | This invention provides chiral, non-racemic compounds and liquid crystal compositions comprising such compounds. The compounds of this invention include those having the formula: ##STR1## wherein k=0 or 1 and when k=1, B=COO, OOC, --C.tbd.C--, or --C.tbd.C--C.tbd.C--; X 1 , X 2 , X 3 and X 4 are either H, an electron donor or an electron acceptor where at least one of the groups X 1 , X 2 , X 3 or X 4 is an electron acceptor and at least one of these groups is an electron donor or H and when one of X 1 or X 3 is an electron donor or H, the other is an electron acceptor and when one of X 2 or X 4 is an electron donor or H, the other is an electron acceptor; and R 1 and R 2 can be various substituted and unsubstituted alkanes and monoalkenes. Compounds provided include those where one of R 1 or R 2 is a chiral non-racemic tail group, particularly a group selected from --O--C*H(CH 3 )R c , --O--C*H(CH 3 )COOR d , and --O--CH 2 C*HF--C*HF--R e in which the * indicates an asymmetric carbon enriched in one stereoconfiguration where R c , R d , and R e can be various substituted and unsubstituted alkanes and monoalkenes. The compounds of this invention are useful in the preparation of FLC mixtures and as non-linear optical materials. | 6 |
CROSS-REFERENCE TO RELATED APPLICAITONS
This application claims benefit under 35 USC 119/120 from U.S. Provisional Application No. 60/199,219, filed Apr. 24, 2000.
BACKGROUND
A glass is a material that when cooled from its heated liquid transforms to the solid state without forming crystals. Such non-crystallized materials are also called amorphous materials. For example, one of the better known amorphous materials is quartz, which can be used to form conventional window glass. Most metals crystallize when they are cooled from the liquid state at reasonable rates, which causes their atoms to be arranged into a highly regular spatial pattern or lattice. A metallic glass is one in which the individual metal atoms have settled into an essentially random arrangement. Metallic glasses are not transparent like quartz glasses and are often less brittle than window glass.
A number of simple metal alloys may also be processed to form a glass-like structure. Binary metal alloys near deep eutectic features of the corresponding binary phase diagrams may be prepared into a glassy structure on cooling from the liquid state at rates greater than 1000 degrees per second. These binary metallic glasses may possess different properties than crystalline metals. These different properties may be useful in certain applications.
Bulk metallic glass forming alloys are a group of multicomponent metallic alloys that exhibit exceptionally high resistance to crystallization in the undercooled liquid state. Compared with the rapidly quenched binary metallic glasses studied prior to 1990, these alloys can be vitrified at lower cooling rates, less than 10 degrees per second.
Many of the recently discovered bulk glass forming alloys can be broadly described as pseudo-ternary alloys of the form ETM 1-x-y LTM x SM y . Typically the early transition metal couple, ETM, is a combination of elements from group IVB of the periodic table; e.g., Zr and Ti. The late transition metals, LTM, are typically combinations of the 3d transition metals from groups VIIIB and IB; e.g., Fe, Co, Ni, and Cu. The simple metal element, SM, is normally chosen groups from IIA or IIIA; e.g., Be, Mg or Al. However, the addition of a SM element is not a requirement for the formation of a bulk glass forming alloy. There are also bulk metallic glass forming alloys based on magnesium.
Examples of some of the composition manifolds that contain ideal bulk metallic forming compositions are as follows: Zr—Ti—Cu—Ni—Be, Zr—Nb—Cu—Ni—Al, Ti—Zr—Cu—Ni, and Mg—Y—Cu—Ni—Li. Each of the chemical species and their combinations are chosen for a given alloy composition such that the alloy composition lies in a region with a low-lying liquid surface. Alloy compositions that exhibit a high glass forming ability are generally located in proximity to deep eutectic features in the multicomponent phase diagram. These materials, including the recently developed families of Zr-based bulk metallic glass alloys show great promise as engineering materials. However, as in many metallic glasses, specimens loaded in a state of uniaxial or plane stress fail catastrophically on one dominant shear band, thus limiting their global plasticity. Specimens loaded under constrained geometries (plane strain) fail in an elastic/perfectly-plastic manner by the generation of multiple shear bands. Multiple shear bands are observed when the catastrophic instability is avoided via mechanical constraint. This behavior under deformation has limited the application of bulk metallic glasses as engineering materials.
SUMMARY
The present application teaches a new class of metallic glass materials that employ the previously unknown physical mechanism of shear band pattern formation. The occurrence of shear band pattern formation dramatically increases the plastic strain to failure, impact resistance, and toughness of the material.
To exploit this phenomenon, a metallic glass matrix is combined with a ductile metal or metal alloy phase. The metallic glasses of this type may be glassy matrix composites based on bulk glass forming compositions in any bulk metallic glass forming alloy system. Formation of these objects is carried out using standard powder metallurgy techniques, at temperatures that are below the melting point of the individual constituents. Combinations of powders comprised of bulk metallic glass forming particles and crystalline ductile metal or metal alloy phases are employed. To prepare a ductile metal/bulk metallic glass matrix composite material, mixtures of metal or metal alloy powders are mixed with the bulk metallic glass powders, followed by processing in the super cooled liquid region (“SLR”). The SLR is defined as the difference in temperature between the glass transition and crystallization temperatures of the glass matrix. This temperature interval is defined as ΔT=(T x −T g ), where T g and T x are the glass transition, and crystallization temperatures, respectively, of the bulk metallic glass constituent which is used to prepare the consolidated powder product or composite, and with the geometry desired. The control of the relative volume fractions of the ductile metal or metal alloy particles and bulk metallic glass matrix is simply controlled by the initial the mixing ratio. The maximum properties allowed by shear band pattern formation upon mechanical deformation are readily controlled in composites prepared in this fashion. This method also allows for bulk metallic glass matrix particles which incorporate crystalline ductile metal phases, formed from the molten state in situ, with a possible further increase in properties. The length scales, or size ranges, associated with the ductile metal or metal alloy phases may be of significantly differing magnitudes. Hence, these differing scales may result in duplex, triplex, or higher order multiplex morphological structures for the added particle sizes; each with a specific purpose. Namely, there will be a preferred size range, of the order of microns in which shear band pattern formation is encouraged. The particles added with larger length scales will further toughen the composite material formed by use of traditional composite toughening mechanisms such as, crack bridging, fiber pull-out, etc. The formation of shear band patterns through the material may cause new effects that had not been previously known in the art.
DETAILED DESCRIPTION
The present invention describes a material formed by a specified combination of ductile metal and bulk metallic glass matrix. More specifically, the system describes crystalline ductile metal particles being existing within a matrix of amorphous bulk metallic glass. Specific materials are described herein, but it should be understood that other materials may be used and other formation techniques. The system operates to toughen bulk metallic glasses using included ductile phases in a composite comprised of a metallic glass matrix.
For introductory purposes only, consider an embodiment for disclosure of the example of shear band pattern forming observed via in situ precipitation from the liquid state in the Zr—Ti—Cu—Ni—Be alloy system. The bulk glass forming compositions in the Zr—Ti—Cu—Ni—Be system are compactly written in terms of a pseudo-ternary Zr—Ti—X phase diagram, where X represents the moiety Be 9 Cu 5 Ni 4 . Results have been obtained for alloys of the form (Zr 100-x-z Ti x M z ) 100-y X y , where M is an element that stabilizes a crystalline beta-phase in Ti- or Zr-based alloys. The composition of specific interest is (Zr 75 Ti 18.34 Nb 6.66 ) 75 X 25 ; i.e., an alloy with M=Nb, z=6.66, x=18.34, and y=25. Upon cooling from the high temperature melt, the alloy undergoes partial crystallization by nucleation and subsequent dendritic growth of the beta-phase in the remaining liquid. The remaining liquid subsequently freezes to the glassy state. This produces a two-phase microstructure containing beta-phase dendrites in a glass matrix.
The inherent properties of the final material impose constraints on the glassy matrix. Upon deformation these constraints lead to the generation of highly organized shear band patterns throughout the material. In the deformed regions of the material regularly spaced shear bands are seen where the spacing is coherent with the microstructural length scale. The patterns formed exist within domains that are dependent on the local orientation of the crystalline phase, and may have a spatial range extending up to 100 microns. Within each domain, regular parallel arrays of shear bands are observed at a spacing of typically 2 to 10 microns. This spacing may coincide with the secondary arm spacing of the beta-phase dendrites. Individual shear bands may occur, and may propagate through the ductile dendrites as highly localized twins.
The materials obtained may have a plastic strain to failure of up to or greater than 20 percent under unconfined loading conditions.
The initiation and propagation of the shear bands may be controlled by the scale and geometry of the ductile phase dispersion. The result is that deformation occurs through the development of highly organized patterns of regularly spaced shear bands that are distributed uniformly throughout the sample.
A monolithic bulk metallic glass object may be prepared from bulk metallic glass forming powders. These bulk metallic glass forming powders could be prepared via mechanical alloying (ball milling), rotary or centifugal atomization, gas or spray atomization, rotating anode, and/or sol-gel processes to name a few examples. The prior art in this area is extensive. This technique uses conventional powder metallurgy processing techniques, such as extrusion, hot-pressing, forging, rolling, and drawing to compact objects from the constituent powders. There are certain advantages to this technique. The compacted powder only requires heating to a relatively low temperature since consolidation of the powder is carried out in the supercooled liquid region or SLR.
In the Zr-based bulk metallic glasses, these operations are typically carried out around 300 to 400 degrees Celsius or 573 to 673 Kelvin (K). For an ideal system, the width of the supercooled liquid region should be relatively wide; e.g. 100 degrees Kelvin (K), in order to facilitate powder metallurgy processing techniques. Certain materials such as Zr-based alloys may facilitate formation in this region. This technique may also be applied to aluminum- and iron-based bulk metallic glass alloy systems. In all of said systems, once the object is formed, it should be cooled sufficiently rapidly so as to retain the metallic glass condition.
A bulk metallic glass matrix composite object that exhibits shear band pattern formation may also be formed by mixing of ductile metal or metal alloy powders with bulk metallic glass powders followed by compaction using powder metallurgy techniques. Specified metals or metal alloy powders are mixed with bulk metallic glass powders. Processing is again carried out in the supercooled liquid region to prepare the consolidated powder product or composite, having the desired geometry. The materials could be extruded under vacuum in an appropriate canister, such as copper, at pressures of the order 100 Mega Pascals (Mpa). The processing temperature could be reduced by using higher compaction pressures. The relative volume fractions of the materials are controlled by controlling an initial mixing ratio of ductile metal to bulk metallic glass. The control of the degree of shear band pattern formation upon mechanical deformation therefore may also be controlled. Since bulk powders are used, it may be easier to provide specified tailored microstructural properties based on different ratios between the ductile metal in the bulk metallic glass matrix material. Consider the following examples.
EXAMPLE 1
A ductile metal reinforced bulk metallic glass matrix composite could be formed via SLR processing by incorporating powders of ductile crystalline Ti—Zr—Nb—Cu—Ni particles with beta-phase crystal symmetry, embedded in a Zr—Ti—Cu—Ni—Be bulk metallic glass matrix. Specific chemical compositions could have crystalline beta-phase particles with chemical compositions near Zr 71 Ti 16.3 Nb 10 Cu 1.8 Ni 0.9 , and a bulk metallic glass matrix with composition Zr 41.2 Ti 13.8 Cu 12.5 Ni 10 Be 22.5 . The latter bulk metallic glass former has a glass transition temperature near 623 K. The SLR width is near 80K. This matrix material is vitrified at 1.8 K/s making it a useful matrix material for composite applications. However, the beryllium containing systems are of reduced interest due to the health hazards associated with beryllium.
EXAMPLE 2
Another ideal example would incorporate as a glass matrix the Zr 58.5 Nb 2.8 Cu 15.6 Ni 12.8 Al 10.3 composition. This alloy exhibits a glass transition temperature near 673 K, and could thus be compacted in this temperature regime. The SLR width is near 100 K. Specific chemical compositions for the crystalline beta-phase particles could again have compositions near Zr 71 Ti 16.3 Nb 10 Cu 1.8 Ni 0.9 . Other crystalline Zr-based alloys warrant examination.
EXAMPLE 3
Another example incorporates Mg 62 Cu 25 Y 10 Li 3 composition as a glass matrix. This alloy exhibits a glass transition temperature near 414 K, and could thus be compacted in this temperature regime. The SLR width is near 75 K. This matrix material is favorable for applications where density is of prime consideration. For the Mg-based composite, a number of crystalline magnesium alloys could be considered.
EXAMPLE 4
Another example uses as a glass matrix the Ti 34 Zr 11 Cu 48 Ni 7 composition. This alloy forms bulk metallic glasses with millimeter dimensions. The critical cooling rate however, is much greater than the previous examples given. This alloy exhibits a glass transition temperature near 673 K, and could thus be compacted in this temperature regime. The SLR width is near 45 K. This alloy has been prepared, in monolithic form, via powder metallurgy methods. To form a composite, specific chemical compositions for the crystalline ductile particles could have compositions comprised of a number of Ti-based alloys. For example, the common alpha-beta alloy Ti-6Al-4V.
Other embodiments are within the disclosed embodiment. | A new metallic glass is formed by adding special additives to a metallic glass matrix; the additives having ductile properties to form as dendrites in the metallic glass. The additives distribute the shear lines in the metallic glass, allowing it to plastically deform more than previous materials. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application 60/927,789 filed 4 May 2007, which is incorporated herein by reference in its entirety for all purposes.
BACKGROUND OF THE INVENTION
[0002] The field of the invention is nuclear magnetic resonance imaging methods and systems. More particularly, the invention relates to the in vivo imaging of tissue temperature.
[0003] When a substance such as human tissue is subjected to a uniform magnetic field (polarizing field B o ), the individual magnetic moments of the spins in the tissue attempt to align with this polarizing field, but precess about it in random order at their characteristic Larmor frequency. If the substance, or tissue, is subjected to a magnetic field (excitation field B 1 ) which is in the x-y plane and which is near the Larmor frequency, the net aligned moment, Mz, may be rotated, or “tipped”, into the x-y plane to produce a net transverse magnetic moment Mt. A signal is emitted by the excited spins after the excitation signal B 1 is terminated, this signal may be received and processed to form an image.
[0004] When utilizing these signals to produce images, magnetic field gradients (G X , G y and G z ) are employed. Typically, the region to be imaged is scanned by a sequence of measurement cycles in which these gradients vary according to the particular localization method being used. The resulting set of received NMR signals are digitized and processed to reconstruct the image using one of many well known reconstruction techniques.
[0005] Hyperthermia has been shown to be highly valuable as an adjunct to radiation therapy in such cases as recurrent cancer in the chest wall. One of the key factors in successful hyperthermia treatment is the measurement and control of temperature in the tumor and also in surrounding normal tissue. While invasive thermometry provides accurate and precise measurements, complete temperature mapping of a region using magnetic resonance imaging is expected to afford improvements in the control of the temperature therapy distribution. Non-invasive thermometry is needed for radiofrequency ablation to heat tumors, for cryoablation to freeze tumors and to provide temperature measurements within the tumor as well as the surrounding tissues.
[0006] Previous work has shown the value of using the temperature sensitivity of the tissue water proton resonant frequency shift (PUS) or the apparent diffusion coefficient (ADC) to measure temperature change. However, tissues containing a mix of water and lipids, e.g. breast, confound most standard frequency shift thermometry approaches since lipids have no chemical shift dependencies with temperature change.
[0007] Recently, a new method known as IDEAL was developed for imaging spin species such as fat and water. As described in U.S. Pat. No. 6,856,134 B1 issued on Feb. 15, 2005 and entitled “Magnetic Resonance Imaging With Fat-Water Signal Separation”, the IDEAL method employs pulse sequences to acquire multiple images at different echo times (TE) and an iterative, linear least squares approach to estimate the separate water and fat signal components. The advantage of the IDEAL method is if the frequencies of the particular metabolites being imaged are known, the number of different echo time repetitions can be significantly reduced. This “a priori” information shortens scan time and enables more pulse sequence repetitions to be devoted to increased image resolution.
SUMMARY OF THE INVENTION
[0008] The present invention is a method for measuring the temperature of tissues containing a mixture of water and fat using an MRI system. Image data are acquired at three or more echo times (TE 1 , TE 2 , TE 3 ) and separate water and fat images are reconstructed. By setting the RF excitation to the Larmor frequency of water, phase shifts caused by temperature can be seen in the phase of fat signals. It has also been discovered that the difference between the water signal phase and the fat signal phase at each image voxel is an indication of the temperature at that location.
[0009] A general object of the invention is to non-invasively produce a temperature map of in vivo tissues which contain a mix of tissues containing both lipids and water. A more accurate measure of temperature is achieved by subtracting the phase of a separate lipid/fat image from the phase of a separate water image. The temperature measurement is self-referenced by the phase difference between water and fat signals and phase shifts over the lengthy medical procedure caused by other factors such as B o field drift do not affect the measurement.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a block diagram of an MRI system which employs the present invention;
[0011] FIG. 2 is a graphic representation of a preferred pulse sequence used to direct the operation of the MRI system of FIG. 1 ; and
[0012] FIG. 3 is a flow chart of the steps in the preferred embodiment of the invention.
GENERAL DESCRIPTION OF THE INVENTION
[0013] The standard IDEAL model for water and fat is shown in Eq. 1.
[0000] S ( t n )=( A w e iφ w +A f e iφ f e iω cs t n ) e iψt n (1)
[0000] If the water frequency changes with temperature this adds a phase change in the water term. However, standard IDEAL post-processing models water as on-resonance, so phase shifts from temperature changes appear in the fat term. This can be written,
[0000] S ( t n )=( A w e iφ w +A f e iφ f e iω cs t n e iω ΔT t n ) e iψt n (2)
[0000] where φ w and φ f are constant phase shifts of water and fat. Also note that the chemical shift frequency is the sum of a baseline chemical shift between water and fat (ω o ) at some nominal baseline temperature (e.g., 37° C.) and a temperature dependent frequency,
[0000] ω ΔT =γαB o ΔT (3)
[0000] where γ is the gyromagnetic ratio (γ/2π=42.58 MHz/T), α=−0.01 ppm/° C. is the PRF change coefficient and B 0 is the main magnetic field strength. If the middle of the three echo times, t 2 , is large compared to the spacing between echoes (t 2 −t 1 and t 3 −t 2 ), then we can ignore the change in phase accumulated during the small time between echoes, ie: assume t 2 −t 1 and t 3 −t 2 are small, such that,
[0000] e iω ΔT t n ≈e iγαB o ΔTt 2
[0000] Therefore, the signal model can now be written
[0000] S ( t n )≈( A w e iφ w +A f e iφ f e iω cs t n e iγαB o ΔTt 2 ) e iψt n (4)
[0000] IDEAL water-fat separation is then performed providing complex estimates of water and fat, ie:
[0000] W=A w e iφ w (5)
[0000] and
[0000] F=A f e iφ f e iγαB o ΔTt 2 (6)
[0000] By measuring the difference in phase between the water and fat at each time point, the temperature can be determined. Specifically,
[0000] Δφ 1 =φ w −φ f (7)
[0000] and
[0000] Δφ 2 =φ w −φ f −γαB o ΔTt 2 (8)
[0000] Temperature change is then estimated as,
[0000]
Δ
T
=
(
Δ
φ
1
-
Δ
φ
2
)
γ
α
B
o
t
2
(
9
)
[0014] Alternatively, temperature can be measured from the water signal alone, so long as the resonant frequency of the scanner has not changed between the acquisitions of the reference image and the subsequent images. This is the usual situation and the signal model of the image acquired during heating/cooling can be written,
[0000] S ( t n )=( A w e iφ w e iω cs t n +A f A w e iφ f e iω cs t n ) e iψt n (10)
[0000] and making the same assumptions as above,
[0000] S ( t n )≈( A w e iφ w e iγαB o ΔTt 2 +A f e iφ f e iω cs t n ) e iψt n (11)
[0000] By measuring the phase of the water only image at time 1 (φ w1 , reference) and time 2 (φ w2 , during heating or cooling), the temperature change is
[0000]
Δ
T
=
(
φ
w
1
-
φ
w
2
)
γ
α
B
o
t
2
(
12
)
[0015] It is also possible to measure the absolute temperature by using phase images to determine the relative frequency between water and fat. In this way, we can determine the absolute temperature in tissues that contain both water and fat, without the need for an external reference.
[0016] Absolute temperature can be measured with one data set acquired at one time point, so long as the relative frequency between water and fat is known for a baseline temperature. For example, it is well known that ω cs =−210 Hz at 1.5 T at 37° C. or −220 Hz at 21° C. In addition, for pulse sequences such as fast spin-echo (FSE) and spoiled gradient echo (SPGR) imaging, as well as other pulse sequences, the relative constant phase of water (ω w ) and fat (φ f ) are equal at t=0. Therefore, the absolute temperature can be determined from a single time point using the following equation:
[0000]
T
ab
s
=
(
φ
f
-
φ
w
)
γ
α
B
o
t
2
+
T
ref
(
13
)
[0017] where T ref is the known reference temperature. This reference temperature is the same temperature at which the relative chemical shift between water and fat (ω cs ) was measured (eg. −210 Hz at 37° C. or −220 Hz at 21° C.).
[0018] Complex images of fat acquired with the IDEAL method can be used to model an estimate of MR main field drift throughout a volume regardless of temperature changes, e.g., a map of the phase change in the subcutaneous fat surrounding the leg can be used to fit a smoothly changing estimate of the main B o field over the whole leg (including muscle that does not contain fat). This method can be used clinically to correct real time temperature maps for errors due to B o field drift over the course of hyperthermia treatment. This method works better than current methods which are based on external fat references placed outside of the leg since the subcutaneous fat is located much closer to the muscle in which we want to estimate the field change.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0019] Referring particularly to FIG. 1 , the preferred embodiment of the invention is employed in an MRI system. The MRI system includes a workstation 10 having a display 12 and a keyboard 14 . The workstation 10 includes a processor 16 which is a commercially available programmable machine running a commercially available operating system. The workstation 10 provides the operator interface which enables scan prescriptions to be entered into the MRI system.
[0020] The workstation 10 is coupled to four servers: a pulse sequence server 18 ; a data acquisition server 20 ; a data processing server 22 , and a data store server 23 . In the preferred embodiment the data store server 23 is performed by the workstation processor 16 and associated disc drive interface circuitry. The remaining three servers 18 , 20 and 22 are performed by separate processors mounted in a single enclosure and interconnected using a 64-bit backplane bus. The pulse sequence server 18 employs a commercially available microprocessor and a commercially available quad communication controller. The data acquisition server 20 and data processing server 22 both employ the same commercially available microprocessor and the data processing server 22 further includes one or more array processors based on commercially available parallel vector processors.
[0021] The workstation 10 and each processor for the servers 18 , 20 and 22 are connected to a serial communications network. This serial network conveys data that is downloaded to the servers 18 , 20 and 22 from the workstation 10 and it conveys tag data that is communicated between the servers and between the workstation and the servers. In addition, a high speed data link is provided between the data processing server 22 and the workstation 10 in order to convey image data to the data store server 23 .
[0022] The pulse sequence server 18 functions in response to program elements downloaded from the workstation 10 to operate a gradient system 24 and an RF system 26 . Gradient waveforms necessary to perform the prescribed scan are produced and applied to the gradient system 24 which excites gradient coils in an assembly 28 to produce the magnetic field gradients G x , G y and G, used for position encoding NMR signals. The gradient coil assembly 28 forms part of a magnet assembly 30 which includes a polarizing magnet 32 and a whole-body RF coil 34 . In the preferred embodiment a 3.0 Tesla scanner sold by General Electric under the trademark “SIGNA” is employed.
[0023] RF excitation waveforms are applied to the RF coil 34 by the RF system 26 to perform the prescribed magnetic resonance pulse sequence. Responsive NMR signals detected by the RF coil 34 are received by the RF system 26 , amplified, demodulated, filtered and digitized under direction of commands produced by the pulse sequence server 18 . The RF system 26 includes an RF transmitter for producing a wide variety of RF pulses used in MR pulse sequences. The RF transmitter is responsive to the scan prescription and direction from the pulse sequence server 18 to produce RF pulses of the desired frequency, phase and pulse amplitude waveform. The generated RF pulses may be applied to the whole body RF coil 34 or to one or more local coils or coil arrays.
[0024] The RF system 26 also includes one or more RF receiver channels. Each RF receiver channel includes an RF amplifier that amplifies the NMR signal received by the coil to which it is connected and a quadrature detector which detects and digitizes the I and Q quadrature components of the received NMR signal. The magnitude of the received NMR signal may thus be determined at any sampled point by the square root of the sum of the squares of the I and Q components:
[0000] M =√{square root over ( I 2 +Q 2 )},
[0000] and the phase of the received NMR signal may also be determined:
[0000] φ=tan −1 Q/I.
[0000] In the preferred embodiment a dual-tuned, proton-carbon transmit and receive local coil is employed such as that described in U.S. Pat. No. 4,799,016 entitled “Dual Frequency NMR Surface Coil.”
[0025] The pulse sequence server 18 also optionally receives patient data from a physiological acquisition controller 36 . The controller 36 receives signals from a number of different sensors connected to the patient, such as ECG signals from electrodes or respiratory signals from a bellows. Such signals are typically used by the pulse sequence server 18 to synchronize, or “gate”, the performance of the scan with the subject's respiration or heart beat.
[0026] The pulse sequence server 18 also connects to a scan room interface circuit 38 which receives signals from various sensors associated with the condition of the patient and the magnet system. It is also through the scan room interface circuit 38 that a patient positioning system 40 receives commands to move the patient to desired positions during the scan.
[0027] It should be apparent that the pulse sequence server 18 performs real-time control of MRI system elements during a scan. As a result, it is necessary that its hardware elements be operated with program instructions that are executed in a timely manner by run-time programs. The description components for a scan prescription are downloaded from the workstation 10 in the form of objects. The pulse sequence server 18 contains programs which receive these objects and converts them to objects that are employed by the run-time programs.
[0028] The digitized NMR signal samples produced by the RF system 26 are received by the data acquisition server 20 . The data acquisition server 20 operates in response to description components downloaded from the workstation 10 to receive the real-time NMR data and provide buffer storage such that no data is lost by data overrun. In some scans the data acquisition server 20 does little more than pass the acquired NMR data to the data processor server 22 . However, in scans which require information derived from acquired NMR data to control the further performance of the scan, the data acquisition server 20 is programmed to produce such information and convey it to the pulse sequence server 18 . For example, during prescans NMR data is acquired and used to calibrate the pulse sequence performed by the pulse sequence server 18 . Also, navigator signals may be acquired during a scan and used to adjust RF or gradient system operating parameters or to control the view order in which k-space is sampled. And, the data acquisition server 20 may be employed to process NMR signals used to detect the arrival of contrast agent in an MRA scan. In all these examples the data acquisition server 20 acquires NMR data and processes it in real-time to produce information which is used to control the scan.
[0029] The data processing server 22 receives NMR data from the data acquisition server 20 and processes it in accordance with description components downloaded from the workstation 10 . Such processing include Fourier transformation of raw k-space NMR data to produce two or three-dimensional images; the application of filters to a reconstructed image and the reconstruction of the metabolic images according to the present invention.
[0030] Images reconstructed by the data processing server 22 are conveyed back to the workstation 10 where they are stored. Real-time images are stored in a data base memory cache (not shown) from which they may be output to operator display 12 or a display 42 which is located near the magnet assembly 30 for use by attending physicians. Batch mode images or selected real time images are stored in a host database on disc storage 44 . When such images have been reconstructed and transferred to storage, the data processing server 22 notifies the data store server 23 on the workstation 10 . The workstation 10 may be used by an operator to archive the images, produce films, or send the images via a network to other facilities.
[0031] A number of different pulse sequences can be used to direct the MRI system to acquire the data needed to practice the present invention. In one preferred embodiment a pulse sequence as shown in FIG. 2 is employed which uses the steady state free precision (SSFP) principle. It includes a selective rf excitation pulse 50 that is repeated at the start of each TR period as well as a slice select gradient pulse 52 that is produced concurrently with the rf pulse 50 to produce transverse magnetization in a prescribed slice. The rf frequency of the pulse 50 is tuned to the Larmor frequency of water spins in the subject being imaged.
[0032] After excitation of the spins in the slice a phase encoding gradient pulse 54 is applied to position encode the NMR signal 56 along one direction in the slice. A readout gradient pulse 58 is also applied after a dephasing gradient lobe 60 to position encode the NMR signal 56 along a second, orthogonal direction in the slice. The NMR signal 56 is sampled during a data acquisition window 62 . To maintain the steady state condition, the integrals of the three gradients each sum to zero. To accomplish this rephrasing lobes 64 are added to the slice select gradient waveform, a rephrasing lobe 66 is added to the readout gradient waveform and a rewinder gradient lobe 68 is added to the phase encoding gradient waveform. As is well known in the art, the pulse sequence is repeated and the amplitude of the phase encoding gradient 54 and its equal, but opposite rewinder 68 are stepped through a set of values to sample 2D k-space in a prescribed manner.
[0033] Referring particularly to FIG. 3 , a scan is conducted using this pulse sequence to direct the above MRI system to acquire spectroscopic image data as indicated at process block 300 . Three images at three different echo times TE are acquired at each prescribed slice location. Three gradient echo image k-space data sets are thus acquired at each time point with TR=100 ms, FOV=180 mm, 128×128 sample pts, one coronal slice 5 mm thick, 310 Hz/pt and TE=[3.38, 4.17, 4.97].
[0034] As indicated at process block 302 , the next step is to reconstruct each 2D slice image from each of the three TE k-space data sets. This is accomplished with a conventional complex, 2DFT transformation of each k-space data set. As indicated at process block 304 , the next step is to produce separate Fat and Water images from the three reconstructed images. The IDEAL method described in the above-cited U.S. Pat. No. 6,856,131 is employed to accomplish this step and its teachings are incorporated herein by reference.
[0035] The resulting Fat and Water images are complex values from which both signal magnitude and phase can be computed at each image voxel as described above. As indicated at process block 306 both a Fat phase image is produced and a Water phase image is produced. A temperature change map is then produced as indicated at process block 308 by subtracting the phase of each Fat phase image from the phase of the corresponding voxel in the Water phase image and calculating the temperature change therefrom between two time points in the procedure as indicated above in equations (7) through (9).
[0036] This temperature map may be displayed for use by a physician or the like during a medical procedure, and if temperature monitoring is to continue as determined at decision block 310 , the system loops back to acquire further data and repeat the processing thereof. In addition, an absolute temperature map may be produced as indicated at process block 312 . Such a temperature map is produced by calculating the absolute temperature at each image voxel using equation (13) described above.
[0037] Variations are possible from the preferred embodiment described above. Increased phase differential between time points can be achieved by lengthening the echo times (TE) during data acquisition. The normal voxel size in the preferred embodiment is 1.4×1.4×5 mm, but spatial resolution can be traded off to gain higher SNR. Total acquisition time for each time point is approximately 40 seconds, and up to 12 slices can be acquired in an interleaved manner during this acquisition time.
[0038] Water-fat separation methods that measure temperature dependent on phase shifts using fat as an internal phase reference show great promise as a new approach for MR thermometry in fatty tissues such as the breast. While the IDEAL water-fat separation method described in U.S. Pat. No. 6,856,134 is the preferred embodiment, other water-fat separation methods such as those disclosed in U.S. Pat. Nos. 5,225,781; 6,016,057 and 6,091,243 can also be used. | The in vivo measurement of tissue temperature is performed during a medical procedure using an MRI system. Fat and Water images are acquired at each temperature measurement time and corresponding phase images are produced. A temperature map is produced by subtracting the phase at each Fat image pixel from the corresponding pixel in the Water phase image to improve measurement accuracy in tissues with fat/water mixtures. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to planters, and more particularly to raised bed planters having means for wicking water from a reservoir into the planter.
BACKGROUND OF THE INVENTION
[0002] Wicking or self-watering planters typically include an enclosure for receiving soil and plant material therein, a reservoir for storing water, and at least one wick extending between the reservoir and the soil for diffusing water from the reservoir into the soil.
SUMMARY OF THE INVENTION
[0003] The invention provides, in one aspect, a gardening bed including a frame and a structural panel coupled to the frame. The panel includes at least two interconnected layers of polymer material, at least one channel defined between the layers, the channel having an opening into which a fluid may be poured, and at least one reservoir defined between the layers in which fluid poured through the channel may accumulate.
[0004] The invention provides, in another aspect, a structural panel for a gardening bed. The structural panel includes a first portion, a second portion extending generally perpendicularly from the first portion, and at least one channel extending through the first portion. The channel has an opening into which a fluid may be poured and at least one reservoir in which fluid poured through the channel may accumulate.
[0005] Other features and aspects of the invention will become apparent by consideration of the following detailed description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a perspective view of a gardening bed in accordance with an embodiment of the invention.
[0007] FIG. 2 is an exploded view of the gardening bed of FIG. 1 .
[0008] FIG. 3 is an enlarged perspective view of a portion of a structural panel of the gardening bed of FIG. 1 .
[0009] FIG. 4 is a cross-sectional view of the gardening bed taken along line 4 - 4 in FIG. 1 .
[0010] FIG. 5 is a perspective view of water being poured into a structural panel of the gardening bed of FIG. 1 .
[0011] Before any embodiments of the invention are explained 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 components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
DETAILED DESCRIPTION
[0012] FIGS. 1 and 2 illustrate a gardening bed 10 including a frame 14 and an enclosure 18 supported on the frame 14 and configured to receive soil and plant matter therein. The enclosure 18 is defined by first and second structural side panels 22 , 26 , and first and second spaced end panels 30 , 34 coupled to the frame 14 . A stand 38 including a pair of generally V-shaped support members 42 may support the gardening bed 10 in an elevated position. In some embodiments, the stand 38 may be removed to allow the gardening bed 10 to be positioned directly on a ground surface.
[0013] With reference to FIG. 3 , the structural side panels 22 , 26 are made of first and second interconnected sheets 46 , 50 of a heat-shrinkable polymer material. The interconnected sheets 46 , 50 may define a self-corrugating polymer panel such as those described in U.S. Patent Application Publication Nos. 2014/0087145, 2014/0087146, and 2014/0087147, the entire contents of all of which are incorporated herein by reference.
[0014] Before assembling the enclosure, each of the sheets 46 , 50 is uniaxially stretched to impart direction or orientation in the polymer chains. The sheets 46 , 50 are oriented so that the stretched direction of the first sheet 46 is generally perpendicular to the stretched direction of the second sheet 50 . A radio frequency (RF) or other suitable welding process is used to create weld spots 54 that permanently bond the sheets 46 , 50 at evenly-spaced intervals. The sheets 46 , 50 are then heated, causing them to shrink along orthogonal axes. This creates undulations 58 in each of the sheets 46 , 50 between adjacent weld spots 54 .
[0015] With continued reference to FIG. 3 , the undulations 58 in the first sheet 46 define a first plurality of channels 62 extending in a first direction 66 and the undulations 58 in the second sheet 50 define a second plurality of channels 70 extending in a second direction 74 that is orthogonal to the first direction 66 . As described in greater detail below, these channels 62 , 70 allow fluid to flow through the structural side panels 22 , 26 and to be stored within the panels 22 , 26 .
[0016] With reference to FIGS. 2 and 4 , each of the structural side panels 22 , 26 has a generally L-shaped cross-section and includes a first or vertical portion 78 , a second or bottom portion 82 , and a bend 84 between the vertical and bottom portions 78 , 82 . The illustrated bend 84 defines an included angle θ ( FIG. 4 ) of about 90 degrees such that the bottom portions 82 are horizontal; however, in other embodiments the angle θ may vary. The vertical portions 78 define side walls 86 , 90 of the enclosure 18 , and the bottom portions 82 collectively define a bottom wall 94 ( FIG. 2 ) of the enclosure 18 for supporting soil and plant material thereon. In the illustrated embodiment, each of the structural side panels 22 , 26 is made of a single, continuous polymer panel that is thermoformed into the illustrated shape after undergoing the heat-shrinking process described above. In other embodiments, the side panels 22 , 26 may be made of multiple discrete segments joined together (e.g., using a polymer welding process, adhesives, mechanical fasteners, etc.).
[0017] The first channels 62 extend continuously through the vertical and bottom portions 78 , 82 of the side panels 22 , 26 ( FIG. 4 ). In the vertical portions 78 , the first channels 62 include openings 98 into which fluid, such as water or a water and nutrient mixture, may be poured. In the bottom portions 82 , the channels 62 , 70 define a reservoir 102 in which the fluid poured through the vertical portions 78 may accumulate. Wicks 106 extend upward from the reservoir 102 and into the soil. The wicks 106 can draw fluid from the reservoir 102 via capillary action to diffuse the fluid into the soil.
[0018] With continued reference to FIGS. 2 and 4 , the illustrated gardening bed 10 also includes an overflow trough or vessel 110 located between and beneath the bottom portions 82 of the side panels 22 , 26 . The overflow trough 110 collects any excess fluid that cannot be accommodated within the volume of the reservoir 102 . Each of the side panels 22 , 26 includes a second bend 104 to direct fluid from the reservoir 102 into the trough 110 . The trough 110 may be removable for manual emptying or may include a valve, hose connector, or other means for draining fluid from the trough.
[0019] In some embodiments, the bends 104 may pinch the channels 62 , creating a restriction to impede the fluid from freely flowing out of the reservoir 102 . As such, excess fluid may only flow out of the reservoir 102 when there is sufficient pressure or head (e.g., due to excess fluid building up in the vertical portions 78 of the panels 22 , 26 ) to force the fluid through the bends 104 . Alternatively or additionally, the angle θ may be reduced so that the fluid is retained in the reservoir under the influence of gravity.
[0020] In operation, a user fills the enclosure 18 of the gardening bed 10 with soil and plant material, such as seeds, seedlings, and the like. As an alternative to pouring water directly on the soil, the user may pour water into the openings 98 in the side panels 22 , 26 ( FIG. 5 ). The water circulates downward through the channels 62 (i.e., between the interconnected polymer sheets 46 , 50 ) and accumulates in the reservoir 102 located in the bottom portions 82 of the side panels 22 , 26 ( FIG. 4 ). The bottom ends of the wicks 106 are immersed in the accumulated water, causing water to be drawn upward and into the soil by capillary action. Excess water may be discharged from the reservoir 102 and into the overflow trough 110 . In the illustrated embodiment, the structural side panels 22 , 26 are semi-transparent, enabling the user to visually monitor the water level in the reservoir 102 and avoid over-watering.
[0021] Various features of the invention are set forth in the following claims. | A gardening bed includes a frame and a structural panel coupled to the frame. The panel includes at least two interconnected layers of polymer material, at least one channel defined between the layers, the channel having an opening into which a fluid may be poured, and at least one reservoir defined between the layers in which fluid poured through the channel may accumulate. | 0 |
This is a division of application Ser. No. 855,275 filed April 24, 1986, now U.S. Pat. No. 4.741,796.
BACKGROUND OF THE INVENTION
This invention relates to an arrangement wherein a plurality of body members are positioned in precise relationship on a carrier body, and, more particularly, it relates to an arrangement wherein manipulators position these bodies at elevated temperatures and in an inert gas environment.
The technical problem is one of positioning and bonding a solid body in a specific spatial relation to another object. It is often necessary to position a solid body relative to another object with a high degree of accuracy and to attach it at the respective positioned location in a manner that will provide long term stability, upon achieving this accuracy.
A light beam wave-guide, for example a glass fibre or optical fibre, is to be affixed to a laser diode with a specified separation larger than or equal to zero or to some predetermined value. Through the use of proper optics a light beam wave-guide is to be attached to a laser diode with a specified separation greater than zero, whereby the light emitted by the diode is, for example, to be efficiently coupled by means of the proper optics to the beam wave-guide. A tapered lens arranged at the end of the glass fibre may, for example, be employed as the suitable optics.
During the attachment of a light beam wave-guide to a laser diode with a specified separation, especially during the application of a single mode optical fibre as a beam wave-guide, particularly stringent requirements are posed with regard to the positional accuracy and to the long term stability of this positional accuracy during operating and storage conditions. The positional accuracy of a single mode optical fibre must then have a long term stability with a maximum tolerance of within or ±/- 0.05 μm. This maximum tolerance must not be exceeded during operation and storage conditions over the range of -40° C. to +60° C.
With regard to the respective light beam wave-guides employed, either smaller or greater accuracies must be maintained for positioning and bonding the light beam wave-guide in front of the respective laser diode.
In the case of multi-mode optical fibres, for example, in the case of graded index fibres with a cone diameter of 50 μm, a position and long term location tolerance Δx, Δy on the order of ±/- 1 μm must be maintained. In the application of a single mode optical fibre which may exhibit a core of 5 μm, for example, a position and long term location tolerance Δx, Δy on the order ±/- 0.05 μm must be maintained.
With presently available mechanical and electro-mechanical adjusting devices, for example, with a stepping motor, with a piezo-crystal etc., the attainment of the previously mentioned adjustment accuracies for short periods, and the retaining of this accuracy for seconds, and even minutes, is relatively free of problems.
It is however impossible, with presently available procedures and devices, to bond the beam wave-guides with the attained accuracy, while maintaining the respective location of the beam wave-guide, after positioning, in the long term.
Previously, a number of different light beam wave-guide bonding methods were, or would be, applied in the construction of laser diode modules. In most of the laser modules on the market today, the laser diode is attached to its own mount assembly which is in turn attached through an intermediate fastening element to a light beam wave-guide bonding point. In this way the light beam wave-guide is either fastened in a capillary made of metal-quartz or similar materials, or directly attached at the point of bonding. The attachment of the light beam wave-guide is thus accomplished through the following different techniques or arrangements.
In one technique, the beam wave-guide is directly cemented to the positioning point. In another technique, the beam wave-guide is cemented into a capillary and the capillary is in turn cemented, soldered, welded etc., at the positioning point. In a third technique, the beam wave-guide is metalized, then soldered into the capillary and the capillary then soldered to the positioning point, etc.
All of these conventional bonding techniques for a light beam wave-guide have to a greater or less extent disadvantages of various kinds, as for example:
(I) During cementing of the beam wave-guide to the positioning point, the beam wave-guide must be held in position at the positioning point to an accuracy of ±/- 0.05 μm during hardening of the cement, which is practically impossible in the present state of the art.
(II) Too little is as yet known about the long term stability of the various cements.
(III) During the soldering of the beam wave-guide at the bonding point with the assembly techniques employed until now for beam wave-guide module construction, a heat source is necessary for heating the solder, which to a large extent also heats the laser diode, so that operation of the laser diode during the positioning procedure is not possible in most cases, whereby adjustment by coupling to light and optical observation during photo-diode operation is impossible and accurate positioning is made substantially more difficult.
(IV) During welding or soldering of a beam wave-guide mounted in a capillary, a considerable displacement of the beam wave-guide may occur, during the cooling process, especially in the case of welding, that is substantially greater than ±/- 0.05 μm.
(V) In all of the light beam wave-guide techniques mentioned in the foregoing, the light beam wave-guide is attached to the mount assembly on which the laser diode is mounted, through intermediate elements, such as through various metals, various materials, screwed and/or soldered and/or cemented. The stability of the beam wave-guide is thereby directly related to the mechanical and thermal behavior characteristics of these intermediate elements, this means, that a displacement or a thermal stress, which must of necessity arise, during temperature cycling between +60° C. and -40° C. with many of the intermediate elements used in the present arrangements of the prior art, are directly carried over into the light beam wave-guide laser coupling and make it practically impossible to maintain long-term stability.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a technique and an arrangement of the type previously referred to including a fabricated component in which a solid body may be positioned with high accuracy and bonded with good long-term stability at the desired location established during positioning.
The invention broadly includes an attachment method and a positioning and attachment procedure for solid bodies, particularly for light beam wave-guides, e.g. for glass fibres, which overcome the disadvantages of prior techniques and achieves substantial simplification over conventional techniques.
BRIEF DESCRIPTION OF THE DRAWING
Features of the invention and additional objects of the invention will be more readily appreciated and better understood by reference to the following detailed description which should be considered in conjunction with the drawing.
FIG. 1 is a cross section-view of an illustrative embodiment for a component.
FIG. 2 is a cross sectional view of the illustrative embodiment of FIG. 1 along line A-B.
FIG. 3 demonstrates an arrangement and a device according to the invention.
FIG. 4 depicts another illustrative embodiment in accordance with the invention.
DETAILED DESCRIPTION
FIGS. 1 and 2 include an optical fibre attachment arrangement or mount 4, 5, 6, 7 and the diode laser chip 1 on a common base 3. By this arrangement the best possible attachment of the solid body 2 is obtained without resorting to intermediate parts or components.
For bonding, the light beam wave-guide 2 is imbedded in solder 6, e.g. in SnPbAg or another solder composition with a specified separation from the laser diode 1. The solder 6, is itself enclosed in a further body 7, shown in FIG. 1 and 2 in the form of a V-grooved-chip, in order to achieve a best possible mechanical solder stabiltiy. The further body 7 comprises semiconductor material, for example silicon. The V-groove of the body member 7 may be etched and may be metalized. The soldered attachment to the base 3 which is common to the laser diode 1 and to the light beam wave-guide 2 is achieved thereby through a low heat conducting fibre support base, solderable at its upper and lower sides. The base 4 may also be metalized with a layer 5 on its upper and corresponding lower sides. With the combined beam wave-guide attachment 4, 5, 6, 7 a positioning of the light beam wave-guide 2 is possible during laser operation at a laser temperature of 25° C.
Suitable materials having low heat conductivity that adapted for this purpose include metalized glasses, metalized ceramics (Porcelain), metallized quartz and also metals such as stainless steel or other metals. It is then possible, through the selection of suitable materials and through suitable geometry of the base 4, to match the vertical thermal expansion (Δy) of the beam wave-guide support base 4 with the vertical thermal expansion of the laser diode base 3, in order to avoid beam wave-guide positional shifts, due to differential thermal expansion, in the range of 0.50 μm. Traverse positional changes (Δx) due to thermal expansion, are fundamentally ruled out through the attachment of the laser diode 1 and the beam wave-guide 2 to a common base.
FIG. 1 illustrates a lengthwise sectional view through a component according to the invention along the axis of the beam wave-guide 2. The axis of the light beam wave-guide 2 is considered to be the z-axis. FIG. 2 illustrates a cross sectional view taken approximately through the middle (line A-B) of the light beam wave-guide attachment 4, 5, 6, 7 of the embodiment of FIG. 1.
FIG. 3 illustrates the light beam wave-guide positioning and bonding procedure. In principle the bonding, by soft soldering, of the light beam wave-guide with a specified spacing relative to the laser diode is demonstrated as shown in FIGS. 1 and 2 and indeed in the region of the beam wave-guide attachment 4, 5, 6, 7 through coating of the light beam wave-guide 2 in the x-direction and y-direction. The attachment of the light beam wave-guide in the z-direction may be accomplished through a capillary on the housing of the laser diode module, not shown in the Figure, or on base 4 itself, when the light beam wave-guide 2 is metallized in the area of the base 4.
Positioning of the beam wave-guide occurs in the fluidized molten solder 6. The light beam wave-guide 2 is held in place upon cooling and solidification of the solder 6, at the end of the positioning procedure. The height of the base 4 presents the only limitation on the positioning play but this may be fixed in advance through correspondingly tighter tolerances.
The upper body member 7 is employed as an attachment accessory, and simultaneously as a heat source for melting the solder 6, used in bonding the beam wave-guide.
In this procedure it is not necessary to employ an external heat source to melt the solder i.e. a hot gas, an arc, a hot iron, etc., with which the laser diode is frequently heated as well. More often it is possible with this procedure to heat only that region of the light beam wave-guide 2, relative to the z-axis, in which the solder 6 is present. Thereby the power dissipation of the semiconductor 7 during current flow is used for heating (Schottky-Contact and bulk resistance), that is, the semiconductor body 7 is clamped between two electrodes 11a and 11b of a current regulated power supply. These electrodes are constructed in the form of a clamp or tongs and fastened to an x, y, z manipulator. A thermal sensor 11c attached to the one leg of the "heating clamp" for temperature control. This thermal sensor may be soldered, welded, cemented, etc. on.
The semiconductor body 7 may be a silicon chip or another type of semiconductor chip in this arrangement.
If a voltage is now applied to the clamp formed electrodes 11a, 11b, a heating current Ih, will flow through the semiconductor body 7, after a defined breakdown voltage (Schottky-contact between the metal of the electrodes 11a 11b and the semiconductor body 7) is reached, which will raise the temperature of the semiconductor body 7 to soldering temperature. With the use of a silicon chip as the semiconductor body 7, the breakdown voltage is about 80V and the heating current required to heat to soldering temperature is approximately 10 to 20 mA. It is important herewith, that the current required for heating is controlled through a current regulated voltage source. The desired temperature of the semiconductor body 7 can then be directly regulated and controlled with the thermal sensor 11c.
The solder 6 necessary for the fastening or securing of the light beam wave-guide 2 can be applied through pre-tinning of the metallized semiconductor body 7 to the respective desired degree. The base 4 is therewith also pre-tinned on its upper surface with the same solder.
In order to immerse the beam wave-guide 2 into the positioning solder 6, the solder preform 6, on the semiconductor body 7, is melted with the "heating clamp" consisting essentially of the electrodes 11a, 11b, as described above, and the semiconductor body 7, which is attached to the "heating clamps", is then lowered, while in the heated condition, with the manipulator, to which the "heating clamp" is attached, over the optical wave-guide fiber 2.
The melted solder 6 surrounded by the bare metallizing of the light beam wave-guide 2 envelops the beam wave-guide 2 and joins with the remaining solder on the upper surface of the base 4, and with that around the light beam wave-guide 2, in the region of the bonding point, so that complete solder immersion of the beam wave-guide takes place. Meanwhile any oxidation of the solder can be prevented through the use of a protective inert gas, and a uniform distribution of the solder achieved by movement of the semiconductor body 7 in the combined x and y directions. It is then possible, while the solder is in the fluid condition, to optimally align the semiconductor body 7 with the V-groove, in the x, y, z direction on the beam wave-guide 2 by means of the heating clamp manipulator, of which the electrodes 11a and 11b are a part and/or the semiconductor body 7 may by positioning of the light beam wave-guide 2 may, by means of an additional light beam wave-guide manipulator 10, be re-positioned so that, for example, the most uniform and narrow gap between the light beam wave-guide 2, V-groove of the semiconductor 7 and the base 4 results, through which the long term stability may be favorably affected.
Upon achievement of the desired position of the light beam wave-guide 2 the positioning solder 6 is allowed to cool down and solidify through a continuous controlled reduction of the heating current, and the light beam wave-guide 2 is bonded at the positioned location. The solder melting and positioning process can thereafter be repeated at will.
Upon proper beam wave-guide bonding the heating clamp is opened without loading of the semiconductor body 7 and the light beam wave-guide component parts 4, 5, 6, 7 thus separated from the heating clamp manipulator. The same applies to the additional light beam wave-guide manipulator 10.
When UV-curable and/or that heat curable adhesives or cements are employed instead of solder, the semiconductor body 7, with the V-groove may be substituted for measuring the cement quantity; for the absolute quantity, and the uniform distribution of the bonding agent 6, that is symmetrical about a plane which is normal to the base of the light beam wave-guide 2 and which contains the axis of the light beam wave-guide 2, around the light beam wave-guide 2, is of great importance.
In general the described procedure can also be applied to other similar components. For example, an infrared-emitting diode (IRED) can be used as element 1. The procedure described can also be employed in other devices for positioning and bonding such as for the positioning and bonding of wires or other objects that must be positioned relative to another object with high accuracy and have great long-term stability.
An important feature of the invention, is the use of another body 7, as an aid for positioning and bonding the solid body 2, and which simultaneously serves as a heat source for the melting of the attaching solder 6. When, therefore, the other element 7, provides these functions without itself adhering to the bonding agent 6, that has solidified at the end of the procedure, the other body 7, together with the heating clamp, can be removed again upon the solidification of the bonding agent 6. Therefore, the further element may in fact be a part of the heating clamp. The further body 7 need not necessarily be a semiconductor element in order to have these characteristics. For example, a carbon glass, already known from its use in hot cathode devices may be employed which, because of the spatial anisotrophy of its electronic transport characteristics, can provide a high heating capacity along with additional favorable mechanical and physical properties. With suitable treatment of the surface of the groove of such a further body 7, and with an additional surface coating is required, which makes the separation of the body 7 possible, after the solidification of the bonding agent, the further body 7 may again be separated from the solidified bonding agent. The nature of such coatings, for example a hard, smooth thin layer which may be evaporated, sputtered or otherwise applied is well known to those skilled in the art.
Another important feature of the invention is, that in the application of a low thermally conducting base 4, only region directly adjacent to the solid body 2, together with the bonding agent 6, need be brought to a higher temperature. If the base 4 is itself a part of the base 3, this advantage can also be achieved by making the entire base 3 of a low thermal conductivity material.
The base 4 and the laser diode 1 may also be arranged on various substrates. In each case the bonding agent employed may be either solder or a cement.
The heating of the bonding agent 6 need not necessarily result from current flow through the further body 7. The heating of the further body 7 can also be brought about through induction, with the aid of alternating electric field, aimed at said radiating in the direction of the further body 7. Therewith the requisite heating of the bonding agent 6 is generated in the interior of the further body 7. The heating of the bonding agent may also be brought about through heat radiation which is absorbed by the further body 7. A heat absorbing upper surface of the other body 7 is advantageous for this purpose. The heat radiation may be produced by a platinum heating resistance, and may additionally be reflected with suitable optics and aimed at the further body 7. The heating of the bonding agent 6 may also be produced through a heating device which is in direct thermal contact with the further body 7 and heats this further body 7 exclusively. For example, a device similar to the tip of a soldering iron may be applied to the further body 7. In each of these cases the further body 7 functions as a heating die that is not heated through the passage of current.
FIG. 4 illustrates a longitudinal sectional view through an additional embodiment of the invention similar to the lengthwise section of FIG. 1. A further body 7 provided with a depression (cavity, groove) may also be employed as the further body, whereby this depression serves as a means of positioning and bonding of the solid element 2 and/or the solid element 12. FIG. 4 shows the depression of the further body 7 at the top and, as an example, is provided with a lens, in the case of FIG. 4, a spherical lens 12. Here the lens 12 may be firmly attached to the further body 7. The solid body 12 may, in this way, be indirectly bonded and positioned through the bonding and positioning of the further body 7 in FIG. 4.
As an example, the solid element 12 in the depression of the further body 7 may be bonded with a type of bonding agent 6 having a higher melting point than the layer of bonding agent 6 between the base 4 and the further body 7 in FIG. 4. An arrangement is thus provided to allow the layer of bonding agent 6 between the base 4 and the further body 7 to melt and flow, upon the heating of the further body 7, without, however, the bonding agent 6, between the solid element 12 and the supplemental element 7, having melted and flowed at this temperature.
The further body 7 of FIG. 4 may be heated in exactly the same way as described in FIGS. 1 through 3 above. The further body 7 may be positioned in both the directions x and z in space, shown in FIG. 4, which together define the mounting surface of the base 4. The positioning in the different directions in space may be accomplished with the aid of a manipulator. Positioning in the y direction, that is positioning parallel to the normal of the mounting surface of the base 4, can in practice follow, without the need for additional bonding agent 6, in that, upon lowering of the solid body 12, a part of the bonding agent 6, is forced out of the intermediate space between the base 4 and the further body 7 and that, in the opposite case, upon lifting of the solid body 12, the bonding agent 6 will be pulled back into the intermediate space between the base 4 and the further body 7.
The further body 7 serves as an assisting body for transferring the thermal energy to the bonding agent 6 in order to cause this to melt and flow.
The bonding agent 6 in the intermediate space between the base 4 and the supplemental element 7 may have a thickness in the order of 0.1 to 0.2 mm. In the application of the spherical lens 12 as solid body, the diameter of this solid body may be 500 μm. If the solid body 12 is a spherical lens and if the center of the spherical lens lies on the optical axis of the emitted light bundle of the object 1, the divergent light bundle emitted can be formed into a parallel ray bundle by means of the spherical lens.
There has thus been shown and described a novel mounting arrangement for an optical fibre coupled to a laser diode which fulfills all the objects and advantages sought therefor. Many changes, modifications, variations and other uses and applications of the subject invention will, however, become apparent to those skilled in the art after considering this specification which disclose preferred embodiments thereof. All such changes, modifications, variations and other uses and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention which is limited only by the claims which follow. | A method and arrangement for the positioning and bonding of a solid body (2), in which one part of the solid body (2) together with the bonding agent (6) is to be attached to a further element (7) and bonded to a base (4) is to be capable of positioning the solid body (2), at the point attained after positioning, with both high precision and high long term stability. The solid body (2) is immersed in the bonding agent (6) and this bonding agent is in turn located in a groove of a further electrically conducting body (7). The further body (7) is heated by current flow to a temperature at which the solid body (2) is movable within the bonding agent. Upon attaining the desired positioning of the solid body (2), the bonding agent is allowed to cool through controlled reduction of the heating current until solidification occurs. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application claims the benefit of U.S. Provisional Patent Application No. 60/934,819, filed on Jun. 15, 2007, the disclosure of which is hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to digital sampling apparatuses and methods, including those used to determine frequencies of periodic digital signals.
BACKGROUND OF THE INVENTION
Determining the frequency of a periodic electrical signal is a common task performed in electronic systems. In the field of radio communications, for example, it is often necessary to determine the frequency of a communication signal in real-time.
Traditionally, analog circuitry has been used to determine the frequency of electrical signals. However, due to the complexity and unreliability of analog circuitry, and the trend toward all-digital radio systems, various digital frequency determining implementations have been proposed. U.S. Pat. No. 6,219,394 (‘the '394 patent’) discloses, for example, a frequency-to-digital converter (FDC) that operates to digitally determine the instantaneous frequency of a periodic digital signal.
FIG. 1 illustrates the two primary components of an FDC 100 , similar to that which is disclosed in the '394 patent. As shown, the FDC 100 comprises a frequency sampling circuit 102 and a digital filter 104 . The frequency sampling circuit 102 is configured to receive an input signal x(t) (or ‘test’ signal) having a frequency f x that is to be determined by the FDC 100 . The sampling circuit 102 samples the input signal x(t) at a known sampling rate f S provided by a sampling clock s(t), and generates a stream of digital bits representing the ratio of f x to f S . The digital filter 104 is configured to receive the stream of digital bits, and, based on the pattern of logic ‘1s’ and ‘0s’ in the stream, operates to recover the ratio of f x to f S . Since the sampling clock frequency f S is a known value, the frequency f x of the input signal x(t) can be determined from the recovered frequency ratio.
While the FDC 100 in FIG. 1 is desirable in that it provides an all-digital solution, the logic gates used to implement the FDC have inherent limits on the speed at which they may operate. Consequently, the FDC 100 is not suitable for determining frequencies of very high frequency signals. There is a need, therefore, for digital circuits and methods that are capable of sampling and determining frequencies of high-frequency digital signals, and which are not limited by inherent speed constraints of the underlying digital circuitry used to perform the sampling.
SUMMARY OF THE INVENTION
Methods and apparatus for sampling and determining the frequency of periodic digital signals are disclosed. An exemplary digital sampling apparatus includes a polyphase sampling apparatus having a plurality of sampling circuits and a plurality of logic level change circuits. The plurality of sampling circuits is configured to sample a periodic digital signal according to a polyphase clock system having multiple phases. The plurality of logic level change circuits is coupled to the plurality of sampling circuits, and is operable to detect logic level changes of the periodic digital signal that occur between phases of the polyphase clocks. The detected logic level changes can be used to determine the frequency of the periodic digital signal.
According to one aspect of the invention, the multiple phases provided by the polyphase clock system are successively distributed in time so that consecutive phases have a periodic phase difference. According to one embodiment of the invention, the periodic phase different between each pair of consecutive phases is the same. In another embodiment, a periodic phase difference between a first pair of consecutive phases is different from one or more other pairs of consecutive phases of the polyphase clock system.
By using the polyphase sampling apparatuses and methods of the present invention, a sampling rate equivalent to a sampling clock having a period equal to the phase difference in time between phases of the polyphase clocks is realized. Accordingly, the effective sampling rate of a given periodic digital signal can be increased, or the sampling of higher frequency periodic digitals signals is possible, while the underlying logic circuitry used to capture the samples is clocked at a much lower rate.
Other features and advantages of the present invention will be understood upon reading and understanding the detailed description of the preferred exemplary embodiments, found hereinbelow, in conjunction with reference to the drawings, a brief description of which is provided below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified block diagram of a prior art frequency to digital converter (FDC);
FIG. 2A is a schematic diagram of a polyphase FDC, according to an embodiment of the present invention;
FIG. 2B is a drawing including a timing chart showing the timing relationship among the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 and a test signal applied to the polyphase FDC in FIG. 2A , and an edge detection chart showing edge detection results from sampling the test signal using the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 ;
FIG. 3A is a schematic diagram of an exemplary polyphase ring oscillator circuit, which can be use to generate the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 for the polyphase FDC in FIG. 2A ;
FIG. 3B is a timing diagram showing the timing relationship among the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 generated by the polyphase ring oscillator in FIG. 3A ;
FIG. 4A is a is a schematic diagram of a polyphase FDC, according to an embodiment of the present invention;
FIG. 4B is a drawing including a timing chart showing the timing relationship among the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 and a test signal applied to the polyphase FDC in FIG. 4A , and an edge detection chart showing edge detection results from sampling the test signal using the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 ;
FIG. 5 is a schematic diagram of a dual-bank polyphase FDC, according to an embodiment of the present invention;
FIG. 6 is a schematic diagram of an edge redistribution circuit, which can be used to simplify the digital sampling of a test signal, in accordance with embodiments of the present invention;
FIG. 7A is a schematic diagram of an asymmetric polyphase FDC, according to an embodiment of the present invention;
FIG. 7B is a drawing including a timing chart showing the timing relationship among the asymmetric polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 and a test signal applied to the asymmetric polyphase FDC in FIG. 7A , and an edge detection chart showing edge detection results from sampling the test signal using the asymmetric polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 ;
FIG. 8A is a schematic diagram of an FDC that employs a plurality of positive edge detectors to sample multiple phases of a test signal, according to an embodiment of the present invention;
FIG. 8B is a timing diagram showing the timing relationship between a sampling clock and the multiple phases of the test signal of the FDC in FIG. 8A , when the frequency of the test signal is less than the frequency of the sampling clock;
FIG. 8C is a timing diagram showing the timing relationship between a sampling clock and the multiple phases of the test signal of the FDC in FIG. 8A , when the frequency of the test signal is greater than the frequency of the sampling clock;
FIG. 9A is a schematic diagram of a negative edge detector, a plurality of which can be used in the FDC shown in FIG. 8A , instead of the plurality of positive edge detectors;
FIG. 9B is schematic diagram of a dual-edge detector, a plurality of which can be used in the FDC shown in FIG. 8A , instead of the plurality of positive edge detectors;
FIG. 10 is block diagram of a frequency-locked loop (FLL) that employs a polyphase FDC, according to an embodiment of the present invention;
FIG. 11 is a block diagram of a polar modulation transmitter; and
FIG. 12 is a block diagram of the FLL in FIG. 10 adapted for use in the phase path of the polar modulation transmitter in FIG. 11 , according to an embodiment of the present invention.
DETAILED DESCRIPTION
Those of ordinary skill in the art will realize that the following detailed description of the present invention is illustrative only and is not intended to be in any way limiting. Other embodiments of the present invention will readily suggest themselves to such skilled persons having the benefit of this disclosure. Reference will now be made in detail to implementations of the present invention as illustrated in the accompanying drawings. The same reference indicators will be used throughout the drawings and the following detailed description to refer to the same or like parts.
Referring first to FIG. 2A , there is shown a polyphase frequency to digital converter (FDC) 200 , according to an embodiment of the present invention. The polyphase FDC 200 comprises a plurality of delay flip-flops (i.e., ‘D’ flip-flops) configured in an array of rows (eight in this example) and columns (three in this example). The clock inputs of each of the flip-flops in the first column (labeled “Col 1 ” in the drawing) of the flip-flop array are configured to receive clock signals from a polyphase clock system comprised of a plurality of clock signals (eight in this example) Φ 1 , Φ 2 , . . . , Φ 8 . Those of ordinary skill in the art will appreciate and understand that the FDC 200 shown in FIG. 2A is an exemplary embodiment, and that the number of clock signals making up the polyphase clock system can be more or less than eight.
Each clock signal of the polyphase clock system has the same frequency, but each clock signal is successively offset from a clock signal that precedes it by a predetermined fixed phase delay. The data (‘D’) inputs of each of the flip-flops in the first column (Col 1 ) of the flip-flop array are configured to receive an input signal (referred to herein as a ‘test’ signal) having a frequency f x that is to be determined by the FDC 200 . The test signal is labeled in the drawings using the signal's frequency symbol ‘f x ,’ and is sometimes referred to as “the test signal f x ” in the description that follows, for the sake of convenience and to emphasize that the test signal has that frequency. Some other signals are labeled in a similar manner for similar reasons.
The data inputs of the flip-flops in the second column (Col 2 ) of the flip-flop array are coupled to the data outputs of the flip-flops in the first column of the array. The upper four flip-flops in the second column of the array are configured to receive the first clock signal Φ 1 of the plurality of clock signals Φ 1 , Φ 2 , . . . , Φ 8 at their clock inputs. The lower four flip-flops in the second column are configured to receive the fifth clock signal Φ 5 at their clock inputs. As can be seen in FIG. 2B , the fifth clock signal Φ 5 is 180 degrees out of phase with the first clock signal Φ 1 . This allows the FDC 200 to sample the test signal in a circular fashion (i.e., according to the following repeating sampling sequence: Φ 1 , Φ 2 , . . . , Φ 8 , Φ 1 , Φ 2 , . . . , Φ 8 , . . . , Φ 1 . . . ).
The data inputs of the lower eight flip-flops in the third column (Col 3 ) of the flip-flop array are coupled to the data outputs of the flip-flops in the second column of the array. An additional flip-flop at the top of the third column (i.e., the uppermost flip-flop in the third column) has a data input that is coupled to the data output of the lowermost flip-flop in the third column of the array. The lower eight flip-flops in the third column of the array are configured to receive the first clock signal Φ 1 at their clock inputs. The uppermost flip-flop in the third column of the array is also configured to receive the first clock signal Φ 1 at its clock input. Finally, the complementary outputs (i.e. the Q and Q outputs) of the flip-flops in the third column of the flip-flop array are coupled to inputs of a plurality of AND logic gates, which provide digital outputs B 1 -B 8 .
FIG. 2B includes a timing diagram and a sampling chart, which can be referred to, to better understand the operation of the polyphase FDC 200 in FIG. 2A . The test signal (indicated by the label ‘f x ’ in the timing diagram) is successively sampled by the plurality of clocks Φ 1 , Φ 2 , . . . , Φ 8 of the polyphase clock system. The samples are captured by the flip-flops in the first column of the array. On the next positive edge of the first clock signal Φ 1 , the samples captured by the upper four flip-flops of the first column of the array are clocked into the upper four flip-flops of the second column of the array. Similarly, on the next positive edge of the fifth clock signal Φ 5 , the samples captured by the lower four flip-flops of the first column of the array are clocked into the lower four flip-flops of the second column of the array. On the next positive edge of the first clock signal Φ 1 , the data samples held by the flip-flops in the second column of the array are clocked into the lower eight flip-flops in the third column of the array. The data sample that was clocked into the lowermost flip-flop is then clocked into the uppermost flip-flop in the third column of the array by the first clock signal Φ 1 , thereby forming a circular like sampling cycle.
The successive samples appearing at the outputs of the flip-flops in the third column of the flip-flop array are logically combined by the AND logic gates to provide an indication as to whether level changes of f x , from a logic ‘0’ to a logic ‘1’ have occurred between the phases of the plurality of clocks Φ 1 , Φ 2 , . . . , Φ 8 . For example, when successive samples of the test signal by the first and second clock signals Φ 1 and Φ 2 are a logic ‘0’ and a logic ‘1,’ the output of the AND logic gate having an output labeled “B 2 ” will provide a logic ‘1’ value, to indicate that a logic level change from a logic ‘0’ to a logic ‘1’ has occurred between rising edges of the first and second clock signals Φ 1 and Φ 2 . The detected low-to-high logic level changes are indicative of positive edge transitions in the test signal. Accordingly, by detecting and monitoring the logic level changes over a known time span, the frequency f x of the test signal can be determined. One way of doing this is to employ a digital filter (for example, a finite impulse response (FIR) decimation filter). The digital filter can be configured to extract a ratio representing the effective sampling rate to the test signal frequency f x , based on the density of logic ‘1s’ appearing at the outputs B 1 -B 8 of the AND logic gates over time. Since the sampling rate f s is a known value, the frequency f x of the test signal can then be determined.
The sampling performance of the FDC 200 in FIG. 2A is equivalent to a sampling clock f s having a period equal to the time between phases of the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 . Hence, the FDC 200 is able to sample the test signal at a very high sampling rate, which in this example is effectively 8*f s , while the sampling logic itself is clocked at a much lower rate.
There are various ways by which the polyphase clocks Φ 1 , Φ 2 , . . . , Φ 8 used to clock the FDC 200 can be generated. FIG. 3A shows an exemplary polyphase clock generator 300 which is suitable for this purpose. The polyphase clock generator 300 is implemented in the form of a ring oscillator and comprises four differential delay elements 302 - 308 , eight differential-to-single-ended (D-SE) converters 310 - 324 for the eight phase endpoints, a programmable divider 326 , and a phase-frequency detector (PFD) and loop filter unit 328 . The eight phases of the polyphase clock system generated at the outputs of the D-SE converters 310 - 324 have a timing relationship as shown in FIG. 3B .
The polyphase clock generator 300 is locked to a reference clock (‘RefClk’ in the drawing), where a variety of ring frequencies can be selected using conventional synthesizer logic. When the plurality of clocks Φ 1 , Φ 2 , . . . , Φ 8 is used to clock the FDC 200 in FIG. 2A , all levels of the test signal will be sampled at an effective rate that is eight times faster than the rate at which the sampling logic is clocked. There will be no aliasing, so long as eight times the ring clock frequency is greater than two times the test signal frequency f x (with margin).
The FDC 200 in FIG. 2A employs AND logic gates to determine and indicate the occurrence of low-to-high logic level changes between clock phases. FIG. 4A shows an FDC 400 that is configured to determine and indicate the occurrence of both low-to-high and high-to-low logic level changes between clock phases, according to another embodiment of the present invention. The FDC 400 includes an array of flip-flops configured in rows and columns similar to the FDC 200 in FIG. 2A . However, rather than using AND logic gates to logically combine the data outputs of the flip-flops in the third column of the array, a plurality of exclusive-OR (XOR) logic gates is used to logically combine the outputs. Use of XOR gates provides the ability to determine occurrences of both low-to-high and high-to-low logic level changes between clock phases.
FIG. 4B shows a timing diagram and sampling chart for the polyphase FDC 400 in FIG. 4A . As can be seen, the bit pattern generated by the double edge polyphase FDC 400 is more dense in logic ‘1s’ than is the bit pattern generated by the FDC 200 shown in FIG. 2A . This is due to the fact that the FDC 400 in FIG. 4A detects both low-to-high and high-to-low logic level changes between clock, while the FDC 200 in FIG. 2A only detect low-to-high logic level changes.
FIG. 5 is a drawing of a polyphase frequency to digital converter (FDC) 500 , according to another embodiment of the present invention. The FDC 500 comprises a dual-bank FDC, which is adapted to receive a differential test signal having a frequency that is half that of the original test signal frequency f x . Each bank operates similar to the FDC 400 in FIG. 4A . The outputs of the XOR gates are summed by a plurality of summers having outputs B 1 , B 2 , . . . , B 8 . The outputs B 1 , B 2 , . . . , B 8 can have values of 0, 1, or 2. Similar to the previously described embodiments, the pattern of 0s, 1s and 2s contains information concerning the ratio of the sampling frequency to the test signal frequency. Because the sampling frequency is known, the test signal frequency f x can be extracted, e.g., by using a digital filter as was explained above.
Generating a divided differential test signal f x , and sampling it with the dual-bank FDC 500 , allows better sampling accuracy. Moreover, it affords the ability to either relax the offset among the sampling clock signals Φ 1 , Φ 2 , . . . , Φ 8 (for the same frequency test signal sampled in the embodiment shown in FIG. 4A ) or sample higher frequency test signals without having to reduce the offset among the sampling clock signals Φ 1 , Φ 2 , . . . , Φ 8 .
In some applications it may be advantageous to not only divide the test signal frequency but to also redistribute its edges. Redistributing the edges of divided test signals can simplify the sampling process and reduce the amount of clock margin needed to perform the sampling. FIG. 6 is a logic processing circuit 600 that can be used for this purpose. The test signal (again labeled using the signal's frequency label ‘f x ’) is passed through a single-end to differential buffer 602 , which creates a differential test signal. Each polarity of the differential test signal is separately divided by two by frequency dividers 604 and 606 , and then shifted using flip-flops 608 - 614 , thereby providing four redistributed signals. The four redistributed signals preserve the timing of the positive and negative transitions of the test signal f x and have frequencies that are half of the original test signal frequency f x . Redistributing the edges is non-destructive in the sense that the average density of logic ‘1s’ remains the same. However, the sampling process is simplified because the on and off times of each redistributed signal are fairly symmetric and each redistributed signal can be individually sampled using one of the polyphase FDCs disclosed herein.
Simulations have shown that non-uniform sample periods (i.e., phase offset variations among the clocks making up the polyphase clock system) have very little effect on the accuracy of the conversion, so long as the non-uniformity is periodically synchronous with the filtering used to extract the frequency. Indeed, when a FIR decimation filter is used, conversion remains very accurate so long as the period of the non-uniform pattern is half the period of the symmetric FIR filter span. This property relaxes the required phase tolerances between clocks of the polyphase clock system and, consequently, simplifies the design of the polyphase clock generator and edge redistribution circuits described above.
FIGS. 7A and B show an example of an ‘asymmetric’ polyphase FDC 700 , which is configured to operate according to a polyphase sampling clock system having non-uniform phases, and associated timing diagram and sampling chart. As can be seen, even with a polyphase clock system having sampling clocks with non-uniform sample periods, the asymmetric polyphase FDC 700 is capable of determining the frequency f x of a test signal. Operation of the FDC 700 is similar to the previously described embodiments. To prevent aliasing, the time for which the test signal is a ‘1’ or a ‘0’ should be greater than the maximum phase delay ΔΦMax among the polyphase clocks.
The asymmetric property of the asymmetric polyphase FDC 700 in FIG. 7 can be exploited to reduce spurious problems that might otherwise develop when the FDC 700 is configured in a radio communications system (such as an RF transmitter or receiver). It can also be used to reduce undesirable side-effects such as tonality, sensitivity to integer clock ratios, and error non-uniformity. For example, any one or more of the delay stages making up the polyphase clock generator (e.g., each stage of the multiphase ring oscillator in FIG. 3A ) can be made to be different than any one of the other clocks. Further, these delay stages can be made to be individually programmable, either dynamically or for different test signal frequencies f x .
The previously described embodiments of the present invention employ a polyphase clock system to achieve faster effective sampling rates than can be achieved using prior art FDCs. According to an alternative embodiment of the invention, a higher effective sampling rate is achieved by sampling multiple phases of the test signal. Similar to the above described embodiments, logic level transitions (i.e., logic low-to-high and/or logic high-to-low transitions) are used to determine the frequency of the test signal. However, rather than determining transitions based on logic level samples of the test signal, a plurality of edge detector circuits are used to directly detect edges of multiple phases of the test signal.
FIG. 8A is a schematic diagram of an FDC 800 employing a plurality of positive edge detector circuits, according to an embodiment of the present invention. Four positive edge detectors are used in this exemplary embodiment. However, any number of asynchronous edge detectors can be used, depending on, for example, design requirements or performance capabilities of available components, as will be appreciated by those of ordinary skill in the art. The four positive edge detectors are configured in four rows. The positive edge detector in the first row comprises D flip-flops Q 7 -Q 10 and an AND gate. Similarly, the positive edge detectors in the second, third and fourth rows, respectively, comprises flip-flops Q 11 -Q 14 and corresponding AND gate; flip-flops Q 15 -Q 18 and corresponding AND gate; and flip-flops Q 19 -Q 22 and corresponding AND gate. Flip-flops Q 1 and Q 2 divide the test signal f x by four (4), and flip-flops Q 3 -Q 6 comprise a shift register, which is configured to generate multiple, shifted versions (i.e., multiple phases) of the divided test signal, as indicated by the labels ‘Q 3 ,’ ‘Q 4 ,’ ‘Q 5 ,’ and ‘Q 6 ’ in the timing diagram in FIG. 8B .
The positive edge detectors in the FDC 800 in FIG. 8A are operable to perform one-shot operations, so that on a rising edge of a divided test signal, an associated positive edge detector provides a logic ‘1’ for one cycle of the sampling clock f s . The results are registered in the four output flip-flops, Q 10 , Q 14 , Q 18 and Q 22 , and, for each period of the sampling clock, are summed by an adder. Similar to the previously described embodiments, the density of logic ‘1s’ in the digital stream, relative to the number of logic ‘0s,’ together with knowledge of the sampling clock frequency f s , allows the frequency f x of the test signal to be determined.
The FDC 800 in FIG. 8A provides an effective sampling frequency of two times (×2) the sampling frequency f s . It is capable of detecting one or two transitions of the test signal in the period of the sampling clock without aliasing. If f x <f s , the sum at the output of the FDC 800 will be 0 or 1. If f s <f x <2f s , the sum will be 1 or 2, as shown in FIG. 8C .
The FDC 800 was shown and described as employing a plurality of positive edge detectors. However, negative and dual-edge (i.e., positive and negative edge) detectors, such as those shown in FIGS. 9A and 9B , respectively, can be alternatively used. Similar to the positive edge detector, the negative and dual-edge detectors each comprises four D flip-flops Q 1 -Q 4 and an AND logic gate. Q 1 serves to reduce meta-stability by re-clocking f x to be synchronous with f s . Q 2 and Q 3 perform a digital one-shot operation, so that on a falling (i.e., negative) edge of f x the output of the AND gate of the negative edge detector ( FIG. 9A ) will be a logic ‘1’ for one cycle of the sampling clock f s . The dual-edge detector in FIG. 9B operates similarly, except that a digital one-shot is generated for one cycle of the sampling clock f s each time a falling or rising edge of f x is detected.
The FDCs of the present invention may be used in a variety of applications. FIG. 10 illustrates, for example, how one of the polyphase FDCs described above can be used in a frequency-locked loop (FLL) 1000 . The FLL 1000 includes a main signal path and a feedback path. The main signal path includes a loop filter 1002 , a digital-to-analog converter (DAC) (e.g., sigma-delta DAC) 1004 , and a voltage controlled oscillator (VCO) 1006 . The feedback path contains a polyphase FDC 1008 and a decimation filter 1010 .
The FLL 1000 operates to force the frequency of the signal at the output of the VCO 1006 toward a reference frequency. The reference frequency is digitally represented by a first digital stream generated by a digital frequency synthesizer (DFS) 1012 , similar to the digital portion of a sigma-delta analog to digital converter. In the main path of the FLL 1000 , the loop filter 1002 filters out noise from the error signal and provides the filtered error signal to the DAC 1004 . The DAC 1004 converts the digital error signal to an analog error signal, which is applied to the VCO 1006 . The VCO 1006 changes its output frequency based on the value of the analog error signal.
In the feedback path, the polyphase FDC 1008 samples the VCO output signal, similar to described above, using a polyphase clock system provided by a polyphase clock generator 1014 . A second digital stream generated by the polyphase FDC 1008 is decimated down to the clock rate of the main path and subtracted from the first digital stream representing the desired frequency (i.e., the reference frequency) to generate the error signal. The VCO 1006 responds to changes in the error signal by changing its output frequency. This feedback operation is performed continuously to force the VCO output frequency to equal the reference frequency.
According to an embodiment of the present invention, the FLL 1000 in FIG. 10 is adapted for use in the phase path of a polar modulation transmitter. As shown in FIG. 11 , a polar modulation transmitter 1100 modulator comprises a data generator 1102 ; a rectangular-to-polar converter 1104 ; an amplitude modulator 1106 and a power driver 1108 configured within an amplitude path of the transmitter 1100 ; a phase modulator 1110 and a voltage controlled oscillator (VCO) 1112 configured within a phase path of the transmitter 1100 ; a power amplifier (PA) 1114 ; and an antenna 1116 .
An incoming digital message is coupled to the data generator 1102 to generate in-phase (I) and quadrature phase (Q) pulse-shaped baseband signals. The rectangular-to-polar converter 1104 converts the I and Q baseband signals into a polar signal comprised of an envelope (i.e., amplitude) signal component ρ(t) and a constant-amplitude phase difference signal component Δθ(t). The amplitude modulator 1106 is configured to receive the envelope signal ρ(t) in the amplitude path, and modulate a power supply voltage (Vsupply) according to the amplitude of envelope signal ρ(t). At the same time, the phase modulator 1110 receives the constant-amplitude phase difference signal Δθ(t) in the phase path, and drives the VCO 1112 to provide an RF drive signal to the PA 1114 .
FIG. 12 illustrates how the FLL 1000 in FIG. 10 is adapted for use in the phase path of the polar modulation transmitter 1100 in FIG. 11 . The desired output frequency is derived from two sources represented in digital form. The first source is a frequency constant, which represents the center frequency of the VCO for a particular channel, for example. The second is the phase difference signal Δθ(t) in the phase path of the transmitter 1100 . The phase difference signal Δθ(t) includes the sample time by sample time change in the desired phase of the modulated signal. These two digital signals are summed by a summer 1202 . The sum is presented to a DFS 1204 , which generates a digital reference frequency (i.e., a desired output frequency). Similar to explained above, a decimation filter 1206 in the feedback path of the FLL 1200 decimates the digital stream generated by the polyphase FDC 1208 down to the clock rate of the main path. The decimated digital signal is then subtracted from the digital reference frequency to generate an error signal. The VCO 1210 responds to changes in the error signal by changing its output frequency. This feedback operation is performed continuously to force the VCO output frequency to equal the frequency represented by the digital reference frequency.
While the above is a complete description of the preferred embodiments of the invention sufficiently detailed to enable those skilled in the art to build and implement the system, it should be understood that various changes, substitutions, and alterations may be made without departing from the spirit and scope of the invention as defined by the appended claims. | Methods and apparatus for sampling and determining the frequency of periodic digital signals. An exemplary digital sampling apparatus includes a polyphase sampling apparatus configured to sample a periodic digital signal according to a polyphase clock system having multiple phases. The multiple phases provided by the polyphase clock system are successively distributed in time so that consecutive phases have a periodic phase difference. By using a polyphase clock system, a sampling rate that is equivalent to a sampling clock having a period equal to the phase difference in time between phases of the polyphase clocks is realized. Accordingly, the effective sampling rate of a given periodic digital signal can be increased, or the sampling of higher frequency periodic digitals signals can be achieved, while the underlying logic circuitry used to capture the samples is clocked at a much lower rate. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application under 35 U.S.C. §120 of U.S. application Ser. No. 10/989,013, entitled “AXIS TRANSLATION INSTALLATION MECHANISM FOR OPTOELECTRONICS MODULES”, filed on Nov. 15, 2004, which is hereby incorporated herein in its entirety.
BACKGROUND ART
[0002] Optoelectronic modules include circuitry for converting between signal processing/transmission in an optical mode and signal processing/transmission in an electrical mode. The conversion may be in a single direction, but many modules provide bidirectional conversions to enable data exchanges in both modes. Optoelectronic modules are used in telecommunications central offices and in centralized computing facilities, where there is a significant demand for high bandwidth communications. As compared to metal interconnects, such as copper wiring, optical interconnects offer benefits with regard to both bandwidth and performance (e.g., less skew), while satisfying requirements relating to eye safety, electromagnetic compatibility, reliability, manufacturability, and cost.
[0003] It is common to couple an array of optoelectronic modules to a single substrate, such as a printed circuit board. Connectivity of a particular module is provided by coupling a module connector to a substrate connector. Edge-card style connectors are often used, but parallel optical links typically require the use of high-density electrical connectors to accommodate the larger number of electrical signals that must be managed. A single optical link may combine twelve optical channels that are separated into twelve electrical signals within the module. It follows that for each such link, there is a need for twelve electrical paths between the module and the substrate. Thus, the edge-card style connectors are sometimes replaced by connectors having pin-and-socket arrangements. The pins are rigid wire strands of electrically conductive material that are received within sockets having a fixed arrangement that corresponds to that of the pins.
[0004] A greater degree of flexibility with regard to the maintenance of the telecommunications central office or the centralized computing facility is available if the optoelectronic modules are replaceable. A difficulty is that the openings for inserting and removing optoelectronic modules through the housing of the host system typically allow the greatest degree of freedom for module movement in the Z axis, i.e., the axis that is parallel to the surface of the substrate on which the substrate connectors are mounted. This is shown in FIGS. 1 and 2 . A printed circuit board 10 having an electrical connector 12 is shown as being within the interior of a housing that includes a bezel, or faceplate 14 . The optoelectronic module 16 enters the housing through an opening within the faceplate, as indicated by the arrow 18 along the Z axis. However, the seating of the module must occur along the Y axis, which is represented by arrowed line 20 . The module connector 22 must properly seat onto the substrate connector 12 , but the direction of movement for seating the module is orthogonal to the greatest degree of freedom of module movement. Either before or after the module connector is seated, an optical fiber 29 is joined to the optoelectronic module to input/output optical signals.
[0005] One solution is to mount a substrate connector that has a seating direction perpendicular to the printed circuit board 10 (i.e., along the Z axis). The module connector 22 must be relocated to the rear surface of the optoelectronic module 16 , rather than the bottom surface as shown in FIGS. 1 and 2 . This allows the user to merely push the module rearwardly until the two connectors are seated together. This solution has benefits, but may impose restrictions on signal density. An alternative solution is described in U.S. Pat. No. 6,074,228 to Berg et al. Pressure contacts are preferably used for the connectors of Berg et al., rather than insertion contacts which require significantly more force in order to provide proper seating. The pressure contacts may be J-shaped leads which deflect slightly when press fit to contact pads of another connector. Since the required mating forces are reduced, the insertion force requirements are relaxed. The substrate connector of Berg et al. has a body that includes a guide member, which is elongated along the Z axis. The elongated body of the substrate connector is surface mountable on a printed circuit board. The connector body also includes a camming element that is comprised of ramped regions. When the replaceable module is slid along the elongated body of the connector, a cam follower of the module raises and lowers the end of the module because of contact with the ramped regions of the camming element. While the raising and lowering of the module brings the module connector into contact with the leads of the substrate connector, the pressure contact may not be sufficient for some applications. Specifically, there may be concerns that less than all of the leads of the substrate connector have a low resistance connection to the contact pads of the module connector.
SUMMARY OF THE INVENTION
[0006] The seating of an optoelectronic module onto a substrate connector includes guiding the module along an initial path portion that is misaligned from the mating direction of the substrate connector and includes providing a positive pressure drive along an end path portion with sufficient force to secure the optoelectronic module to the substrate connector. For applications in which the substrate and module connectors are electrical connectors that are coupled using a pin-and-socket arrangement, the positive pressure drive is enabled to push the main body of the optoelectronic module with sufficient force to ensure entry of the pins into the sockets.
[0007] In a system for controlling the coupling of module connectors of a number of optoelectronic modules to an array of substrate connectors on a substrate, such as a printed circuit board, each optoelectronic module is associated with a device having a slide configured to receive the optoelectronic module so as to enable sliding movement of the module and includes a drive mechanism coupled to the slide to displace the slide toward and away from the substrate. In the sliding movement of the module, the module remains non-coplanar with the substrate connector to which it is to be coupled. However, the drive mechanism then displaces the slide toward and away from the substrate, with the displacement being such that the module connector is aligned to couple with the substrate connector.
[0008] The method of controlling coupling of a module connector to a substrate connector may be described as including the step of sliding the optoelectronic module along a plane that is parallel to the substrate surface on which the substrate module is fixed. During this sliding movement, the module connector remains at a distance from the substrate surface such that the two connectors remain in a non-coplanar relationship. The method includes mechanically applying a coupling force to push the optoelectronic module toward the substrate in a controlled alignment to securely couple the module and substrate connectors. In a decoupling operation in accordance with the method, a decoupling force that is the reverse of the coupling force is mechanically applied to unseat the module connector from the substrate connector. The optoelectronic module is then slid along the same plane followed during the initial insertion, but in the reverse direction.
[0009] As one possibility, the seating device includes a slide that remains stationary as the optoelectronic module is slid into place. The slide has a slide surface which defines the initial path portion for movement of the module. After the sliding action has been completed, a cam is pivoted to press the slide surface toward the substrate. A cam handle remains exposed to provide access by a user. When the cam handle is rotated in one direction, the connector of the optoelectronic module is seated to the substrate module. Rotation of the cam handle in the opposite direction unseats the connectors.
[0010] In another embodiment, the seating device includes a sliding cam. The device has a slide that is perpendicular to the mating direction of the connectors. The positive pressure drive of the device includes an actuator and slots that are aligned with the mating direction. In this embodiment, movement of an actuator in the mating direction controls movement of the slide. For applications in which the substrate is mounted horizontally, the slide structure is moved horizontally to a position that aligns the substrate and module connectors and then is moved vertically to bring the two connectors into contact.
[0011] In a rocking slide cam embodiment, the angle of the optoelectronic module varies with approach toward a seated condition of the connectors. For example, a number of actuator pins may be received within a corresponding number of grooves configured to determine the variation in module angle. In this embodiment, an actuator and the optoelectronic module may be in a fixed relationship with travel of the module along the initial path portion. However, the actuator is moved relative to the optoelectronic module during the end path portion, when the force is applied for seating the module connector with the substrate connector.
[0012] The seating device also has a mechanical toggle switch embodiment. In this embodiment, linkage may be used to translate motion of an actuator along an axis that is perpendicular to the mating direction into motion of the optoelectronic module in the mating direction.
[0013] The positive pressure drive may also be provided by a stroke multiplier mechanism in which motion of an actuator in a direction perpendicular to the mating direction is translated to motion in the mating direction by orientations of at least two slots. For example, a first slot in a fixed rail may have an orientation opposing a second slot in a movable slide. Additionally, vertical slots in the rail may be used to constrain the motion of the slide vertically, so that force applied to the actuator is desirably coupled to the slide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a side view of an optoelectronic module to be seated within the interior of a host system.
[0015] FIG. 2 is a side view of the optoelectronic module positioned above the connector to which the module is to be seated.
[0016] FIG. 3 is a Z axis view of a force latch mechanism as one embodiment for seating an optoelectronic module in accordance with the invention.
[0017] FIGS. 4, 6 , 8 and 10 are front view of different steps in the operation of the force latch mechanism of FIG. 3 .
[0018] FIGS. 5, 7 , 9 and 11 are rear views of the different steps for operating the force latch mechanism of FIG. 3 .
[0019] FIG. 12 is a perspective view of a sliding cam mechanism in accordance with a second embodiment of the invention.
[0020] FIG. 13 is a side view of the sliding cam mechanism of FIG. 12 with an optoelectronic module in a raised position.
[0021] FIG. 14 is a side view of the sliding cam mechanism of FIG. 12 with the module in its seated position.
[0022] FIG. 15 is a rocking slide cam mechanism in accordance with a third embodiment of the invention.
[0023] FIGS. 16-19 illustrate different steps in the operation of the rocking sliding cam mechanism of FIG. 15 .
[0024] FIG. 20 is a toggle switch mechanism in accordance with a fourth embodiment of the invention.
[0025] FIGS. 21 and 22 are side views of steps for operating the toggle switch mechanism of FIG. 20 .
[0026] FIG. 23 is a side view of a stroke multiplier mechanism in accordance with a sixth embodiment of the invention.
DETAILED DESCRIPTION
[0027] The invention is a means for seating an optoelectronic module, such as the module 16 shown in FIGS. 1 and 2 , to a connector 12 on a substrate 10 , such as a printed circuit board. A user is able to insert and withdraw the module through an opening in the faceplate 14 without withdrawing the substrate from the host system. In the embodiments to be described below, the module moves in the Z axis direction 18 before force is applied in the Y axis direction 20 , but the directions are not necessarily horizontal and vertical. While the seated connectors 12 and 22 will be described as being electrical connectors, in some applications the invention may be used to properly seat optical connectors. In such applications, the optical fiber 29 is replaced with electrical input/output members, since the module 16 is one in which conversions between an optical mode and an electrical mode are performed. As will be recognized by a person skilled in the art, the ability to connect and disconnect the fiber 29 may be replaced with a “pigtailed” module in which the fiber is fixed with respect to the module.
[0028] A first embodiment of the seating device is shown in FIG. 3 . This embodiment takes the form of a force latch mechanism 24 that is able to simultaneously apply force in two perpendicular directions so as to install or remove the optoelectronic module 16 . The mechanism includes a slide member 26 , a rail 28 , and a slide pin 30 . A recess 32 within the module 16 is aligned to receive the slide 26 . While not shown in FIG. 3 , the module rests on the upper surface of the slide 26 .
[0029] The module connector 22 is shown as being positioned above the substrate connector 12 . In operation, the module 16 slides along the top surface of the slide 26 with the two connectors remaining misaligned relative to the distance from the substrate on which the connector 12 resides. In the embodiment of FIG. 3 , the substrate connector 12 includes an array of pins 34 that project upwardly for reception within a corresponding array of sockets within the module connector 22 . Alternatively, the socket-and-pin arrangement may be reversed.
[0030] FIGS. 4 and 5 respectively show front and rear views of the force latch mechanism 24 , but without a module. For purposes of illustration, the slide 26 has been removed from the mechanism 24 in FIG. 5 . A cam 36 is attached to the rail 28 at a sliding cam pin 38 . The cam includes a cam handle 40 that is accessible to a user during a seating or unseating operation.
[0031] In a seating operation, the module is slid along the surface of the slide 26 to the position shown in FIG. 3 . After the module is fully inserted, the user pushes the cam handle 40 in the direction indicated by arrows 42 and 44 . The initial movement of the module may be considered to be along the Z axis, but the orientation of movement is not critical to the invention.
[0032] The force applied to the cam handle 40 causes the cam pin 38 to slide along the first path portion of a slot 46 within the rail 28 . When the cam pin reaches the end of the first path portion, the cam handle 40 may be pivoted upwardly such that the cam pin follows an arcuate second path portion of the slot 46 .
[0033] The front and rear views of FIGS. 6 and 7 , respectively, show the condition of the force latch mechanism 24 when the cam pin 38 has reached the end of the first path portion of the slot 46 . Because a fixed rail pin 48 engages a slot 50 within the cam 36 , the movement of the cam pin along the first path portion induces some pivoting, as indicated by arrow 52 . That is, the combination of the cam pin within the rail slot and the rail pin within the cam slot determines movement of the cam as the user applies pressure to the cam handle 40 of FIG. 4 . The cam pin reaches the end of the first path portion simultaneously with the rail pin reaching the end of the cam slot. At this point, the cam contacts the slide pin 30 that is entrapped within a vertical opening 56 .
[0034] FIGS. 8 and 9 illustrate the next step in the seating operation. Here, the cam is rotated as the user applies pressure to the cam handle (not shown). The cam rotates about the rail pin 48 . This forces the slide pin 30 to move downwardly within the vertical opening 56 , thereby displacing the slide 26 downwardly. Since the module is mounted to the slide, the module also moves downwardly.
[0035] In FIGS. 10 and 11 , the cam handle has been fully rotated. Consequently, the slide and module have been forced downwardly to achieve mating with the substrate connector 12 of FIG. 3 . Sufficient force is provided to ensure that the pin-and-socket arrangement of the two connectors 12 and 22 provides low resistance coupling of the pins 34 with the optoelectronic module 16 .
[0036] The steps for removing the optoelectronic module 16 of FIG. 3 are the reverse of those described with reference to FIGS. 4-11 . The cam handle 40 is rotated in a counterclockwise direction and is pulled rearwardly to the position shown in FIG. 4 . This allows the module to be easily removed from the slide 26 . While the manipulation of the cam handle has been described as being manual, the force latch mechanism 24 may be adapted to hydraulic, pneumatic or electromechanical systems.
[0037] FIG. 12 illustrates a second embodiment of the invention. In this embodiment, the seating device is a sliding cam mechanism 58 . The mechanism couples perpendicular motion by use of a slide 60 having diagonal slots 62 and 64 . A rail system is composed of the slide 60 , an actuator 66 , and a rail 68 . In this embodiment, the optoelectronic module 16 travels in the Z axis and engages the slide by means of a groove. The slide may be considered to be a sliding cam. The rail may be connected to the substrate by screws or other fasteners which pass through a pair of openings 70 and 72 within a bracket 74 .
[0038] FIG. 13 shows the optoelectronic module 16 in a raised position, while FIG. 14 shows the module in a fully seated position. Once the module is inserted, the actuator 66 accomplishes the Y axis (vertical) motion of the module by coupling the paths of various slots with the module. As best seen in FIG. 13 , the actuator extends to a sliding member 76 that lies within a rail slot 78 of the rail 68 . The sliding member 76 has projections which extend into the diagonal slots 62 and 64 on the slide 60 . Since the slots extend diagonally upward, horizontal motion of the sliding member 76 and its projections is translated into vertical motion of the slide 60 and the module that is coupled to the slide. A pair of pins 80 and 82 extending from the slide project into vertical slots 84 and 86 within the rail 68 . As represented by arrow 88 , motion of the slide 60 is confined to the vertical by the use of the pins 80 and 82 within the vertical slots 84 and 86 . The vertical slide-rail constraint can be achieved in other manners, such as by the use of dovetail joints or folded edges that capture the slide.
[0039] The operational steps of a third embodiment are illustrated in FIGS. 15-19 . Here, the seating device is a rocking slide cam mechanism 98 . In this embodiment, the number of components is reduced, but the complexity of individual components is increased. A rail 90 receives the optoelectronic module 16 . The slots 92 and 94 within the rail are configured to cause the module to rock as pressure is applied to an actuator 96 . That is, rocking motion occurs as opposed to the straight vertical descent of the embodiment of FIGS. 12-14 . The illustrated embodiment operates well with the MEG array connector known in the art.
[0040] In FIG. 15 , the optoelectronic module is inserted into the rocking slide cam mechanism 98 . A user can apply pressure directly to the module or to the actuator 96 . A rigid protrusion 100 extends beyond the module and initially rides within a slot groove 102 .
[0041] The arrow 104 in FIG. 15 represents the movement of the module 16 relative to the actuator 96 and the rail system 90 . After the module has been properly seated, the actuator is pressed inwardly, as represented by arrow 106 in FIG. 16 . Within each slot 92 and 94 resides an actuator pin 108 and 110 . Immediately prior to the application of force to the actuator 96 , the actuator pins are at the ends of the slots, as shown in FIG. 16 . As the module is pushed rearwardly, the two actuator pins 108 and 110 follow their respective grooves, but the grooves have different geometries such that the pins follow different paths.
[0042] Referring now to FIG. 17 , when the protrusion 100 at the end of the module 16 clears the slot groove 102 , the rear of the module is no longer supported by the rail system 90 . However, the two actuator pins 108 and 110 control the position of the module by means of their engagement with the respective slots 92 and 94 . The slots in the rail system are designed such that the module exhibits a slight tilt, which is intended to accommodate the high mating force required for high density electrical connectors.
[0043] The rearward movement of the module 16 causes the protrusion 100 to abut a hard stop 112 . The contact of the protrusion with the hard stop prevents any further movement of the module along the Z axis (arrow 106 ). In this embodiment, the actuator is able to release from its neutral position, so as to be movable relative to the module. As the user continues to push the actuator 96 , the actuator moves relative to the module, as represented by arrow 114 in FIG. 18 . Movement of the module tracks the geometries of the slots 92 and 94 . The module is forced downwardly to mate with the electrical connector (not shown). In FIG. 19 , the actuator 96 has reached its final position. In this position, the module 16 is locked into its seated position with no tilting. An unseating operation follows the reverse of the seating operation.
[0044] The geometry of the slots 92 and 94 can be designed to accommodate any type of connector. Thus, the principle may be modified for any particular application.
[0045] FIG. 20 illustrates a toggle switch mechanism 116 in accordance with another embodiment of the invention. The mechanism includes an actuator 118 , a rail 120 , and a slide 122 . The cooperation of components converts the Z axis motion of the actuator 118 into Y axis translation of the module 16 by means of links 124 and 126 . Each link has a first end that is pivotally connected to the actuator, such that the first ends move linearly with the actuator, but are able to rotate. The opposite end of each link is coupled to a vertical slot 128 and 130 within the rail. A bracket 132 may be used to mount the mechanism to a substrate, such as a printed circuit board.
[0046] As best seen in FIG. 21 , the rail 120 includes a second pair of vertical slots 134 and 136 . Engaging each slot is a projection 138 and 140 that is fixed to the slide 122 that supports the module 16 . The engagement of the projections with the vertical slots limits the movement of the slide 122 to vertical movement. The mechanism is shown in the raised position in FIG. 21 . In this position, the projections 138 and 140 are at the upper extents of the slots 134 and 136 . Also, the links 124 and 126 are at only a slight decline.
[0047] The slide 122 has a pair of diagonal grooves 142 and 144 . The movement of the actuator 118 is coupled to the slide 122 by means of the grooves. For example, the pivoting ends of the links 124 and 126 may be secured by pivot pins having ends that extend into the diagonal grooves. Thus, as the actuator is pushed inwardly, the links will pivot at their upper ends and will ride along the respective slots 128 and 130 at the their lower ends. Simultaneously, the pivot pins through the upper ends of the links will travel along the diagonal grooves 142 and 144 to apply downward pressure on the slide 122 . This causes the projections 138 and 140 from the slide to travel downwardly along the second pair of vertical slots 134 and 136 within the rail 120 . Eventually, the mechanism will reach its lowered position shown in FIG. 22 , with the connector of the module 16 properly seated to the substrate connector (not shown).
[0048] Yet another embodiment is shown in FIG. 23 . The stroke multiplier mechanism 146 includes an actuator 148 , a slide 150 , and a rail 152 . The optoelectronic module 16 is shown as resting in position on the slide. In this figure, the coupler 154 for receiving an input/output optical fiber is included. A pair of opposing diagonal slots 156 and 158 multiply the motion of the input actuator 148 . The first of the diagonal slots 156 is in the fixed rail 152 , while the second slot 158 is in the movable slide 150 . Vertical slots 160 and 162 constrain the motion of the slide vertically. The vertical slots may be either in the rail or the slide. After the module has been engaged to the slide, it is also restricted to vertical movement.
[0049] By modifying the angle of the opposing diagonal slots 156 and 158 , it is possible to adjust the stroke multiplication to the degree required for a particular connector. The sliding cam mechanism 58 of FIG. 12 may be considered to be a specific embodiment of a stroke multiplier, if one of the “opposing slots” is identified as the horizontal rail slot 78 .
[0050] While a number of mechanisms have been described and illustrated for converting the direction of motion orthogonally so as to seat an optoelectronic module, the invention extends beyond the illustrated embodiments. Moreover, the conversion need not be directly orthogonal, as can be seen by the rocking slide cam mechanism of FIGS. 15-19 , which takes advantage of module tilting to provide the force necessary to properly mate the module connector to the substrate connector. | An optoelectronic module is seated onto a substrate connector by guiding the module along an initial path portion that is misaligned with respect to the mating direction defined by the substrate connector and further includes providing a positive pressure drive along an end path portion with sufficient force to secure the optoelectronic module to the substrate connector. Where the mating is via a pin-and-socket arrangement, the positive pressure drive requires sufficient force to push the main body of the module to ensure entry of the pins into the sockets. Typically, there is a conversion from force applied in one direction to module motion in the orthogonal direction. However, a rocking cam embodiment is also described. | 7 |
This application is a divisional of U.S. patent application Ser. No. 10/335,954 filed Jan. 3, 2003, now U.S. Pat. No. 7,381,887 which claims priority under 35 U.S.C. §119(a) on Japanese Application 2002-013226 filed Jan. 22, 2002, all of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to solar cells, particularly a solar cell with its back surface having a paste electrode of Al thereon, and relates to methods and apparatuses for manufacturing the solar cell.
2. Description of the Background Art
FIG. 9 shows a structure of a solar cell with its back surface provided with a paste electrode made of Al. The structure of the solar cell is hereinafter described in connection with a manufacturing process shown in FIG. 10 . For a crystalline silicon-based cell, after a p-type silicon substrate 1 is etched, an n-type diffusion layer 2 is deposited on one side of the substrate that serves as a photo-receiving plane and an anti-reflection film 3 is formed thereon in order to decrease the surface reflectance. On the other side of the substrate that is opposite to the photo-receiving plane (the above-mentioned other side is herein referred to as “back surface” as appropriate), a paste of Al is screen-printed, dried at approximately 150° C. and thereafter fired in the air at approximately 700° C. to form a paste electrode 4 of Al. Moreover, a silver paste is screen-printed on some parts of the back surface and the photo-receiving plane according to a pattern, dried and thereafter fired in an oxidizing atmosphere at a high temperature to form paste electrodes 5 and 6 of silver. The resultant device is immersed in a flux, silver paste electrodes 5 and 6 are then solder-coated, and the device is rinsed and dried to produce the solar cell. The solar cell generally has a size of, for example, 10 cm, 12.5 cm or 15.5 cm per side.
In the screen-printing process, a cell to be subjected to printing is fixed on a stage, and a screen mask is lowered to adjust the distance between the cell and the screen mask to an appropriate one. The Al paste is supplied onto the screen mask and a squeegee is moved while pressurizing the paste so as to transfer the Al paste onto the cell through the screen mask.
FIG. 11A is a plan view of a p-type silicon substrate 11 showing an Al paste electrode 14 formed on the back surface of the substrate. FIG. 11B shows a cross section of the substrate along line a-a in FIG. 11A The thickness of the Al paste which has been dried is 45 to 55 μm, the average thickness being approximately 50 μm.
In order to manufacture solar cells excellent in long-term reliability at low cost, there has recently emerged a need for decrease of the amount of the Al paste used in the process that constitutes a considerable part of a solar cell. In addition, as it is known that decrease of the thickness of the Al paste electrode is effective for lessening any warp of the solar cell and, in this sense, it is urgently required to decrease the amount of the Al paste.
The decrease of the amount of the Al paste and the decrease of the thickness after drying to 40 μm or less for example, are unsatisfactory for the following reason. Referring to FIG. 12 , after the Al paste is fired, ball-shaped Al particles 19 of a diameter ranging from several tens of μm to several hundred μm are generated on the outer edge of the electrode. This trouble called ball-up causes a problem that the cell cannot be commercialized due to the defect in appearance.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a thin solar cell produced with a decreased amount of an Al paste, without the trouble of ball-up. Another object of the present invention is to provide a method of manufacturing such a solar cell as discussed above as well as an apparatus used therefor.
A solar cell of the present invention has an Al paste electrode on its back surface, and at least a part of an outer edge of the Al paste electrode has a greater thickness than that of any remaining part of the Al paste electrode. Preferably, only one side, only two sides opposite to each other, or only two sides adjacent to each other, of the outer edge of the Al paste electrode is/are thicker than any remaining part of the Al paste electrode. It is also preferable that the thickness of the Al paste electrode successively changes.
According to a method of manufacturing a solar cell of the present invention, screen printing is performed by pressurizing an Al paste through a screen mask to transfer the Al paste to the back surface of the solar cell. The distance between the screen mask and the back surface of the solar cell in the screen printing is changed depending on a part of the back surface that is to be printed, and a part more distant from the screen mask is printed with a thicker Al paste while a part less distant from the screen mask is printed with a thinner Al paste.
The distance between the screen mask and the back surface of the solar cell may be changed by providing a spacer to at least a part of a space between a frame of the screen mask and a mask holder, by providing a spacer to at least a part of a region to be screen-printed that is located along and outside the perimeter of the solar cell, by providing a spacer to at least a part between the solar cell and a stage for securing the solar cell thereon, or by inclining the stage for securing the solar cell thereon.
Accordingly, the solar cell of the present invention may be manufactured by a screen printer having a stage for securing the solar cell thereon that is inclined to change the distance between the screen mask and the back surface of the solar cell. The solar cell of the present invention may also be manufactured by moving a squeegee faster above a part of the back surface of the solar cell that is to be printed with a thicker Al paste. Moreover, the solar cell of the present invention may be manufactured by performing printing of the Al paste at least once before, after or before and after the screen printing for a part of the back surface of the solar cell that is to be applied with a thicker Al paste.
Further, the solar cell of the present invention may be manufactured by performing spray coating of the Al paste at least once before, after or before and after the screen printing for a part of the back surface of the solar cell that is to be applied with a thicker Al paste. The solar cell of the present invention may be manufactured by using a screen mask having a pressed part used for applying a thinner Al paste. The manufacturing apparatus of the present invention thus includes the screen mask with a pressed part for applying a thinner Al paste.
A solar cell of the present invention may be manufactured by using a screen mask with the distance between an edge of a pattern of the screen mask and a frame of the screen mask that is closest to the edge being at most 30 mm, preferably at most 20 mm. The manufacturing apparatus of the present invention thus includes the screen mask with the distance from the frame being at most 30 mm, preferably 20 mm.
The solar cell of the present invention may be manufactured by using a squeegee applying printing pressure which is changed depending on a part to be printed, and accordingly a thicker Al paste is formed on a part applied with a lower printing pressure relative to a part applied with a higher printing pressure. The manufacturing apparatus of the present invention includes a squeegee applying a decreased printing pressure by a part of an edge of the squeegee which is shorter than a remaining part of the edge of the squeegee. Further, the manufacturing apparatus of the present invention includes a squeegee having a part of an edge and another part thereof that are attached at respective angles different from each other to apply a lower printing pressure by the part of the edge than that applied by that another part.
According to the present invention, a thin solar cell can be provided that uses a decreased amount of an Al paste without being accompanied by a problem of ball-up which is a defect in appearance, as well as a method of manufacturing the solar cell and an apparatus used therefor. Moreover, according to the present invention, the solar cell can be produced without substantially changing the conventional materials and process. In addition, the present invention is effective in that the cell cracks less frequently since the outer edge of the aluminum electrode has an increased thickness.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A to 1E each show a cross sectional view of a solar cell according to the present invention.
FIGS. 2 to 4 each show a cross sectional view of a screen printer used for the present invention.
FIG. 5 is a cross sectional view of a screen mask according to the present invention.
FIG. 6 is a plan view of a screen mask according to the present invention.
FIG. 7A is a front view of a squeegee according to the present invention and FIG. 7B is a left side view thereof.
FIG. 8A is a front view of a squeegee according to the present invention and FIG. 8B is a left side view thereof.
FIG. 9 is a cross sectional view showing a structure of a solar cell having an Al paste electrode formed on the back surface thereof.
FIG. 10 is a flowchart illustrating a process of manufacturing the solar cell having the Al paste electrode formed on the back surface thereof.
FIG. 11A is a plan view of a p-type silicon substrate having an Al paste electrode formed thereon and FIG. 11B is a cross sectional view along line a-a in FIG. 11A .
FIG. 12 is a cross sectional view of a p-type silicon substrate with an Al paste electrode formed thereon where the trouble of ball-up occurs.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
<Solar Cell>
The present invention has a characteristic that, at least a part of an outer edge of an Al paste electrode formed on the back surface of a solar cell has a greater thickness than that of any remaining part of the electrode.
The outer edge of the Al paste electrode has a thickness which is made greater than that of any remaining part, since the ball-up tends to occur on the outer edge of the Al paste electrode and the increased thickness of the electrode makes the ball-up less prone to occur. Specifically, the ball-up is less prone to occur when the thickness of the electrode is at least 45 μm, while the ball-up is more prone to occur when the thickness is 40 μm or less. In view of this, even if the Al paste electrode has a thickness of 40 μm or less in order to reduce the amount of the Al paste used for forming the Al paste electrode, the thickness of the outer edge of the electrode is preferably at least 45 μm for preventing the ball-up and the thickness is more preferably at least 55 μm.
A reason for increasing the thickness of at least a part of the outer edge of the Al paste electrode is that, the ball-up does not uniformly occur on the electrode. In other words, the probability of occurrence of the ball-up is higher on a side of the electrode that enters a firing furnace first, while the probability thereof is lower on a side of the electrode that enters the fixing furnace last. Moreover, in consideration of the challenge to decrease the amount of Al paste to be used, any part where the ball-up tends to occur is preferably made thicker.
Specifically, as shown in FIGS. 1A to 1C , only one side of the outer edge of an Al paste electrode 14 that is put into a firing furnace first is preferably larger in thickness. In this case, preferably the thickness is gradually varied as shown in FIG. 1A according to any method of varying the thickness of the printed electrode for example. Alternatively, only two sides including the side entering the furnace last are preferably made thicker as shown in FIG. 1D . Further, as the probability of occurrence of the ball-up is higher on the outer edge of the Al paste electrode while the ball-up rarely occurs on the central part of the electrode, all of the four sides constituting the outer edge of the electrode are made thick as shown in FIG. 1E . It is to be noted here that the electrode is not always put into the furnace in the direction perpendicular to opposite two sides of the electrode, or the electrode may be polygonal in shape. In these cases, preferably only two sides adjacent to each other of the outer edge of the Al paste electrode are made thick (not shown).
<Manufacturing Method>
The solar cell of the present invention has the characteristic that the outer edge of the Al paste electrode is relatively thick. The thickness of the electrode may be varied from part to part of the electrode by, for example, changing the distance between the screen mask and the back surface of the solar cell, changing any conditions of the printing speed or pressure for example, changing the number of times the printing is done, changing the specification of the screen mask, or changing the specification of the squeegee.
A method of manufacturing a solar cell according to the present invention has a characteristic that, the distance between the screen mask and the back surface of the solar cell undergoing screen printing is varied according to a part of the electrode to be printed so that a part of the electrode at a relatively long distance from the screen mask has a thicker Al paste printed thereon while a part at a relatively short distance therefrom has a thinner Al paste printed thereon. When there is a longer distance between the screen mask and the back surface of the solar cell, a greater amount of an Al paste is allowed to pass through the screen mask and thus a greater amount of the Al paste can be transferred onto the back surface of the solar cell to print the Al paste of a greater thickness. The relation between the distance from the screen mask to the back surface of the solar cell and the thickness of the Al paste varies depending on the viscosity, for example, of the Al paste to be used. If an Al paste may be printed to have a thickness of approximately 40 μm with the distance of 0.3 to 0.6 mm between the screen mask and the back surface of the solar cell, the thickness of approximately 45 μm of the paste is achieved by providing a distance of 1.5 to 2.0 mm between the screen mask and the back surface of the solar cell.
Preferred methods of varying the distance between the screen mask and the back surface of the solar cell according to a part to be printed are now described. Referring to FIG. 2 , a spacer 27 may be provided between a frame 24 of a screen mask 23 and a mask holder 22 , a spacer 28 may be provided to at least a part of the perimeter of a region of a cell 25 (hereinafter referred to as “solar cell” as appropriate) that is to be screen-printed, a spacer 29 may be inserted into at least a part of the region between a stage 26 holding cell 25 and cell 25 , or stage 26 holding cell 25 may be inclined. Any of the above-discussed methods allows the screen mask 23 which is moved down for printing to be inclined with respect to the back surface of the solar cell, and thus the distance between the back surface of the solar cell and the screen mask is varied according to a part to be printed.
Another method of manufacturing a solar cell according to the present invention as shown in FIG. 3 has a characteristic that a squeegee 31 is speedily moved above a part 38 where an Al paste is to be printed to a greater thickness in screen-printing. The squeegee is moved faster and accordingly, the screen mask separates more speedily from the back surface of the solar cell as the squeegee passes. Then, a greater amount of an Al paste is passed through the screen mask and transferred onto the back surface of the solar cell and the part is printed with a thicker paste relative to any part above which the squeegee moves slower. The squeegee moves at a speed which is different depending on the specification, for example, of a screen printer. If the squeegee can be moved at a speed of 30 to 50 mm/sec to print an Al paste to a thickness of approximately 40 μm, a thickness of approximately 45 μm is achieved by moving the squeegee at a higher speed of 120 to 200 mm/sec.
Still another method of manufacturing a solar cell according to the present invention has a characteristic that, any part to be printed with a thicker Al paste is subjected to at least one printing operation of the Al paste before, after, or before and after screen printing. The same part is printed a plurality of times to generate a thicker printed paste relative to other parts. One example of this method is shown in FIG. 4 , according to which a printer is controlled as follows. After screen printing and before returning of a squeegee 41 with a scraper (ink turner) 48 provided thereon, a new cell 45 is fixed on a stage 46 and, in the course of returning of squeegee 41 and scraper 48 back to the original position, scraper 48 is lowered onto a part 49 to be printed with a thicker paste to pressurize a screen mask 43 . By this method, pre-printing can be performed by scraper 48 before screen printing by squeegee 41 , which is preferable in that the pre-printing is performed with easy manipulation after the screen printing. Scraper 48 may be lowered by 1.0 mm or less to print an Al paste of 5 to 20 μm in thickness, which may be different depending on the specification of the Al paste. In addition, the Al paste used for the first printing can be used for the second and subsequent printing operations. If an Al paste contains a glass component, an Al paste of a different kind may be used.
A further method of manufacturing a solar cell according to the present invention has a characteristic that, a part where a thicker Al paste is to be printed undergoes at least one spray-coating of an Al paste before, after, or before and after screen printing. The spray coating allows that part to be printed with a thicker paste relative to other parts. Although another coating method except for the spray coating may be employed, the spray coating is a simplest one and thus preferable. When the spray coating is made, such an organic solvent as n-butyl carbitol acetate is preferably added to the Al paste for decreasing the viscosity of the paste relative to the viscosity for the screen printing. Moreover, the Al paste used for the first printing can be used for the second and subsequent printing operations. If an Al paste contains a glass component, an Al paste of a different kind may be used.
The solar cell of the present invention may be manufactured by a screen mask as shown in FIG. 5 . Specifically, screen mask 53 has a pressed section 53 a corresponding to a part 51 for printing a thin Al paste. The pressed section 53 a is thinner than a non-pressed screen mask section 53 b . Accordingly, the pressed section of the increased density passes less Al paste, resulting in a thinner Al paste in screen printing. Regarding the pressing work, calendar roll may be used for pressurizing.
A further method of manufacturing a solar cell according to the present invention has a characteristic as shown in FIG. 6 . Specifically, in order to provide a section 63 a of a screen mask for printing a thicker Al paste and a section 63 b for printing a thinner Al paste, the distance X between a pattern edge 60 and the closest frame 64 of the screen mask is set to 30 mm or less. As this distance X is 30 mm or less, the speed at which the screen mask separates from the back surface of the solar cell by the tension of the screen mask increases when the screen mask is pressurized by a squeegee. Then, the amount of the Al paste passed through the screen mask to be transferred onto the back surface of the solar cell increases and accordingly the thicker Al paste can be printed, as achieved by increasing the speed of movement of the squeegee. With a shorter distance X, a thicker paste can be printed and thus the distance is preferably 20 mm or shorter.
A further method of manufacturing a solar cell according to the present invention has a characteristic that the pressure of the squeegee in screen printing is different depending on the part to be printed. A lower printing pressure results in a smaller amount of an AL paste which is wiped off and thus results in a thicker printed Al paste. The relation between the printing pressure and the amount of printed Al paste is different depending on the type of the Al paste and the speed of movement of the squeegee, for example. If a printing pressure of 5.0 to 6.0 kg/cm produces an amount of the printed paste of 35 to 40 μm, the printing pressure may be reduced to 2.0 to 2.5 kg/cm to produce the printed paste of 40 to 45 μm. The printing pressure may be varied by the squeegee through the following methods for example. Referring to FIGS. 7A and 7B , a certain part 71 a of the edge of a squeegee 71 may be cut off to become shorter than another part 71 b of the edge so as to decrease the printing pressure. Alternatively, as shown in FIGS. 8A and 8B , a certain part 81 a and another part 81 b of the edge of a squeegee 81 may be attached at different angles respectively so as to decrease the printing pressure of the edge part 81 a relative to that of the edge part 81 b of squeegee 81 .
<Manufacturing Apparatus>
A screen printer according to the present invention has a characteristic that a stage on which a solar cell is secured is inclined to vary the distance between the screen mask and the back surface of the solar cell according to the part to be printed.
A screen mask according to the present invention has a characteristic that a part of the screen mask that is used for printing a thin Al paste is pressed. Further, a screen mask of the present invention has a characteristic that the distance between the pattern edge of the screen mask and the closest mask frame is 30 mm or less, and preferably 20 mm or less.
A squeegee according to the present invention has a characteristic that a part of the edge of the squeegee is made shorter than another part of the edge in order to decrease the printing pressure of the shorter edge part. Further, a squeegee of the present invention has a characteristic that a certain part of the edge of the squeegee and another part thereof are attached at different angles respectively so as to decrease the printing pressure of that certain part relative to the printing pressure of that another part.
The above-described screen printer, screen masks and squeegees are appropriate for an apparatus for manufacturing the solar cell as described above that has the characteristic that at least a part of an outer edge of an Al paste electrode has a greater thickness than that of any remaining part of the electrode.
EXAMPLE 1
A p-type silicon substrate in the shape of a square of 125 mm×125 mm with a thickness of 330 microns was texture-etched. On one side of the substrate, an n-type diffusion layer having a sheet resistance of approximately 50 ω was formed at 900° C. through thermal diffusion of P. On the diffusion layer, a silicon nitride film with a thickness of approximately 60 nm was formed through plasma CVD so as to serve as an anti-reflection film. Then, on the back surface of the substrate, a paste of Al was screen-printed, dried at 150° C. and put into an IR furnace with the thickest part entering the furnace first. The paste was fired at 700° C. in the air to produce a paste electrode of Al. Moreover, silver pastes were respectively screen-printed on the back side and the light-receiving plane in accordance with a pattern, dried, and thereafter fired at 600° C. for 2 minutes in an oxidizing atmosphere to produce paste electrodes of silver. Finally, the silver paste electrodes were each coated with a solder layer and accordingly, the solar cell was completed.
For the screen printing, a printer SS150 manufactured by Seishin Trading Co., Ltd. was used, and 3718G1 manufactured by MURATA MFG. CO., LTD. was used as the Al paste. Further, as shown in FIG. 2 , using screen mask 23 having a thickness of 150 μm and formed of a mesh made of SUS150 and a frame having a size of 320 mm×320 mm, spacer 27 is inserted into one side of frame 24 of the screen mask and secured to mask holder 22 , and then printing was done. (Spacers 28 and 29 were not provided in this Example.) Spacer 27 used here was a plastic plate having a width of 15 mm, a length of 150 mm and a thickness of 1 mm. The inserted spacer 27 inclined screen mask 23 with respect to solar cell 25 in lowering a mask holder 22 and screen printing.
The resultant Al paste electrode had a cross section as shown in FIG. 1 A, with its thickness successively changing from the thickest part toward the thinnest part. After drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 45 μm and 39 μm, with the average thickness of 42 μm. A conventional Al paste is 45 to 55 μm in thickness with the average thereof being approximately 50 μm. Then, the amount of the Al paste used in Example 1 was smaller by 16% as a whole relative to the conventional paste, and thus a thin solar cell was achieved. It is noted that the ball-up did not occur after firing. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of inserting the spacer, by means of conventional materials and process.
EXAMPLE 2
A solar cell was manufactured as done in Example 1 except that spacer 27 shown in FIG. 2 is removed and spacer 28 made of plastic and having a width of 15 mm, a length of 150 mm and a thickness of 1 mm was attached to stage 26 along one side of cell 25 to perform screen printing.
A resultant Al paste electrode had a cross section as shown in FIG. 1A , with its thickness successively changing from the thickest part toward the thinnest part. After drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 45 μm and 40 μm, with the average thickness of 42 μm. Then, the amount of the Al paste used in Example 2 was smaller by 16% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of attaching the spacer, by means of conventional materials and process.
EXAMPLE 3
A solar cell was manufactured as done in Example 1 except that, on the top surface of stage 26 shown in FIG. 2 , an adhesive cellophane tape 29 of 150 mm in length was affixed, the thickness of the cellophane tape 29 was adjusted to 150 μm, and thereafter cell 25 was fastened thereon to perform screen printing (spacer 27 was removed here).
A resultant Al paste electrode had a cross section as shown in FIG. 1A , with its thickness successively changing from the thickest part toward the thinnest part. After drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 46 μm and 40 μm, with the average thickness of 43 μm. Then, the amount of the Al paste used in Example 3 was smaller by 14% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of affixing the spacer, by means of conventional materials and process.
EXAMPLE 4
As shown in FIG. 3 , a solar cell was manufactured as done in Example 1 except that screen printing was done with squeegee 31 moved at a high speed of 160 mm/sec above the part 38 and moved at a speed of 40 mm/sec equal to that of Example 1 above the remaining part (with spacer 27 removed here).
A resultant Al paste electrode had a cross section as shown in FIG. 1B . After drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 45 μm and 41 μm, with the average thickness of 42 μm. Then, the amount of the Al paste used in Example 4 was smaller by 16% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of increasing the speed of moving the squeegee, by means of conventional materials and process.
EXAMPLE 5
A solar cell was manufactured as done in Example 1 except that screen printing was done with squeegee 31 moved at a high speed of 160 mm/sec above the parts 38 and 39 and moved at a speed of 40 mm/sec equal to that of Example 1 above the remaining part (with spacer 27 removed here), as shown in FIG. 3 .
A resultant Al paste electrode had a cross section with two protruding parts (not shown). After drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 45 μm and 41 μm, with the average thickness of 43 μm. Then, the amount of the Al paste used in Example 5 was smaller by 14% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of increasing the speed of moving the squeegee, by means of conventional materials and process.
EXAMPLE 6
After Example 1 was carried out, a cell was newly fastened onto the stage. Spacer 27 was removed, scraper 48 was thereafter placed over squeegee 41 as shown in FIG. 4 , and then the scale of the printer was adjusted to lower scraper 48 at the position above the part 49 by 0.5 mm relative to other parts so as to start printing. When scraper 48 with squeegee 41 was moved back to scrape the Al paste, scraper 48 at the position above the part 49 is lowered by 0.5 mm to cause the Al paste to be printed on that part 49 . Then, as Example 1, squeegee 41 was moved to carry out screen printing.
The part 49 was printed twice. Accordingly, after drying and before firing, the thickest part 49 and the thinnest part of the Al paste had respective thicknesses of 45 μm and 41 μm, with the average thickness of 42 μm. Then, the amount of the Al paste used in Example 6 was smaller by 16% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of lowering the scraper by 0.5 mm, by means of conventional materials and process.
EXAMPLE 7
As shown in FIG. 2 , a solar cell was manufactured as done in Example 1 except that screws (not shown) for fastening stage 26 were adjusted to lower the left side of stage 26 by 0.5 mm and then secure the stage as it is so as to perform screen printing (without spacer 27 ).
Accordingly, after drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 48 μm and 40 μm, with the average thickness of 42 μm. Then, the amount of the Al paste used in Example 7 was smaller by 16% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of changing the angle of placement of the stage, by means of conventional materials and process.
EXAMPLE 8
As shown in FIG. 5 , the part of screen mask 53 that corresponds to the region 51 was pressed by a calendar roll. Consequently, the non-pressed part 53 b of screen mask 53 was 70 μm in thickness while the pressed part 53 a was 59 μm in thickness. A solar cell was manufactured as done in Example 1 except that this screen mask was used to perform screen printing (without spacer 27 ).
Accordingly, after drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 45 μM and 39 μm, with the average thickness of 42 μm. Then, the amount of the Al paste used in Example 8 was smaller by 16% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of pressing the screen mask, by means of conventional materials and process.
EXAMPLE 9
As shown in FIG. 6 , in order to produce the part 63 a and the part 63 b of screen mask 63 respectively for printing the Al paste to larger and smaller thicknesses, the distance X between the pattern edge 60 and the closest frame 64 of the screen mask was adjusted to 20 mm. In addition, since frame 64 was of small size, an adapter (not shown) was used for printing. A solar cell was then manufactured as done in Example 1 except for the above-discussed procedure (without spacer 27 ).
After drying and before firing, the thickest part and the thinnest part of the Al paste had respective thicknesses of 45 μm and 42 μm, with the average thickness of 43 μm. Then, the amount of the Al paste used in Example 9 was smaller by 14% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of changing the specification of the screen mask, by means of conventional materials and process.
EXAMPLE 10
A solar cell was manufactured as done in Example 1 except that an Al paste was uniformly screen-printed on the entire back surface of the p-type silicon substrate to a thickness, after being dried, of 36 μm, the paste was then dried, and one side corresponding to the outer edge of the resultant Al paste electrode was subjected to screen printing again (without spacer 27 ).
The resultant Al paste electrode had a cross section as shown in FIG. 1C . The thickest part and the thinnest part of the Al paste had respective thicknesses of 55 μm and 36 μm, with the average thickness of 40 μm. Then, the amount of the Al paste used in Example 10 was smaller by 20% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of performing screen printing twice, by means of conventional materials and process.
EXAMPLE 11
A solar cell was manufactured as done in Example 1 except that an Al paste was uniformly screen-printed on the entire back surface of the p-type silicon substrate to a thickness, after being dried, of 36 μm, the paste was then dried, and two opposing sides corresponding to the outer edge of the resultant Al paste electrode were subjected to screen printing again (without spacer 27 ).
The resultant Al paste electrode had a cross section as shown in FIG. 1D . The thickest part and the thinnest part of the Al paste had respective thicknesses of 55 μm and 36 μm, with the average thickness of 41 μm. Then, the amount of the Al paste used in Example 11 was smaller by 18% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of performing screen printing twice, by means of conventional materials and process.
EXAMPLE 12
An Al paste was uniformly screen-printed on the entire back surface of the p-type silicon substrate to a thickness, after being dried, of 36 μm, the paste was then dried, and one side was spray-coated, that one side being a place where the outer edge of the resultant Al paste electrode was to be located. For the spray coating, 20% by mass of n-butyl carbitol acetate was added to the Al paste which was used for the screen printing in order to decrease the viscosity of the paste. An air gun was used for the spray coating to form a spray coating of 20 mm in width. A solar cell was accordingly produced as done in Example 1 except for the above-described process (no spacer 27 was attached).
The resultant Al paste electrode had a cross section as shown in FIG. 1C . The thickest part and the thinnest part of the Al paste had respective thicknesses of 53 μm and 36 μm, with the average thickness of 40 μm. Then, the amount of the Al paste used in Example 12 was smaller by 20% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of adding one spray coating process, by means of conventional materials and process.
EXAMPLE 13
An Al paste was uniformly screen-printed on the entire back surface of the p-type silicon substrate to a thickness, after being dried, of 36 μm, the paste was then dried, and four sides were spray-coated, that four sides being a place where the outer edge of the resultant Al paste electrode was to be located. For the spray coating, the Al paste (diluted) used in Example 12 was employed. An air gun was used for the spray coating to form a spray coating of 20 mm in width. A solar cell was accordingly produced as done in Example 1 except for the above-described process (no spacer 27 was attached).
The resultant Al paste electrode had a cross section as shown in FIG. 1E . The thickest part and the thinnest part of the Al paste had respective thicknesses of 53 μm and 36 μm, with the average thickness of 42 μm. Then, the amount of the Al paste used in Example 13 was smaller by 16% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of adding one spray coating process, by means of conventional materials and process.
EXAMPLE 14
As shown in FIG. 7A , a certain part 71 a of the edge of squeegee 71 that is a side contacting the screen mask was cut off over 100 μm and 20 mm in width. FIG. 7B shows a left side of this squeegee 71 . A solar cell was accordingly produced as done in Example 1 except for the use of the squeegee (no spacer 27 was attached).
The thickest part and the thinnest part of the Al paste had respective thicknesses of 45 μm and 41 μm, with the average thickness of 42 μm. Then, thex amount of the Al paste used in Example 14 was smaller by 16% as a whole relative to the conventional paste. It is noted that the ball-up did not occur after firing the Al paste. This example accordingly produced the solar cell having electric characteristics and reliability comparable to those of conventional products, through a simple operation of cutting off the edge of the squeegee, by means of conventional materials and process.
Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims. | A thin solar cell is provided, a decreased amount of an Al paste used for the solar cell without occurrence of a problem of ball-up which is a defect in appearance. A method of manufacturing such a solar cell as well as a manufacturing apparatus used therefor are provided. This manufacturing method is applicable with substantially no change in the conventional material and process. The solar cell has an Al paste electrode on the back surface and at least a part of an outer edge of the Al paste is thicker than any remaining part. | 8 |
RELATE US APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/499,384, filed 3 Sep. 2003.
FIELD OF THE INVENTION
[0002] The present invention relates to the automated creation of documents, and in particular, to the mark-up of transactional values within such documents.
BACKGROUND TO THE INVENTION
[0003] It is well known to generate customised documents, either manually or using an automated system, from precedents or templates.
[0004] If this is done manually, then a printed standard form or other precedent, containing blank spaces for particular relevant information, will be filled in an edited on each specific occasion it is used. Instructions may be included in the standard document to help the user insert the correct or appropriate information.
[0005] If this is done using an automated system, then an electronically stored document or template will be used, in conjunction with various logical rules and other criteria, to prompt the user for the correct information and to assemble a customised document by associating various relevant rules with variables within the template. For example, the HotDocs® system using a library of Form Templates, which store both static and dynamic areas of text, that are initially customised by the user, in conjunction with a questionnaire to produce a completed customised document. Necessary information relevant to the dynamic text areas may either be input directly by a user, or gathered from an Answer File. The Answer File contains information which is repeatedly used in the same or similar customised document. Various logical rules and calculation criteria are used to associate information with the template to produce a final customised document. This document may then be edited, printed or stored.
[0006] Other known automated systems include that described in WO01/04772. In this system, a server computer runs a document generation program and is capable of communicating with local or remote client computers over a local area network (LAN) or a wide area network (WAN), such as the internet. A standard document, comprising various items of known information and associated logical rules, is first translated into a form suitable for processing by the document generation program. When instructed to generate a customised document, the server first generates one or more web pages which are sent to client computers for user input of the further information required to evaluate the logical rules. Users may then submit the further information to the server. Once all the required further information has been captured, the server generates a customised document on the basis of the standard document and received further information.
[0007] For a fully customised document, which contains no conditional text as all of the information required to be complete, there is no need to provide any form of temporary document which indicates where information needs to be provided. However, it is not always possible for the user to provide enough information to allow the document generation program to generate a fully customised document. The document generation program therefore needs to find a way in which this missing information can be included in a partially customised document. For example, there may be various transaction values, such as currency values, missing, or there may be insufficient information to resolve all of the conditional clauses within the template. Therefore, the partially customised document must have the same information content as the template it is generated from, as well as the ability to cope with and indicate to the user the effect of, missing transaction values and conditional information.
[0008] WO03/061474 describes a system for the generation of partially customised documents. Although the system provides a mark up of the information which is not included in the partially customised document, such as conditional clauses, there is no facility to indicate missing or indefinite transaction values. Information relating to unresolved conditional clauses are marked-up in a prescribed manner, which may or may not be suitable for a particular user's needs.
[0009] There therefore exists a need to provide a method by which transaction values can be marked-up in a partially customised document. The mark-up used also needs to be flexible, to accommodate a particular user's needs.
SUMMARY OF INVENTION
[0010] The invention aims to address the problems of the prior art described above. The invention provides a document generation system for generating a customised document using content elements selected by rules operating on input information, the operating information comprising transaction values. The system comprises at least one computer having a document generation program stored thereon, means to associate further rules with the transaction values, and means to evaluate said further rules to produce an indication whether the transaction values are definite, indefinite or absent in a partially customised generated document.
[0011] The effect of the transaction values is represented by means of a mark-up. The mark-up may be user-defined, such as by selecting rules from a pre-determined menu.
[0012] The invention also provides a computer implemented method of document generation, wherein rules associated with the content elements are evaluated to produce a partially customised document, and specific highlight rules are evaluated to indicate, in the partially customised document, whether transaction values are definite, indefinite or absent. Such a computer implemented method may be implemented as a computer program product and stored on a computer readable medium.
[0013] The invention provides the advantages that not only can a partially customised document containing definite or indefinite transaction values, or containing content elements relating to absent transaction values be generated, but whether a particular transaction value is definite indefinite or absent can be indicated in a particular highlight style.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The invention will now be described by way of example only, and with reference to the accompanying drawings in which:
[0015] FIG. 1 illustrates a first network system in which embodiments of the invention may be carried out;
[0016] FIG. 2 illustrates a second network system in which embodiments of the invention may be carried out;
[0017] FIG. 3 illustrates a third network system in which embodiments of the invention may be carried out;
[0018] FIG. 4 is a flow diagram showing the stages in producing a customised document;
[0019] FIG. 5 is a schematic illustration of the relationship between the transaction values, the template and the generated document; and
[0020] FIG. 6 is a schematic illustration of the relationship between mark-up rules and transaction values.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0021] The system in which embodiments of the present invention are implemented will now be briefly described. The system comprises one or more data processing means, which, where a plurality of processing means are used, are connected together using communication means. For example, client/server architecture may be used, with one of the data processing means functioning as a server, and others as clients. However, a single processing means may function as both server and client. Various configurations of client/server architecture are shown in FIGS. 1, 2 and 3 .
[0022] FIG. 1 shows a server computer 10 connected to two local client computers 20 and 22 , connected by means of a local area network (LAN) 30 , forming an intranet. Each computer 10 , 20 , 22 , runs an operating system program, such as Microsoft Windows 2000 Professional™ and network programs such as Novell Netware™. The server computer 10 also runs a Web server application such as Microsoft Internet Information Server™, and each of the local client computers 20 , 22 also run a browsing application such as Microsoft Internet Explorer™. The server 10 and local computers 20 , 22 communicate using transmission control protocol/internet protocol (TCP/IP) and hypertext transfer protocol (HTTP), or alternatively, a language such as XML. The invention is not limited to any particular hardware architecture. For example, the invention could be implemented as a stand alone computer such as, for example, a PC.
[0023] FIG. 2 shows a single server computer 11 connected to four client computers, 31 , 33 , 35 and 37 , using a LAN, each of which runs the operating systems and browser applications mentioned above, and which communicate with the server computer 10 using TCP/IP and HTTP protocols.
[0024] FIG. 3 shows a server computer 12 connected to two local client computers 40 and 42 using a LAN, and also connected to two remote client computers 44 and 46 through the internet 48 . Each runs the operating and browser systems and browser systems mentioned above, and proxy servers and firewalls may be used to protect the intranet from unauthorised access from the internet. Again, communication within the intranet is via TCP/IP and HTTP protocols.
[0025] As FIG. 3 is the most general arrangement, embodiments of the invention will be described with respect to such a network.
[0026] One or more of the computer systems 12 , 40 , 42 , 44 and 46 runs a word processing application such as Microsoft Word™, which is used to create document templates and may be used to view fully or partially customised documents generated by a document generation system. The document template comprises one or more content elements for possible use when generating a customised document and one or more associated rules for determining, on the basis of further information provided by a user, how to use the content elements (which may be conditional clauses or statements) when generating a customised document.
[0027] Server computer 12 also runs a document generation program, which, when provided with a template, generates one or more input forms to capture information from a user, the input forms being generated on the basis of rules contained in the template. The document generation program then generates a fully or partially customised documents on the instructions of a user. The document generation program may be run as a server program and is instructed to perform tasks by users of client browser applications.
[0028] To generate either a fully or partially customised document from a template, a user instructs the document generation program by sending URL GET or POST request from a client computer, 40 , 42 , 44 or 46 , to the server 12 . The document generation program then initiates a session with the client computer. The document generation program may generate one or more Web input forms based on the chosen template, which are passed via a Web server application to the client computer. This Web input form uses standard HTML (hyperlink mark-up language) features such as buttons, free-form entry boxes, tick boxes, pull-down menu list boxes, radio buttons and other graphical user interface (GUI) means for inputting information. The document generation program may generate multiple input forms for distributing to and capturing further information from the users of one or more further client computers 40 , 42 , 44 46 . The document generation program may also produce multiple forms for capturing information from the user of a single client computer in several stages. However, in the following embodiments, it is assumed that only one user of a client computer is involved.
[0029] FIG. 4 is a flow diagram showing the process followed by the document generation program. At step 50 , the document generation program waits for an instruction from the user to generate a new customised document from a template. On receiving such an instruction, the document generation program generates, at step 51 , a first input form on the basis of the rules contained in the template. The user then enters information, using the input form, which is received by the document generation program at step 52 . Then, at step 53 , the document generation program determines whether the received information is sufficient to evaluate all the rules. If yes, the process continues to step 56 where the document generation program generates a customised document. If no, then the process continues to step 55 , where the document generation program determines whether or not it should proceed to generate a partially customised document. If it should, then the process continues to step 56 where such a document is generated. If there is no request from the user to produce a partially customised document (for example, a tick box on the Web input form has been left blank), then the process returns to step 51 , and generates further Web input forms for capturing further information from the user. This process is completed until sufficient information is captured to produce either a fully customised document, or a satisfactory partially customised document.
[0030] The partially customised document contains not only the content elements, the inclusion of which has been determined by the various rules within the template, but also the rules which have not been evaluated. Therefore, the partially customised document contains the same information content as the template, and also illustrates the effect of the remaining conditional statements on the final, fully customised document. The partially customised document will form the template of the fully customised document, when the document generation program next generates a form to capture the remaining information. The association between the content elements and rules which have not been evaluated in the partially customised document may be represented by means of a mark-up.
[0031] Embodiments of the present invention provide a mark-up scheme that is not only able to indicate incomplete conditional statements (by including content elements and their associated rules) but can also indicate missing or indefinite transaction values. FIG. 4 is a schematic diagram of the relationship between the template, the transaction values and the customised document. FIG. 5 is a schematic illustration of how the mark up rules relate to the transaction values and a marked-up, partially customised document.
[0032] The mark-up rules primarily govern what information is inserted when a transaction value is missing, what information is inserted when a transaction value is indefinite, and how conditional text is represented when its associated usage statement cannot be determined in any definite manner, either through missing or indefinite transaction values. A simple example of a series of rules which enable the document generation program to cope with missing or indefinite transaction values in this manner, is described below.
[0033] When a transaction value is missing, its name is inserted in coloured italics (for example, blue), embraced by curly { } brackets:
“The company name is “{Company Name}”.”
[0035] When a transaction value is indefinite, the alternatives are delimited using the pipe | character:
“ABC Holdings is a |registered company |partnership |PLC|.”
[0037] When conditional text, which is dependent on transaction values, cannot be resolved, this is indicated in the partially customised document as superscript coloured text (for example, red) inserted between square [ ] brackets of the same colour:
“ABC Holdings [ Type IS “registered company” (company number ABC/213) whose registered office is at] [ Type IS NOT “registered company” of] Floor 14, ABC House, London E5.”
[0039] Similar mark-up rules may be defined for all the other content elements that may appear in a template, such as calculations involving transaction values, the inclusion or attachment of other documents or data files, drafting notes to aid the user or clause labels and cross-references.
[0040] The scheme of mark-up rules given above is merely an illustration of a possible format for such a scheme. It is possible for the user to design their own set of mark-up rules, based on personal preference, or to select a set of pre-defined mark-up rules from a series of options given in the document generation program. This will result in any documents being generated by the document generation program, containing transaction values, having the chosen mark-up. The mark-up relating to the content elements and associated rules can also be chosen by the user, to suit personal preferences, and is therefore more flexible than in existing systems.
[0041] The use of such a mark-up enables the production of several types of documents, which would fall under the general heading of partially customised documents, which are not available with existing prior-art systems. For example, the document generation program may generate a fully customised document, in which all of the transaction values are known. This may also be referred to as a transaction document.
[0042] It is possible to generate different types of partially customised documents. For example, work-in-progress transaction documents, in which most, but not all of the transaction values are known, and which contains marked-up placeholders for missing or indefinite transaction values may be produced. Alternatively, sub-template documents may be produced. In these, some of the transaction values are known to have specific values, and therefore the sub-template only contains the portions of the original template which are relevant to these known values.
[0043] It is also possible to produce a fully re-generated template, for which no transaction values have been supplied, but marked up to show where values are missing and their effect on the customised document that the document generation program will eventually generate from the template. This re-generated template will have the same information content as the original template.
[0044] Various modifications to the invention, which are within the scope of the appended claims, will be clear to those skilled in the art. | The invention provides a document generation system for generating a customised document using content elements selected by rules operating on input information, the operating information comprising transaction values. The system comprises at least one computer having a document generation program stored thereon, means to associate further rules with the transaction values, and means to evaluate said further rules to produce an indication of whether transaction values are definite, indefinite or absent in a partially customised generated document. The effect of the transaction values is represented by means of a mark-up. | 6 |
BACKGROUND
[0001] 1. Field
[0002] The present invention relates to steel frame building and more particularly to such building that are designed to facilitate the precise location of the column which results in rapid, low cost building assembly without the need for cutting, rerilling or welding of any of the structural members.
[0003] 2. Prior Art
[0004] There are a number of prior art steel buildings containing features designed to facilitate the assembly of these buildings as evidence by the patents reference below.
[0005] U.S. Pat. No. 4,342,177 illustrates a steel frame building in which the roof beams are connected to the columns by means of a plate using bolts. However, this attachment does not allow for height adjusttment. The columns are C-shaped and cannot be easily slipped over a foundation assembly.
[0006] U.S. Pat. No. 5,577,353 illustrates a steel frame building in which the components of the trusses are held together with pre-drilled truss plates and bolts and the trusses are attached to the columns by means of pre-drilled plates and bolts. However, there is no provision for height adjustment at the column attachment. There is no provision to allow the trusses to be conveniently broken in two for transport and there is no provision to allow the columns to slip over the foundation members.
[0007] U.S. Pat. No. 5,979,119 illustrates an assembly of structural building components designed to be attached to a column. The attachment method permits the adjustment of the angle at which beams are connected however, height adjustment is achieved by clamping rather than positive bolting.
[0008] In prior art structures, the mounting system for columns was typically bolts placed in the concrete footer before the concrete had set. This is shown in FIG. 12, where a column 31 A is connected to a flange 32 A. The flange is secured to a footer 35 by means of bolts 34 . The position of the bolts is usually determined by a steel tape measure, which usually results in location errors in the order of ¼ to ½ inch. These errors require the framing members to be cut and fitted on the site, a slow and costly process. The reason for these errors are many and include the use of a tape measure, the use of aggregate in the concrete which makes it difficult to precisely set a bolt in place and the fact that the bolt is let stand while the concrete sets up. During the set up process, the bolt can be moved by a variety of forces including the bolt's own weight, pent up pressure points created by forcing the bolt into the concrete, wind, rain and inadvertent contact by workmen.
[0009] In the prior art assembly procedure, once the concrete has set up and the bolts have been secured in the concrete, the next task is the lifting of the column over and on to these bolts. The column typically has a lower flange with holes used to accommodate the bolts and connect the column to the footing. The column with its flange is lowered down on to the bolts and nuts are used to secure the bolts to the flange. However, at this time, with the column suspended in the air, it is difficult to correct for the horizontal plane location errors of the bolts, while at the same time connect the column to the bolts and erect the column in a perfectly vertical position. This prior art assembly procedure does not lend itself to precisely locating the column and results in building members not fitting together and requiring time consuming and costly redrilling and cutting on the job site to complete the assembly of the building.
[0010] All of the above mentioned disadvantages of the prior art are addressed and overcome in the present invention which is described below.
BRIEF DESCREPTION OF THE FIGURES
[0011] [0011]FIG. 1 is an exploded view showing a column used in the assembly of a steel building. This Figure also shows the gutter, truss and foundation assemblies used in conjunction with the column.
[0012] [0012]FIG. 2 shows all the components of FIG. 1 in their assembled positions.
[0013] [0013]FIG. 3 is a cross section of a steel building using the columns shown in FIGS. 1 and 2 to support a roof truss.
[0014] [0014]FIG. 4 is a detailed drawing of the connection of a truss to the column of FIG. 2.
[0015] [0015]FIG. 5 is a detailed drawing illustrating the method of connection of the upper members of the two halves of a truss that is used in the construction of a building in accordance with the present invention.
[0016] [0016]FIG. 6 is a detailed drawing illustrating the method of connection of the two halves of a truss along its lower chord.
[0017] [0017]FIG. 7 is a first drawing of a portion of a special truss which includes an extended end used to provide a building overhang.
[0018] [0018]FIG. 8 is a second drawing of a portion of a second special truss with an extended end used to provide a building overhang.
[0019] [0019]FIG. 9 is a side view of the post portion of a stockade fence fabricated in accordance with the present invention.
[0020] [0020]FIG. 10 is a rear view of the fence of FIG. 9.
[0021] [0021]FIG. 11 is a side view of a plastic fence post, such as a PVC or vinyl post covering a steel post.
[0022] [0022]FIG. 12 is a cross sectioned view of a prior art concrete footer and mounting assembly for a steel column.
[0023] [0023]FIG. 12A is a cross sectional view of a concrete footer and mounting assembly for a steel column in accordance with the present invention. A chair, fabricated from reinforcing bars, which is shown in this Figure, is used to aid in supporting and accurately positioning a collar used to hold a steel column.
[0024] [0024]FIG. 12B shows a side view of a U-bolt used to connect a leveling plate to a chair.
[0025] [0025]FIG. 13 is a perspective of a chair showing the typical location of reinforcement bars used to construct the chair and the position of a leveling plate and collar on the chair.
[0026] [0026]FIG. 14A is a cross sectional view of a top and bottom adjustment plate which are used to facilitate precisely locating the collar.
[0027] [0027]FIG. 14B is a plan view of the bottom adjustment plate of FIG. 4A.
[0028] [0028]FIG. 15 is a cross sectional view of a chair-type anchor system for mobile homes.
SUMMARY
[0029] It is an object of the present invention to use precisely located foundation assemblies to quickly, easily and accurately locate the building columns in both the horizontal and vertical planes.
[0030] It is an object of the present invention to provide a means of simply and easily adjusting the height of the trusses on the job site.
[0031] It is an object of the present invention to provide a means of simply and easily adjust the height of the gutters on the job site.
[0032] It is an object of the present invention to provide roof trusses which can be easily divided in half to facilitate transportation.
[0033] It is an object of the present invention to provide trusses which can be quickly and easily attached to columns and which also provide a roof overhang.
[0034] It is an object of the present invention to provide a mounting system for the columns in a steel building that provides excellent strength against uplift loads.
[0035] It is an object of the present invention to provide a mounting system for the columns in steel buildings which reduces the time by as much as 90 percent and reduces the cost of construction by an average of thirty percent.
[0036] The present invention provides a framing assembly system for steel building that substantially reduces the assembly time while maintaining excellent strength and mechanical integrity. In fabricating this type of building, foundation assemblies are first precisely located in both the horizontal and vertical planes when placed in concrete footings. The foundation assemblies include their own low vertical columns. Once the concrete has set, the main building columns are put in place over the low columns and bolted into place using pre-drilled and aligned holes that pass through the main building columns and the low foundation assembly columns, thereby eliminating the difficult task of holding the columns erect while trying to precisely locate the main columns in both the horizontal and vertical planes. Trusses are also connected to the top of the main columns by means of bolts passes through pre driled holes. A series of holes centered in a straight vertical line at regular intervals enables the assemblers to adjust the height of the trusses by selecting an appropriate set of holes through which to pass the bolts, thereby permitting the assembler to provide a desired roof pitch.
[0037] The gutters are supported by a short support arms which are placed into the hollow top of a structural adjustment sleeve that rest on the main columns. The gutter's height may be adjusted by means of bolts passed through any one of a plurality of pre-drilled holes that pass through the structural adjustment sleeve and the gutter support arm.
[0038] The trusses are divided in two at their middle to facilitate transportation. The truss halves are reconnected at the building site by bolting their lower chords together with the aid of a long square steel insert placed into the lower chords at the mid-section of the full truss. The top of the truss halves are connected together by means of bolting them to a steel tie plate.
[0039] To provide a secure anchoring of the main columns to the concrete footer, a chair, formed of reinforcing bars, is accurately and securely positioned in the building footer. A leveling plate connected to a collar is attached to the top of the chair by way of “U” bolts at a precise location. The “U” bolts permit the collar to be easily moved to a precise location. The chair and plate are adjusted in height and in the horizontal plane with a laser measuring system. The collar is locked in place prior to the concrete's being poured about the chair by tightening the “U” bolts. Once the concrete has set up, the collar is held pernanently in its precise location, greatly facilitates rapid assembly and reduced assembly cost of the building.
[0040] To improve the strength of the collars against uplift loads, the chair of each column is attached by reinforcement bars to the chair of the next column, making it impossible to pull a single collar upward and out of the footer, without pulling the entire footer upward. The result of this construction technique is a vastly improved uplift load capacity for the structure.
DETAILED DESCRIPTION OF THE INVENTION
[0041] [0041]FIG. 1 is an exploded view showing a main column 5 used in the assembly of a steel building along with a gutter 2 , a truss assembly 4 and a foundation assembly 6 . Only a portion of the truss is shown in this Figure. This portion is made up of a left truss connection plate 4 C, a lower chord 4 A, a top member of the truss 4 B, and an attachment plate 4 C. At the top of this drawing is an adjustable rain gutter 2 with a support arm 2 A, which contains a series of evenly spaced holes 2 B. Directly beneath the support arm 2 A, is a structural adjustment sleeve 3 which includes a line of vertically positioned evenly spaced holes 3 A.
[0042] Directly beneath the structural adjustment sleeve 3 is the column 5 , which contains holes at its top 5 A and holes at its bottom 5 B. Directly beneath the column 5 is the foundation assembly 6 , which includes a low column 6 D, a series of vertical holes 6 A in the low column 6 D, a horizontal plate 6 B which is attached approximately midway up from the bottom of the low column and stabilizing tubes 6 C which extend horizontally and are attached to the bottom of the low column.
[0043] The column assembly is shown completely assembled in FIG. 2. In this Figure, the support arm 2 A for the gutter 2 is placed into the top of the structural adjustment sleeve 3 . The bottom end of the structural adjustment sleeve is placed over the column 5 . The truss connection plate 4 C is U-shaped and wraps around to enclose a portion of the structural adjustment sleeve. The column 5 is hollow and is placed over the low column of the foundation assembly 6 .
[0044] A major advantage of the assembly shown in FIGS. 1 and 2 is that all the components are bolted together. There is no need to weld any component, facilitating assembly on the job site. In addition, where height adjustment is required, it is provided by series of vertical holes. For example, the truss assembly can be moved up or down along the structural adjustment sleeve to a desired height and then locked at that height by placing a bolt through the truss connection plate 4 C into one of the holes in the structural adjustment sleeve 3 that is at a desired level. A similar assembly and adjustment is carried out for the gutter. The gutter arm which supports the gutter contains a series of vertical holes 2 B, which can be aligned with the holes 3 A in the structural adjustment sleeve. The gutter is moved up or down to a desired location and a bolt is placed through the structural adjustment sleeve holes and the holes in the support arm for the gutter to lock the gutter in a desired location.
[0045] The foundation assembly 6 is set in concrete before any assembly begins. The plate 6 B, which extends out horizontally from the low column portion of the foundation assembly lies on the top of the concrete and sets the depth to which the foundation assembly is placed in the concrete. It is accurately positioned in the vertical plane to set the elevation of the main column which will rest on this plate. Of equal importance is the fact that this plate is set to lie in the horizontal plane which insures that the orthogonally positioned low column is perfectly vertical and will support the main column in a perfectly vertical position. The foundation assembly is precisely located with respect to the various other main columns so that when a main column is placed over a low column of the foundation assembly, it is accurately located, enabling the components of the building to be assembled without cutting or drilling on site.
[0046] The precise location of the foundation assemblies is typically carried out with a laser interferometer which is vastly more accurate than the usual steel tape measure method used at most prior art construction sites. In addition, a laser leveling device is used to insure that the top surface of all the foundation plates are at precisely the same elevation, often within an error allowance as small as +/−0.001 inch. The present invention insures that the columns are precisely located in the both the horizontal and vertical planes, which means that they are at the correct elevation and are plumb and square.
[0047] The stabilizing tubes, which are connected to the bottom of the foundation assemblies, are horizontally positioned rods. They anchor the foundation assemblies to the concrete footing and aid in preventing the foundation assemblies from being pulled from the concrete by uplift loads. A second anchoring system, which employs a “chair” to provide even greater uplift load capacity, is describes later in this section.
[0048] The short column 6 D of the foundation assembly is typically rectangular in cross section as is the main column. Where the main column is hollow, the low column is typically made to be slightly smaller in cross sectional than the main column so that the low column fits inside the base of the main column. Where the main column is solid, a collar is substituted for the low column. The collar grips the main column from the outside, making it possible to use solid or closed ended columns for this type of construction.
[0049] In the assembly of the trusses and hollow columns, each column is placed over the foundation assembly and locked into place by placing bolts through holes 5 B in the main column and 6 A in the low column portion of the foundation assembly. This method of positioning the foundation assembly and the method of connection between the column and the foundation assembly provide a substantial advantage in assembly over the prior art. This method is simple and fast, while at the same time insuring the accurate location and positioning of the columns in both the horizontal and vertical planes. This is not the case in prior art systems. In prior art systems, the mounting system for the columns is simply bolts which are placed in the concrete. The location of the bolts is usually not precise and the concrete footing is not perfectly level, making it necessary to cut or redrill the flange at the base of the column used to connect to the column to the bolts. It is also necessary to place shims under the column in an attempt to position it vertically and at the correct elevation. These operations are difficult because they are often carried out while the column is suspended from a crane. If the column is simply bolted in, any errors in location of the column usually result in the need for cutting and fitting other building members which do not fit properly because of the column position error.
[0050] [0050]FIG. 3 shows a cross section of a steel building using the columns and trusses of the present invention. The roof truss is supported on two column, with one column being located on each end of the truss. Each column is supported by its own foundation assembly. There is a dashed line 9 which divides the trusses in the middle. This is the line on which the trusses are separated for transportation. The ability to separate the truss into two halves substantially reduces the overall length which must be transported.
[0051] [0051]FIG. 4 is a detailed drawing of the connection of the truss to the column. The structural adjustment sleeve is cut away at the top to reveal the position of the gutter support arm 2 A within the column. The truss connection plate 4 C is shown to partially wrap around the structural adjustment sleeve. Bolt and nut assemblies 3 B and 3 C pass through the truss connection plate and the structural adjustment sleeve to secure the truss to the column assembly. Purlins 8 are attached to the roof truss on its upper member 4 B and also to the side of the column. The purlins are used to tie one set of columns and trusses to the next They run lengthwise along the building and are attached on the top of the roof and along the sides to tie the building elements together.
[0052] [0052]FIG. 5 is a detailed drawing illustrated the method of connection of the two halves of the truss. This connection in this Figure is made at the top, center of the truss, where each half is joined. The main connection element is the steel tie plate 14 , which lies on the under side of the upper member of both halves of the truss, 4 B on the left and 4 E on the right. This plate is bolted to the upper member of the truss as shown by galvanized hexagonal bolts, such as by bolt 15 , which passes through the plate and through the member 4 B. At the peak of the truss, a square galvanized steel purlin 13 is attached by abolt 15 A which goes through the trusses and into the connection plate. Above this purlin is mounted an extruded aluminum ridge cap 12 , which covers the purlin, but allows air into and out of the building without accepting rain water into the building. The air enters through a side vent 12 A in this extrusion.
[0053] [0053]FIG. 6 is a detailed drawing illustrating the method of connection of the two halves of the truss along their lower chord. The lower chord of the trusses is U-shaped with the open portion of the U facing upward. The left hand lower chord is designated 4 A, while the lower right hand chord is designated 4 F. These chords are divided at line 19 on this drawing. Into the opened portion of the lower cord of the truss is inserted a square steel insert section 16 . This insert section typically extends over several feet, often having a length of three feet or more. It is bolted to the truss in several places by bolt and nut sets, such as a set 17 . It can be seen from FIGS. 5 and 6 that the two halves of the truss are easily connected by merely bolting them to the tie plate 14 and the insert 16 .
[0054] The truss shown in FIG. 3 has no overhang, making it primarily useful for industrial or farm buildings. However, the truss used in the construction of steel frame buildings described herein can be modified to include an overhang. Overhangs are included in the trusses shown in FIGS. 7 and 8. FIG. 7 is a first drawing of a portion of truss with an extended end used to provide a building overhang, while FIG. 8 is a second drawing of a portion of the truss showing a different extended end to provide a building overhang. In FIG. 7, upper member 4 B is extended to the left with a section of steel beam 20 . A return beam 21 is located below beam 20 to produce a step in the beam at location 22 which rest on the structural adjustment sleeve. Members 20 and 21 extend out to the left to provide an overhang. In this configuration the truss drops down at the step 21 below the top of the structural adjustment sleeve on the inside of the building.
[0055] In FIG. 8 the truss drops down below the structural adjustment sleeve on the outside of the building. This latter truss is extended by a top member 20 A and a bottom member 21 A. Either configuration can be used to advantage to produce the overhang typically found in home structures.
[0056] [0056]FIG. 12 is a cross sectional view of a prior art concrete footer 35 with a reinforcing bar 36 , and mounting assembly for a steel column 32 B. Note that in this prior art system, the mounting assembly is not connected to the reinforcing bar. The mounting assembly consists of a flange 32 A connected to the bottom of the column and straight bolts such as bolt 33 B, which pass through the flange and are secured to the flange with nuts, such as nut 34 B. The bottom of the bolts are placed in the concrete footer before it sets. Nothing holds these bolts other than the concrete. An uplift load on one column sufficient to lift out these bolts will detach the column from the footer. In the present invention the columns are secured to the steel in the footer providing a much improved uplift load.
[0057] [0057]FIG. 12A is a cross sectional view of a concrete footer 5 and a mounting assembly for a steel column, which consists of a collar 31 , a pin 43 passing through the collar, a plurality of U-bolts, such as U-bolt 37 , nuts on the U-bolts, such as nut 34 , a mounting plate 32 and beneath the plate a framework of reinforcing bars 38 , referred to as a chair.
[0058] A typical framework for a chair is shown in FIG. 13. It consists of a series of bars, such as bars 38 A, through 38 D; all of which are inverted U-shaped bars with their lower ends being pressed in to the earth 39 below the footers bottom level 39 A. These bars are placed into the footer cavity before the footer is poured. The chair also includes straight rods 38 E through 38 H which run orthogonally across the top of the U-shaped bars 38 A through 38 D. These straight bars are attached to the U-shaped bars by wires which are twisted about the bars where they contact one another.
[0059] The bottom of the U-bars in the chair are pounded into the earth 39 in the area where the footer is to be poured. A mounting plate 32 with a collar 31 attached is secured to the straight bars by a series of U-bolts, such as bolt 37 shown in FIGS. 2A and 2B. This plate allow movement of the collar along the bars to a selected position where the U-bolts can be tightened to hold the collar in place. The pounding of the chair into the ground secures its position and prevents the unintended movement of the collar. The level of the collar is set by pounding the chair up or down. The course position of the collar in the horizontal plane is adjusted by loosening the wires holding the straight bars to the U-shaped bars and by moving the position of the straight bars. The collar is moved for fine positioning by leaving the “U” bolts loose. The collar is easily moved at this stage because it does not have the weight of the column on it.
[0060] As noted above, a laser interferometer is typically used to set the location of the collar to an accuracy of one thousandth of an inch, rather than one fourth or one half of an inch. The footer is then poured, locking the collar at a precise location. The column is then dropped into the collar and the column's position is accurately determined by the collar.
[0061] Each collar is attached to a chair and each chair is attached to the next adjacent chair so that each collar is attached to the steel reinforcement running through out the length of the footer, unlike prior art systems where the column mounting bolts were not attached to the reinforcing rods. The result of the use of the chairs and their interconnection is a greatly improved uplift load strength.
[0062] The techniques described above for mounting columns are not limited to building construction, but can be applied to fence construction as illustrated in FIGS. 9 and 10. FIG. 9 is a side view of a portion of stockade fence, fabricated in accordance with the present invention. FIG. 10 is a rear view of the same fence as shown in FIG. 9.
[0063] [0063]FIG. 9 shows a steel fence post 23 A. Attached to the right side of the fence post in FIG. 9 are three “C” channels 25 A, 25 B, and 25 C, all of which have their open face directed away from the post so that they can accept wooden cross member of a stockade fence. The “C” channels typically have inside dimensions of 1 inch in width by 3 inches in height. The separation between the channels is typically 25½ inches with the bottom channel usually being 8½ inches above ground level.
[0064] The post 23 A is supported by a low column base 26 A which is installed in the ground before the fence is erected. The column is usually secured in concrete. Then, the hollow steel post is placed down over the short column. A pin may be placed through the low column and post to lock the post to the column.
[0065] It can be seen in the rear view of FIG. 10 that two fence posts 23 A and 23 B are separated from each other. Typically this separation is 5 feet on centers. The channels 25 A, B, and C extend across the post horizontally with one end of each channel being attached to one post, while opposite end is attached to the remaining post. The channels have pre-drilled holes, such as hole 27 , which are typically placed 16 inches apart on centers. These holes are designed to accept screws which hold the fence cross members to the “C” channels.
[0066] The lower portion of the posts are shown as being broken away in FIG. 10 to illustrated the location of the low column 26 A and 26 B which are installed within the fence posts 23 A and 23 B. In erecting the fence, the low columns are set in the ground and are usually held in place with concrete. Their short height makes working with the columns much easier than trying to set 6 foot post in concrete, while at the same time holding the posts erect. It is obviously much easier to set the low columns a precise distance apart and maintain that distance as well as maintain them in a vertical position while the concrete sets. Once the columns have been set, the post are merely placed over the columns, and pinned in place. The “C” channels are attached and a section of stockade fence is attached by screwing the cross members to the “C” channels.
[0067] Replacement is also made easier by this system. The posts are not set in concrete and can be removed merely by removing the pins. New posts are installed by simply slipping them over the columns. A section of stockade fence is replaced by unscrewing the old section from the “C” channels and replacing it with a new one. The placement of the columns in concrete, the pinning of the posts to the columns and the reinforcing of stockade fence with steel “C” channels greatly strengthens the fence, enabling it to withstand horizontal wind loads as well as up lift forces.
[0068] [0068]FIG. 11 shows a steel post 23 A supporting a plastic post 28 . The steel post is supported by a short column base 26 A as described above. Over the steel is placed a plastic post such as a PVC or Vinyl post which is covered at its upper end with a cap 24 A.
[0069] The steel post supports the plastic post and since it used the low column support 26 A, it has all the advantages of the above described system. Plastic fence systems are currently available that are designed to have cross members attached to plastic posts to produce a fence. By placing the steel post inside the plastic post, all the advantages of the present invention are easily added to readily available plastic fence systems.
[0070] The strength of the chair and the linked steel along the footing give the chair and the short column or collar attached to the chair great strength against hurricane uplift loads. This strength can be used to secure mobile homes and trailers against hurricane force winds. The use of the chair for anchoring mobile homes is shown in FIG. 15. In this Figure, the collar 31 is connected at its lower ends to the mounting plate which is connected to chair 38 . Its upper end contains a series of holes, such as hole 47 which permit a bolt 48 to be passed through the collar. Located above and fitting within the collar is a collar adapter. This adapter includes an anchor plate 49 at its top and holes through its side to permit the bolt 48 to pass through the adapter and the collar and lock these two elements together. The adapter can be adjusted in height above the ground by selecting a particular one of the set of holes in the collar to pass the bolt. This allows the adapter to be brought to the height necessary to connect the adapter plate to the I-beam 43 on which a mobile home is constructed. There are typically two such I-beams; however, only one is shown in the drawing. An identical anchoring system is used for the second I-beam. The connection to the I-beams is made using I-beam adapter clamps such as clamp 44 which rest on both the anchor plate 49 and the I-beam as shown in FIG. 15. The I-beam adapter clamps are held in place and tightened to hold the I-beams to the anchor plate by means of a bolt and nut set such as set 45 .
[0071] Upon the disclosure of the above mounting and frame construction system to those skilled in the art, many variations will become apparent, all of which are considered as being within the spirit and scope of the present invention. For example, rather than a low column or a collar which grips the outside of the column, a bracket can be substituted which attaches to the side of the column. Rather than loosening wires in a chair or U bolts to adjust the position of a collar or low column, two plates such as plates 41 and 42 with holes 41 A and 41 B and slots 42 A and 42 B respectively, as shown in FIGS. 14A and 14B, can be used with bolts passing through the holes and slots to connect the plates to the collar and chair and to permit the collar to be moved into position using the slots for movement. The collar is clamped into place by tightening the bolts.
[0072] Although the overall assembly system disclosed herein may at first appear as merely another building technique, it has not been previously employed in the industry, despite its very considerable advantages. As an example of time saving provided by this system, a 1440 square foot building can literally be assembled in hours after the footer has been set, as opposed to conventional construction which takes typically one to two weeks. The construction cost is reduced drastically as well. The construction cost for a conventional building of this type is typically $50 to $60 per square foot, while the cost of a building using the present invention is $35 to $40.
[0073] There is typically an overall 30% reduction in cost. The practical result of these very significant savings is illustrated by HUD's consideration of a design embodying the present invention for use for Habitat for Humanity as well as consideration by M.I.S.S. (Mothers and Infants Striving for Success) in Martin County, Fla. for shelters. Other applications include classrooms and other structures for F.E.M.A. as well as greenhouses for the Virginia State University. | A framing assembly system for steel building that substantially reduces assembly time while maintaining excellent strength and mechanical integrity. In fabricating this type of building, foundation assemblies are first placed in concrete footings at a precise location in both the horizontal and vertical planes. Once the concrete has cured, columns are placed over the foundation assembly and bolted into place using pre-drilled holes in the columns and foundation assembly, thereby eliminating the difficult task of holding the columns erect while at the same time trying to precisely position the column in the horizontal and vertical planes. Trusses are connected to the top of the columns by means of bolts passes through pre-drilled holes. A series of holes centered in a straight vertical line at regular intervals enables the assemblers to adjust the height of the trusses by selecting an appropriate pair of holes through which to pass the bolts, thereby permitting assemblers to easily and quickly produce a desired roof pitch using only simple hand tools. | 4 |
BACKGROUND OF THE INVENTION
[0001] Portable insulated cooler chests for storing and transporting small quantities of food and beverages are well-known to the art as are cooler chests having a liquid dispensing apparatus integrated therewith. Representative of the current state of the portable cooler prior art are U.S. Pat. No. 5,222,631 (Hood) and U.S. Pat. No. 4,162,029 (Gottsegen et al.).
[0002] The present invention relates to improvements in the dispensing apparatus of portable coolers to permit the inexpensive and efficient dispensing of ice-cooled liqueurs in the manner of comparatively expensive bar-top, electric powered, refrigerated dispensers sold under the TAP MACHINE® trademark and well-described, for example, in issued U.S. Pat. Nos. 5,427,276, 5,456,387 and 5,494,195.
SUMMARY OF THE INVENTION
[0003] The apparatus of the new invention provides a lightweight, portable cooler chest having a storage arrangement for securely stowing and cooling, with ice rather than electric refrigeration, a plurality of bottles of beverages, typically alcoholic liqueurs whose taste is enhanced when served at very low temperatures. Importantly, a closed fluid reservoir or well having a pair of integral bottle mounting sockets formed in its top wall plate is supported in the chest adjacent to and above an external spigot mounted at the lower portion of the cooler chest. A delivery tube connects the reservoir or well to the spigot to permit gravity flow of the chilled fluid to the spigot.
[0004] Special new mounting valves are provided for attachment to liqueur bottles whose refrigerated fluid contents are to be dispensed. Importantly, the valves are adapted to be locked into the well sockets to hold integrally inverted bottles securely in place in the well wall, and, when inverted and engaged with activation pins formed on the bottom of the well, to permit fluid to escape from the inverted bottles to the well for subsequent selective dispensing through the spigot.
[0005] For a more complete understanding of the present invention, reference should be made to the following detailed description of the new cooler chest taken in conjunction with the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is an exploded perspective view of the fundamental cooler chest of the present invention;
[0007] FIG. 2 is an exploded perspective view of the inverted bottles, new mounting valves, and fluid well of the present invention;
[0008] FIG. 3 is a perspective view of the closed cooler chest with external spigot;
[0009] FIG. 4 is a bottom plan view of the well;
[0010] FIG. 5 is a top plan view of the well;
[0011] FIG. 6 is a cross-sectional end view of the well taken along line 6 - 6 of FIG. 3 ;
[0012] FIG. 7 is a cross-sectional view of the cooler taken along line 7 - 7 of FIG. 3 ;
[0013] FIG. 8 is a cross-sectional view of the cooler taken along line 8 - 8 of FIG. 3 ;
[0014] FIG. 9 is a cross-sectional view of the cooler taken along line 9 - 9 of FIG. 3 ;
[0015] FIG. 10 is a bottom perspective view of the well;
[0016] FIG. 11 is a longitudinal cross-section of the well taken along line 11 - 11 of FIG. 10 ;
[0017] FIG. 12 is a perspective view of the well cover with integral twin bottle support sockets;
[0018] FIG. 13 is a perspective view of the well cover with twin bottle support sockets and hinged twin integral caps for the sockets, and;
[0019] FIG. 14 is an exploded perspective view of the new bottle mounting valve.
DETAILED DESCRIPTION OF THE INVENTION
[0020] Referring to FIG. 1 , the cooler chest 10 of the invention comprises a molded outer polycarbonate shell 11 having vertical end walls 12 , 13 ; vertical front and rear walls 14 , 15 , and a bottom wall 16 . An inner shell 17 having vertical end walls 22 , 23 ; side walls 24 , 25 ; and a bottom wall 26 is nested in the outer shell to define an insulating dead air space between the shells 11 , 17 . Advantageously, the inner shell has a circumscribing groove 18 formed at its upper edges which groove tightly engages a corresponding rim 19 in an air-tight fit.
[0021] A molded cover 40 formed of polycarbonate and having integral cylindrical holders 41 for supporting beverage cups or the like is hingedly connected to the outer shell 11 by hinges 42 fastened to the edge of the cover and the upper edges of the rear wall 15 .
[0022] Conventional liquid drains 53 , having selectively openable stoppers 54 , are mounted in drain holes 25 formed at the bottom portions of the end walls 12 , 13 , 22 , 23 adjacent the bottom of the cooler chest to permit drainage of water from melted ice. Conventional, pivoting carrying handles 56 are secured to end walls 12 , 13 by mounting hardware 57 , 58 attached to the end walls by appropriate fasteners (not shown).
[0023] In accordance with the invention, the inner shell 17 is divided by a vertical wall partition 60 into a dispensing portion 67 and a bottle storage portion 61 which includes a molded bottle spacer 62 which rests on the bottom wall 26 of the inner shell. As shown in FIGS. 8 and 9 , multiple bottles are adapted to be stored in the storage portion 61 in openings 63 in spacer 62 which openings are generally congruent with the bases of the bottles to be stored. The spacing of the bottles B permits the loading of ice cubes or ice chips around and between the stored bottles.
[0024] In accordance with the invention, shelf ledges 65 , 66 are formed on inner shell side walls 24 , 25 in the dispensing portion 67 to engage and to support a unique fluid reservoir 70 assembly which comprises a full cooler width, top cover plate 71 having a pair of special bottle receiving sockets 72 with grooves 73 and splines 74 ; a sealing gasket 75 ; and a fluid well 76 . The reservoir 70 is assembled by fastening the cover plate 71 to the well 76 with the gasket 75 therebetween by screws (not shown) passing through plate holes 71 ′, gasket holes 75 ′, and well holes 76 ′ formed in circumscribing lip 96 .
[0025] A pair of special unitary locking-mounting valves 80 are provided, each having an upper portion in the form of a locking collar 81 with grooves 83 and splines 84 adapted to mate with grooves 73 and splines 74 ; and a lower valve body portion supporting a spring-biased stopper 85 normally seated in an orifice 86 in a horizontal internal wall of the valve body. The locking-mounting valves 80 are secured to the tops of chilled bottles B by threads 80 ( a ). The bottles are then inverted for support in sockets 72 . The lowermost edges of the valve 80 form crenellations 88 to permit air flow into the bottle.
[0026] As will be understood and in accordance with the invention, the beverage bottles B are fitted with the mounting-locking valves 80 which are threaded onto the threaded bottle tops after the regular threaded bottle cap closures are removed. The valves 80 are spring-loaded into a normally closed position and have a splined, grooved exterior surface to be described in greater detail hereafter.
[0027] Specifically, and as shown in FIG. 2 and FIG. 14 , the locking-mounting valve 80 has an upper valve body portion 81 and a lower valve body 82 . The upper valve body portion has a cylindrical collar 87 with internal threads 80 ( a ) which, as explained, are adapted to threadingly engage the bottle top threads T (not shown) which are exposed upon the opening of the bottles B by removing the caps C. Washer 88 seals the collection of bottles B to the threads 80 ( a ).
[0028] In accordance with the invention, a frusto-conical array of upper locking splines 84 separated by upper locking grooves 83 are formed integrally with the outer surfaces of the upper valve body 82 . The upper splines 84 taper in width from top-to-bottom while the upper grooves 83 therebetween correspondingly taper from bottom-to-top.
[0029] The upper valve body portion 81 has an exterior cylindrical surface 110 below the locking splines 84 and grooves 83 . Disposed within the upper valve body portion is a spring retainer having depending legs 111 .
[0030] The lower valve body portion 82 includes an inner surface portion 113 adapted to engage the upper valve body portion 110 in a tight fit in which the fitted portions are permanently bonded by heat welding to complete the assembly of the entire unitary locking-mounting valve. A valve orifice 86 ( a ) is formed in annular orifice plate 86 formed integrally with the lower valve body 82 .
[0031] Before heat fusing the upper and lower valve body portions 110 , 113 , the locking-mounting valve assembly 80 is completed by inserting a coil biasing spring 114 in the annular space between the legs 111 and the lower extremity of the upper valve body so that it will engage the valve stopper 85 , which has an annular stopper disc 115 of greater diameter than that of orifice 86 ( a ) and a downwardly projecting actuator tab 116 .
[0032] Sealing elastomeric washer 117 rests on the orifice 86 ( a ) and seats the stopper disc 115 . Sealing elastomeric washer 118 is included in the assembly.
[0033] In accordance with the invention, the well 76 is generally oval having arcuate end walls 77 and straight side walls 78 . The bottom wall 79 of the well 76 has a sloped outlet trough portion 90 leading to an exit nozzle 91 disposed on the underside of the well. The nozzle 91 receives a flexible delivery tube 92 over its ridged outer surface 93 . The tube 92 is connected at its other end to a spigot inlet 94 as shown in FIG. 7 . As will be understood, the well is adapted to be charged with fluid from the inverted securely mounted bottles. The fluid will be dispensed through the tube to the spigot 100 .
[0034] The reservoir 70 is affixed to the cooler chest by fastening the plate 71 by screws (not shown) through holes 71 ″ to ledges 65 , 66 . Integral caps 120 ( FIG. 13 ) may be attached by living hinges 121 to plate 71 to cover and close sockets 72 when not receiving bottles B. The plate 71 is stiffened by integral edge ribs 122 .
[0035] Projecting upwardly from the well of the bottom wall 79 are spaced integral cruciform actuating posts 95 which are each coaxial with the twin mounting sockets 72 in the top cover plate 71 . In accordance with the invention, when inverted bottles B are placed in the sockets 72 , the splines 83 and grooves 84 will lockingly engage the splines 73 and grooves 74 to hold the inverted bottles securely in place and in communication with the posts 95 in the well 76 . The height of the posts 95 is sufficient to engage and to displace the spring-biased stoppers 85 out of their normally orifice closing position in the valve body 80 . This movement will permit the flow of liquid from the bottles B into the well 76 . With the valve open, air will flow from the well through the orifice and up into the bottles B to fill the void left by the exiting of fluid from the bottle through the valve body and to permit controlled fluid flow. Importantly, the crenellations 88 on the valve body 80 permit air to flow back into the valve 80 until the fluid level in the well reaches the equilibrium level of the orifice 86 and fluid flow stops.
[0036] To fill the well 76 to an operative level of fluid, the bottles B with the valves 80 attached are inverted and inserted into the sockets 72 having mating splined/grooved surface. As has been explained, the bottles B will be firmly secured to the housing by virtue of the engagement of the valve body splines/grooves with the associated splines/grooves of the sockets 72 at the top plate 71 .
[0037] The fluid in the well may be selectively dispensed externally through the spigot 100 disposed in orifice 123 in front wall 14 and operable by selective depression of a resilient elastomeric actuator 101 , to permit liquid to pass downwardly by gravity flow out of the spigot opening 102 . Specifically, the spigot is a simple, normally closed valve, the stopper 101 having a convex head 103 and shaft 104 which normally bias the bulbous stopper 105 into sealing relation with the discharge orifice 102 . Depression of the head 103 displaces the stopper out of sealing relation to permit discharge of fluid. When the fluid level in the well recedes, additional flow from the bottles will restore it to its equilibrium level. Any simple normally closed spigot, faucet, or tap hardware may be employed in the practice of the invention, as should be understood.
[0038] Advantageously, the spigot 100 is disposed in recessed portion 105 formed in the outer shell wall 14 so that the spigot 100 does not project beyond the major dimensions of the cooler chest body. Similarly, the drainage holes 25 are disposed in recessed portions 106 formed in the end walls 12 , 13 of the outer shell.
[0039] It will be appreciated that the new and improved cooler chest provides an economical apparatus for transporting and dispensing popular alcoholic beverages of the type best served when well chilled. The new reservoir and mounting-locking valve mechanisms allow ordinary liqueur bottles to be securely mounted in an inverted position for selective dispensing of chilled beverages from a cooler chest without removing the bottles.
[0040] It should be understood, of course, that the specific form of the invention herein illustrated and described is intended to be representative only, as certain changes may be made therein without departing from the clear teachings of the disclosure. Accordingly, reference should be made to the following appended claims in determining the full scope of the invention. | A liquid dispensing cooler for beverages in the form of an insulated ice chest having an insulated base, insulated side walls, insulated end walls and an insulated cover; a spigot mounted in one of the chest walls above the base and having a controllable dispensing valve adjacent an exterior surface of the chest wall; at least one inverted bottle having a valve body mounted thereon, said valve body having locking grooves and splines formed thereon on upper portions and having an air venting means integrally formed by crenellations on lowermost portions thereon; a reservoir with a reservoir top wall having a circular opening with locking grooves and splines formed thereon adapted to engage and to support an inverted bottle through said grooves and splines on the valve body; and a delivery tube communicating between the reservoir and the spigot to permit gravity flow of liquid from the reservoir to the spigot. | 5 |
FIELD OF THE INVENTION
This invention relates to the field of robotics, specifically how robots can aid humans in transporting heavy loads over rough terrain.
BACKGROUND OF THE INVENTION
The task of transporting heavy objects over rough terrain has previously been solved by the use of wheeled and treaded vehicles. These vehicles include jeeps, motorcycles, tanks, and All-Terrain-Vehicles (ATV). The limitations of these devices are the types of terrain that they can operate on, and their maneuverability on that terrain. On roads or other relatively smooth terrain, these devices are successful. But when the terrain is very irregular, as in jungles, these devices become useless. Another limitation of these devices is due to their size. The size problem has been solved by a class of inventions called motorized wheelbarrows and carts (as in U.S. Pat. Nos. 5,465,801; 5,284,218; 5,211,254; and 4,811,988). These inventions all use wheels as the means to contact the ground and provide the locomotion. On smooth roads, wheel devices provide suitable means for locomotion. On very rough and irregular terrain wheeled devices consume a significant amount of power, provide poor ride quality, damage the terrain, and encounter problems with traction. Often, these wheeled devices cannot even traverse the rough terrain.
The solution to providing means for locomotion on rough and irregular terrain comes from legged robots and machines. Legged versus wheeled locomotion has the advantages of requiring less energy, attaining higher speeds, greater mobility, better isolation from terrain irregularities, and less environmental damage (Bekker 1960; Song and Waldron 1989). The problem with having legged machines navigate through rough terrain is the technology is such that it cannot support a fully autonomous legged machine. A few six-legged machines have been built that can walk on irregular terrain (Adaptive Suspension Vehicle built by Ohio State University, Song and Walkron 1989; MECANT I, Hartikainen et. al 1992) but they are large, bulky, and move slowly.
BRIEF DESCRIPTION OF THE DRAWINGS
The objects and advantages of the Human Assisted Walking Robot (HAWR) will become apparent from the following detailed description of preferred embodiments thereof in connection with the accompanying drawing in which like numerals designate like elements, and in which:
FIG. 1 is an isometric CAD drawing showing the entire HAWR as viewed from the front right side of the HAWR.
FIG. 2 is an isometric CAD drawing showing the HAWR as viewed from the top right side of the HAWR. The cargo bin has been removed for a better view of the underlying components.
FIG. 3 is a schematic for the controller circuit.
FIG. 4 is an isometric CAD drawing showing only the transmission and the double four-bar linkage for the right leg of the machine. The components associated with the left leg of the machine have been omitted for clarity.
FIG. 5 is an isometric CAD drawing showing the rigid frame of the machine.
FIG. 6 is an isometric CAD drawing showing the HAWR as viewed from below on the front left side of the HAWR. The left leg and its driving hardware and the cargo bin are not shown so that the right leg and its driving hardware can be viewed more easily.
FIG. 7 is an isometric CAD drawing showing the HAWR as viewed from the front right side of the HAWR. The left leg and its driving hardware are not shown so that the right leg and its driving hardware can be viewed more easily.
FIG. 8 is an isometric CAD drawing showing the shank leg assembly.
FIG. 9 is a plot of the path of the foot in the vertical plane.
SUMMARY OF THE INVENTION
The present invention solves the problems inherent in wheeled transport vehicles and legged robots by providing a human assisted walking robot formed by a motor, a cargo bin, a pair of legs mounted to the carrier; and a stabilizing support mounted at its proximal end to the carrier and having a wheel rotatably mounted to the distal end. The motor drives the first and second leg members resulting in a walking motion. Each leg is formed by a thigh link and a shank link. A four-bar linkage is coupled between the motor and the thigh and shank of each leg so that rotational motion generated by the motor produces a walking motion by the legs.
The present invention has other objects and advantages which are set forth in the Description of the Preferred Embodiment. The features and advantages described in the specification, however, are not all inclusive, and particularly, many additional features and advantages will be apparent to one of ordinary skill in the art in view of the drawings, specification and claims herein.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Depicted in FIG. 1 . is a Human Assisted Walking Robot (HAWR) designed to transport loads over rough terrain. The HAWR uses two legs, a right leg 1 and a left leg 2 , to support the load, carried in a cargo bin 3 , The human operator grasps the HAWR at a set of handles 4 in FIG. 2 to provide stabilizing forces and navigate the HAWR. By grasping the handles 4 , the operator can provide stabilizing forces needed to keep the machine balanced upright. A wheel 5 , or multiple wheels, can be used to help the operator stabilize the robot. In the preferred embodiment no wheel is used. The user controls a power unit 6 by means of an apparatus 7 which then controls the walking speed of the robot. Power unit 6 can be any type of motor, with the preferred type being an internal combustion engine.
In general there are two ways to control the speed of the HAWR:
In the first method, the direct control, apparatus 7 directly adjusts the flow of power from power unit 6 . For example if power unit 6 is an internal combustion engine, then apparatus 7 controls the engine throttle and therefore the torque output of the engine. Or if power unit 6 is an electric motor, then the apparatus 7 could be a device, such as a potentiometer or rheostat, that controls the output torque of the motor.
In the second method, indirect control, a feedback controller 8 in FIG. 3 is employed to regulate the walking speed of the HAWR similar to cruise control in automobiles. The input to controller 8 is directly assigned by the operator via a transducer 9 . Transducer 9 can be a speed setting switch, a force sensor, or any other transducer device that is able to get the operator's input. In the preferred embodiment, the transducer 9 is a multiple position switch, where each position corresponds to a different speed. A tachometer, encoder, or any other device which can determine the speed of the walking robot is employed as the speed sensor 10 . In the preferred design, the speed sensor 10 is a tachometer. Also in the preferred design, feedback controller 8 is a microprocessor, but it could be an electronic circuit instead. An electronic amplifier 36 is used to amplify the command from the computer 8 . This amplifier, in return, drives a small DC motor 37 . Motion of the DC motor 37 allows for adjustment of the engine throttle. The engine 6 then drives the HAWR mechanism through a centrifugal clutch 38 .
The following describes the mechanism of HAWR. The power to the walking mechanism of the robot is provided by the onboard power unit 6 in FIG. 2. A clutch is used to disengage the power unit 6 from the rest of the system. This clutch, in many cases is integrated with the power unit. Many two-stroke internal combustion engines are available with centrifugal clutches, which is the preferred design. Depending on the output speed of the power unit 6 , a transmission system may be necessary to modulate the rotational speed of the power unit. Because the typical speed of two-stroke internal combustion engines is around 8000 rpm, a transmission 11 is employed to reduce the engine speed. The preferred transmission is a gear type, but it could also be a hydrostatic having a continuous gear ratio with the possibility for forward and reverse settings. The transmission 11 has two output shafts, one to power the left leg 2 of the walking robot, and the other to power the right leg 1 of the walking robot. The power unit 6 and transmission 11 are mounted to rigid frame 12 in FIG. 5 . From this point on, the left and right sides of the walking robot are identical, and thus the left leg will be omitted in FIGS. 4, 6 , and 7 so that the components can be more easily viewed. The right side of the output shaft of the transmission 11 is used to drive the double four-bar linkages 13 which governs the movement of the right leg 1 . The connection between transmission 11 and double four-bar linkage 13 is through a chain and sprocket system 14 . A transmission sprocket 15 in FIG. 7 is rigidly connected to the right side of a transmission output shaft 35 . A drive chain 16 connects transmission sprocket 15 and a driver sprocket 17 . Driver sprocket 17 is rigidly connected to a thigh driver-link 18 and a shank driver-link 19 , such that thigh driver-link 18 and shank driver-link 19 rotate with the same speed of driver sprocket 17 . This indicates that when the transmission output shaft 35 rotates, both thigh driver-link 18 and shank driver-link 19 rotate also. The angular speed of the thigh driver-link 18 and the shank driver-link 19 depend on the relative size of transmission sprocket 15 and driver sprocket 17 . The thigh driver-link 18 and the shank driver-link 19 are considered the inputs to the double four-bar linkage 13 . The double four-bar linkage 13 consists of two four-bar linkages:
A thigh linkage 20 which consists of three moving links: the thigh driver-link 18 (input to the linkage 20 ), a thigh coupler-link 22 , and a thigh rocker-link 23 (output of the linkage 20 ). A full rotation of thigh diver-link 18 causes thigh rocker-link 23 to rock back and forth. In other words the thigh linkage 20 governs the trajectory of the rocking motion of thigh rocker-link 23 in response to continuous rotation of thigh driver-link 18 .
A shank linkage 21 which consists of three moving links: the shank driver-link 19 (input to the linkage 21 ), a shank coupler-link 24 , and a shank rocker-link 25 (output of the linkage 21 ). A full rotation of shank diver-link 19 causes shank rocker-link 25 to rock back and forth. In other words the thigh linkage 21 governs the trajectory of the rocking motion of shank rocker-link 25 in response to continuous rotation of shank driver-link 19 . The rocking motion of shank rocker-link 25 is transferred to a shank leg 26 as described below. Rigidly connected to shank rocker-link 25 is an upper sprocket 27 . Rigidly connected to shank leg 26 is a lower sprocket 28 . A leg chain 29 connects upper sprocket 27 and lower sprocket 28 . As shank rocker link 25 rocks, it rotates upper sprocket 27 , which rotates lower sprocket 28 , which rotates shank leg 26 .
The foot 30 is mounted to the end of shank leg 26 . Therefore the motion of foot 30 is governed by the double four-bar linkage 13 . The two four-bar linkages 20 and 21 (in double four-bar linkage 13 ) work in conjunction to form a suitable trajectory for the position of foot 30 in FIG. 9, in the vertical plane. The designers must arrive at the proper lengths of the double four-bar linkage links such that a proper trajectory is generated for foot 30 .
FIG. 9 shows the preferred trajectory for foot 30 relative to rigid frame 12 where it is similar to how humans walk. Imagine the path that a walking human's foot traces out relative to a fixed point on the body, e.g. the hip. The path is relatively flat during the time that the foot was in contact with the ground. If the path we not relatively flat, then it would mean that the human's hips are moving up and down a significant amount during walking. As we know from watching other people walk, the hips stay relatively level during walking, meaning the foot path is relatively flat while the foot is in contact with the ground. When the foot reaches the end of the flat part, i.e. the human's leg is fully extended behind the body, it is time for the foot to come off the ground and move forward for the next step. The path that the foot takes to return forward must lie above the flat portion, or else the foot would bump into the ground. In other words, one must lift one's foot off of the ground while bringing it forward. Referring to FIG. 9, we see that the machine's foot 30 lifts off of the ground as it moves from point B to point A. Also note that the path reaches a height of about 10 inches above the flat portion. This rise corresponds to the lifting of foot 30 10 inches off of the ground. The reason for this rise is so that the machine can step over objects, such as rocks, or onto objects, such as stairs.
As mentioned previously, the designer of the HAWR must arrive at a proper trajectory for the path of foot 30 . A proper trajectory has two main properties:
1. For 180 rotation of the input—thigh driver-link 18 and shank driver-link 19 , foot 30 travels from A to B and for remaining 180 degree rotation, foot 30 travels from B to A. This means that if the input—thigh driver-link 18 and shank driver-link 19 —rotates at constant speed, the time it takes for the foot 30 to go from A to B is the same as the time for the foot 30 to go from B to A.
2. This trajectory must be such that the foot 30 is in contact with the ground from A to B (on the relatively flat portion of the trajectory). And that the return path (from B to A) lies above the flat portion so that the foot does not bump into the ground.
The motion of the foot 30 (end point of right leg 1 ) has been described. The trajectory of the end point of left leg 2 is identical to that of the end point of the right leg because the motion generating mechanisms are identical for both sides. However the left foot double four-bar linkage is 180° out of phase with the motion of the right double four-bar linkage. The means that when the foot 30 of the right leg 1 is at point A, the foot of the left leg will be at point B. The opposite is also true; when the left leg is at point A, the right leg will be at point B. This is similar to human walking; the left leg is basically doing the same thing as the right leg, except half a step (180° of the cycle) out of phase.
To produce walking we need to have at least one foot on the ground. This is guaranteed by having the left foot be at point A Oust striking the ground) when the right foot is at point B Oust stepping off of the ground). The next requirement for walking is that the machine is propelled forward. If we look back at FIG. 9 we see the path of the foot relative to the rigid frame 12 or the body of the machine. When the foot is on the ground (i.e. between points A and B), if the foot is moving horizontally backward relative to the body of the machine, then the machine is moving horizontally forward relative to the foot. Because the foot is in contact with the ground, we can extend our observation to conclude that the body is moving horizontally forward relative to the ground. This only covers what happens while the foot is on the path between points A and B. However, recall that when one foot reaches point B, it lifts off of the ground, and the other foot (which is at point A) becomes the ground contact foot. Therefore, because the contact foot is always between points A and B, the motion of the machine relative to the ground must be horizontally forward.
This machine offers a significant advantage over other types of rough terrain walking machines that have been previously mentioned. It will be appreciated that this walking robot has only one powered degree of freedom and can traverse many different types of terrain. The simplicity of such a device allows it to be reliable and low, cost. It will also be appreciated that legged means of locomotion provides for a significant advantage over wheeled means enabling a wider range of terrain to be traversed.
To reduce the vibrations transferred to the cargo and the operator a fluid filled shock absorber 31 is incorporated in the leg design. The shock absorber 31 provides damping and compliance to the relative motion between a bottom-half shank leg 32 and a top-half shank leg 33 . Extending from bottom-half shank leg 32 are three slide-shafts 34 . Drilled in top-half shank leg 33 are three corresponding holes. The three slide-shafts 34 fit into the holes of top-half shank leg 33 . Top-half shank leg 33 and bottom-half shank leg 32 can only slide axially, relative to each other. The shock absorber 31 in FIG. 4 is mounted to the top-half shank leg 33 . The other end of the shock absorber 31 contacts the bottom-half shank leg 32 . The foot 30 is mounted to the end of bottom-half shank leg 32 . The foot 30 has a rubber bottom surface, which provides increased traction with the ground.
From the above description, it will be apparent that the invention disclosed herein provides a novel and advantageous human assisted walking robot. The foregoing discussion discloses and describes merely exemplary methods and embodiments of the present invention. One skilled in the art will readily recognize from such discussions that various changes, modifications and variations may be made therein without departing from the spirit and scope of the invention. Accordingly, disclosure of the present invention is intended to be illustrative, but not limiting, of the scope of the invention, which is set forth in the following claims. | A human assisted walking robot formed by a motor, a cargo bin, a pair of legs mounted to the carrier; and a stabilizing support mounted at its proximal end to the carrier and having a wheel rotatably mounted to the distal end. The motor drives the first and second leg members resulting in a walking motion. Each leg is formed by a thigh link and a shank link. A four-bar linkage is coupled between the motor and the thigh and shank of each leg so that rotational motion generated by the motor produces a walking motion by the legs. | 1 |
BACKGROUND OF THE INVENTION
Recently, much attention has been focused on GaN-based compound semiconductors (e.g., Ga x Al 1−x N, IN x Ga 1−x N, and Al x Ga y In 1−x−y N, where 0≦x≦1 and y≧0.1) for blue, green, and ultraviolet light emitting diode (LED) applications. One important reason is that GaN-based LEDs have been found to exhibit efficient light emission at room temperature.
In general, GaN-based LEDs comprise a multilayer structure in which n-type and p-type GaN are stacked on a substrate (most commonly a sapphire substrate), and IN x Ga 1−x N/GaN multiple quantum wells are sandwiched between the p-type and n-type GaN layers. A number of methods for growing the multilayer structure are known in the art, including metalorganic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE) and hydride vapor phase epitaxy (HVPE).
It is also known in the art that these conventional growth methods for compound semiconductor structures, except for MBE, have proven problematic with respect to forming a p-type GaN-based layer suitable for LED applications. In general, GaN layers formed by known growth methods, such as MOCVD, and doped with p-type material such as magnesium, behave like a semi-insulating or high-resistive material. This is thought to result from hydrogen passivation caused by hydrogen that is present in the reaction chamber complexing with the p-type dopant and thus preventing the dopant from behaving as an active carrier. Because of this phenomenon, p-type GaN having a sufficiently low resistivity to form the p-n junction required for LED and laser diode (LD) applications cannot be produced by MOCVD or HVPE techniques.
Various attempts have been made to overcome the difficulties in obtaining p-type GaN-based compound semiconductors. In one technique, known as low-energy electron-beam irradiation (LEEBI), a high-resistive semi-insulating GaN layer, which is doped with a p-type impurity, such as Mg, and formed on top of multilayers of GaN-based compound semiconductors is irradiated with an electron beam having an acceleration voltage of 5 kV to 15 kV while maintaining the semiconductor material at temperatures up to 600° C., in order to reduce the resistance of the p-doped region near the sample surface. However, with this method, reduction in the resistance of the p-doped layer can be achieved only up to the point that the electron beam penetrates the sample, i.e. a very thin surface portion of less than about 0.5 μm deep. Furthermore, this method requires heating the substrate to temperatures up to approximately 600° C in addition to high-voltage acceleration of the electron beam.
Thermal annealing in a non-hydrogen atmosphere has also been used to activate the p-type dopants. For example, heat treatment at 700° C. to 800° C. in a nitrogen atmosphere is typically used to activate the Mg dopants. However, the high temperature required for activation may degrade the light-emitting efficiency of the device by damaging the lattice structure of the III-V nitride material.
In order to improve the efficiency of GaN-based semiconductor devices such as LEDs and laser diodes, it is necessary to develop improved processes for preparing p-type GaN materials which overcome or reduce these problems.
SUMMARY OF THE INVENTION
The present invention is a method of reducing the resistivity of a p-doped III-V or p-doped II-VI semiconductor material and a method of manufacturing a p-type III-V or p-type II-VI semiconductor material.
In one embodiment, the invention involves reducing the electrical resistivity of a p-doped III-V semiconductor material or a p-doped II-VI semiconductor material by placing the semiconductor material in an electric field.
In another embodiment of the invention, a p-type III-V semiconductor material or p-type II-VI semiconductor material is manufactured by growing a p-type III-V semiconductor material or p-type II-VI semiconductor material by MOCVD or HVPE using reaction gases including a p-type impurity to form a p-doped III-V semiconductor material or p-doped II-VI semiconductor material. An electric field of sufficient strength is then applied to the p-doped III-V semiconductor material or p-doped II-VI semiconductor material for sufficient time to reduce the resistivity of the semiconductor material.
In a specific embodiment, a p-type a III-V nitride, such as Al x Ga y In 1−x−y N, Ga x Al 1−x N or In x Ga 1−x N, is grown by MOCVD using a nitrogen source and one or more gas selected from the group consisting of an aluminum source, a gallium source and an indium source. Nitrogen source gases include ammonia and hydrazine. Aluminum source gases include trimethyl aluminum and triethyl aluminum. Gallium source gases include trimethyl gallium and triethyl gallium. Indium source gases include trimethyl indium and triethylindium.
In general, a greater decrease in resistivity of the semiconductor material is achieved the higher the electric field and the longer the period of time that the semiconductor material is in the electric field. Typically, the semiconductor is placed in the electric field for at least about 1 minute. More preferably, the semiconductor is placed in the electric field for a time period in a range of between about 10 minute and about 900 minute. The electric field is preferably at least about 10,000 volts/cm. More preferably, the electric field voltage is in the range of between about 10,000 volts/cm and about 1,000,000 volts/cm. However, even higher electric fields can be achieved when the semiconductor material is placed in a vacuum environment.
In a preferred embodiment, the semiconductor material is heated during application of the electric field. Preferably, the semiconductor material is heated to about 300° C. to about 600° C. When the semiconductor material is a III-V nitride, the temperature is typically kept at or below about 600° C. to avoid decomposition of the material. Optionally, the III-V nitride is placed in a nitrogen atmosphere during heating to further inhibit decomposition of the material.
The method of the invention is particularly useful in preparing III-V nitride-based LEDs and laser diodes, such as Ga x Al 1−x N, In x Ga 1−x N, and Al x Ga y In 1−x−y N, where 0≦x≦1 and y≧0.1. These semiconductor materials typically have a direct band gap between 1.95 eV and 6 eV and may be suitable for construction of green, blue and ultraviolet LEDs, and of green, blue and ultraviolet laser diodes. Of particular interest are blue LEDs, which can be fabricated from III-V nitrides, such as InGaN. Since blue is a primary color, its presence is necessary to produce full color displays or pure white light.
However, p-n junction diodes have been difficult to prepare from III-V nitrides because it is difficult to obtain a good quality p-type semiconductor layer. Generally, III-V nitrides semiconductors are n-type materials even when they are not doped with an n-type dopant. This is because the materials form nitrogen lattice vacancies during crystal growth or during thermal annealing. In addition, III-V nitride semiconductors are typically grown by a vapor phase growth method such as MOCVD or HVPE. In such growth methods, compounds are used which contain hydrogen atoms, or hydrogen is used as a carrier gas. The gaseous compounds which contain hydrogen atoms are thermally decomposed during the growth of the III-V semiconductors and hydrogen is released. The released hydrogen atoms are trapped in the growing semiconductor, and complex with p-dopants to inhibit their acceptor function.
The method of the invention is particularly useful for reducing the resistivity of III-V nitrides because thermal annealing III-V nitrides causes lattice vacancies which decrease the light-emitting efficiency of the material. Utilizing the method of the invention, the resistivity of a semiconductor material can be reduced without heating the material or with heating the material to relatively low temperatures compared to the temperature required for the thermal annealing process, thus reducing the number of lattice vacancies in III-V nitrides and improving the light-emitting efficiency of the material.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of one embodiment of an apparatus for practicing the method of the invention.
FIG. 2 is a schematic representation of another embodiment of an apparatus for practicing the method of the invention.
FIG. 3 shows a graph of the sheet resistivity of a magnesium-doped p-type layer of an InGaN/GaN LED versus temperature of two samples that have been thermal-annealed in a nitrogen atmosphere for 30 minute.
FIG. 4 is a plot of sheet resistivity of a magnesium-doped p-type layer of an InGaN/GaN LED versus voltage applied to the InGaN/GaN LED during electric-field-assisted activation, wherein the InGaN/GaN LED was held at a fixed temperature of 380° C. during application of the electric field for 30 minute, according to one embodiment of the invention.
FIG. 5 is a plot of sheet resistivity of a magnesium-doped p-type layer of an InGaN/GaN LED versus voltage applied to the InGaN/GaN LED during electric-field-assisted activation, wherein the InGaN/GaN LED was held at a fixed temperature of 400° C. during application of the electric field for 30 minute, according to another embodiment of the invention.
FIG. 6 is a plot of sheet resistivity of a magnesium-doped p-type layer of an InGaN/GaN LED versus voltage applied to the InGaN/GaN LED during electric-field-assisted activation, according to one embodiment of the method of the invention.
FIG. 7 is a graph of current verses the applied voltage in the forward bias mode of an InGaN/GaN LED having a Mg-doped p-type GaN layer that has been treated with the method of the invention with a piece of the same sample that was untreated.
FIG. 8 is a graph comparing the electoluminescence intensity of an InGaN/GaN LED having a Mg-doped p-type GaN layer that has been treated with the method of the invention with the electoluminescence intensity of a piece of the same sample that was untreated.
DETAILED DESCRIPTION OF THE INVENTION
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
A III-V material is a semiconductor having a lattice comprising at least one element from Group III(A) or III(B) of the Periodic Table and at least one element from Group V(A) or V(B) of the periodic table. Preferably, the III-V semiconductor material comprises at least one element from column III(A) and at least one element from Group V(A) of the Periodic Table. A III-V nitride is a semiconductor having a lattice comprising nitrogen and at least one element from Group III(A) or III(B) of the Periodic Table. Optionally, a III-V nitride can have one or more elements other than nitrogen from Group V(A) or V(B) of the Periodic Table. In one embodiment, the III-V nitride is represented by the formula Ga x Al 1−x N, In x Ga 1−x N, or Al x Ga y In 1−x−y N, where 0≦x≦1 and y≧0.1
A II-VI material is a semiconductor having a lattice comprising at least one element from Group II(A) or II(B) of the Periodic Table and at least one element from Group VI(A) or VI(B) of the Periodic Table.
In the present invention, a dopant means a p- or n-type impurity present in the semiconductor material. The p-type impurities (also called an acceptor) for III-V semiconductor materials include Group II elements such as cadmium, zinc, beryllium, magnesium, calcium, strontium, and barium. Preferred p-type impurities are magnesium and zinc. n-type impurities (also called donors) are used to prepare an n-type layer of a p-n junction diode. n-type impurities for III-V semiconductor materials include Group IV elements such as silicon, germanium and tin, and Group VI elements such as selenium, tellurium and sulfur.
III-V nitride semiconductor materials grown by MOCVD typically use a nitrogen source (e.g., ammonia or dimethylhydrazine) and at least one source gas for depositing a Group III element, such as a gallium source (e.g., trimethylgallium or triethylgallium), an aluminum source (e.g., trimethyl aluminum or diethyl aluminum) and an indium source (e.g., trimethylindium or diethylindium). When the III-V nitride semiconductor material is a p-type material, it is doped with a p-dopant, preferably Mg or Zn. When a p-type III-V nitride semiconductor material is prepared using MOCVD, the reaction gas used to form the semiconductor layer contains a p-type impurity source. For example, Mg-doped III-V nitride semiconductor layer can be prepared using MOCVD in the presence of cyclopentadienylmagnesium as the p-type impurity source, and a Zn-doped III-V nitride semiconductor layer can be prepared using diethylzinc or dimethylzinc as the p-type impurity source.
FIG. 1 is a schematic representation of one embodiment of a suitable apparatus for practicing the method of the invention. As shown therein, apparatus 10 includes negative lead 12 connecting high-voltage variable DC power supply 14 to first metal plate 16 (i.e., negative electrode). First metal plate 16 is placed on top of variable temperature heat stage 18 and is in contact with III-V or II-VI semiconductor material 20 of the workpiece (in FIGS. 1 and 2 , III-V or II-VI semiconductor material 20 and substrate 22 are the workpiece to be treated by the method of the invention). In general, the III-V or II-VI semiconductor epitaxial layers are grown on substrate 22 such that at least one surface of substrate 22 is covered with one or more epitaxial layers, at least one of which is a p-type epitaxial layer. One or more n-type semiconductor epitaxial layers and one or more undoped semiconductor epitaxial layers may also be present. Typically, II-VI or III-V semiconductor material 20 is placed on top of first metal plate 16 such that the p-type epitaxial layer is in contact with first metal plate 16 . Optionally, it is possible to have other layers, such as a metal, semiconductor or insulator, in between the first metal plate and the p-type layer. Variable-temperature heat stage 18 can be used to heat the semiconductor material during application of the electric field. Positive lead 24 of power supply 14 is connected to second metal plate 26 (i.e., positive electrode), which is placed in contact with substrate 22 . If substrate 22 is an electrically conducting substrate, insulating material 28 may optionally inserted between substrate 22 and second metal plate 26 to prevent the current flow, as shown in FIG. 2 .
Using the apparatus depicted in FIGS. 1 and 2 , an electric field is applied to a p-doped II-VI or III-V semiconductor material ( 20 ) to reduce the resistivity of the material. As discussed above, a greater decrease in resistivity of the semiconductor material is achieved as the strength of the electric field is increased and as the period of time that the semiconductor material is exposed to the electric field is increased. Typically, the resistivity of the p-type semiconductor material ( 20 ) is reduced by at least about one order of magnitude. In one embodiment, the resistivity of the p-type semiconductor material is reduced by at least about two orders of magnitude. The p-doped II-VI or III-V semiconductor material and the first and second metal plates of the apparatus of FIGS. 1 and 2 can be placed in an environment of less than atmospheric pressure in order to achieve a higher electric field. Typically, the electric field is at least about 10,000 volts/cm.
In general, the resistivity of a semiconductor is reduced by placing it in an electric field for at least about 1 minute. More preferably, the semiconductor is placed in the electric field for a time period in a range of between about 10 minute and about 900 minute.
Optionally, the semiconductor material is heated during application of the electric field, typically to at least about 300° C. When the semiconductor material is a III-V nitride, the temperature preferably is kept at or below about 600° C. to avoid decomposition of the material. Optionally, the III-V nitride is placed in a nitrogen atmosphere during heating to further inhibit decomposition of the material.
III-V semiconductor materials and II-VI semiconductor materials are typically grown by a vapor phase growth method such as MOCVD or HVPE. In such growth methods, compounds are used which contain hydrogen atoms, or hydrogen is used as a carrier gas. The gaseous compounds which contain hydrogen atoms are thermally decomposed during the growth of the III-V or II-VI semiconductor material and hydrogen is released. The released hydrogen atoms are trapped in the growing semiconductor, and complex with p-dopants to inhibit their acceptor function.
Application of an electric field after growth of the semiconductor layers is believed to disrupt the hydrogen-p-dopant complexes and expel the released hydrogen from the semiconductor material, thereby restoring the acceptor function of the p-dopants. The function of p-dopants in III-V and II-VI semiconductor materials can be restored by an electric field because hydrogen trapped in the material is typically present as a positively charged ion. The positively charged hydrogen complexed with p-dopants is drawn to the negatively charged electrode and is expelled from the semiconductor material. Thus, more of the p-dopants in the semiconductor material are free to act as acceptors, resulting in a decrease in the resistivity of the material. In addition, the III-V semiconductor material or II-VI semiconductor material can be heated during application of the electric field to within a few degrees (about 10° C.) of the decomposition temperature of the semiconductor material to further reduce the resistivity of the material.
The following are examples of embodiments of the invention, and are not intended to be limiting in any way.
EXAMPLES
I. Thermal Annealing Control
Two InGaN/GaN LED structures having a Mg-doped p-type GaN layer were heated for 30 minutes at 27° C., 370° C., 380° C., 390° C., 440° C., 500° C. and 550° C. under a nitrogen atmosphere. The LED structure consisted of a Si-doped (Si concentration=˜4×10 18 cm −3 ) n-type GaN layer, a multiple-quantum-well InGaN/GaN active region, and a Mg-doped (Mg concentration=˜5×10 19 cm −3 ) p-type GaN layer. The LED structure was grown on a 430-μm-thick sapphire substrate. The sheet resistance of the Mg-doped layer was measured after 30 minute at each temperature by placing indium performs on the exposed surface of the Mg-doped layer. Point resistance was measured by an ohm meter. A graph shown in FIG. 3 indicates that no decrease in the resistance of the Mg-doped GaN layer was observed between the annealing temperatures of 27° C. to 450° C.; the resistivity of the Mg-doped GaN layer did not begin to drop significantly until the annealing temperature reached about 500° C.
II. Electric-Field-Assisted Activation of Acceptors at 380° C.
An InGaN/GaN LED structure having a Mg-doped p-type GaN layer similar to the structure used in Example 1 was heated to a fixed temperature of 380° C. in an ambient atmosphere. An electric field was applied to the LED for 30 minute at 300 volts, 400 volts, 500 volts, 600 volts, 900 volts, 1000 volts, 1200 volts and 1300 volts using the apparatus depicted in FIG. 1 . The sheet resistance of the Mg-doped layer was measured after 30 minute at each voltage setting by placing indium performs on the exposed surface of the Mg-doped layer. Point resistance was measured by an ohm meter. A graph shown in FIG. 4 indicates that resistance dropped sharply upon application of the electric field.
III. Electric-Field Assisted Activation of Acceptors at 400° C.
An InGaN/GaN LED structure having a Mg-doped p-type GaN layer similar to the structure used in Example 1 was heated to a fixed temperature of 400° C. in an ambient atmosphere. An electric field was applied to the LED for 30 minute at 500 volts, 1000 volts, 1500 volts, 2000 volts, and 2600 volts using the apparatus depicted in FIG. 1 . The sheet resistance of the Mg-doped layer was measured after 30 minute at each voltage setting by placing indium performs on the exposed surface of the Mg-doped layer. Point resistance was measured by an ohm meter. A graph shown in FIG. 5 indicates that resistance dropped sharply upon application of the electric field and continued to drop steadily as the voltage was increased.
IV. Electric-Field Assisted Activation of Acceptors at 400° C.
An InGaN/GaN LED structure having a Mg-doped p-type GaN layer similar to the structure used in Example 1 was heated to a fixed temperature of 400° C. in an ambient atmosphere. An electric field was applied to the LED for 30 minute at 1500 volts, 2000 volts, and 2600 volts using the apparatus depicted in FIG. 1 . After 30 minute at each voltage setting, sheet resistance measurements of the Mg-doped layer were carried out by standard circular transmission line measurements (CTLM) on the exposed top surface of the Mg-doped layer of the GaN LED. All metalization alloying temperatures were kept below 400° C. A graph shown in FIG. 6 indicates that resistance dropped steadily as the voltage was increased from 1500 volts to 2600 volts. The sheet resistance of the Mg-doped layer before the electric field was applied was too high to be measure by CTLM, but is conservatively estimated to be about 1×10 6 Ω/sq.
V. Electric-Field Assisted Activation of Acceptors at 400° C.
An InGaN/GaN LED structure having a Mg-doped p-type GaN layer similar to the structure used in Example 1 was heated to a fixed temperature of 400° C. in an ambient atmosphere. An electric field was applied to the LED for 900 minute at a fixed voltage of 2100 volts using the apparatus depicted in FIG. 1 . After application of the electric field for 900 minute the sheet resistance was measured by CTLM to be 82,810 Ω/sq.
VI. Current/Voltage Characteristics of a GaN LED Treated with the Method of the Invention
An InGaN/GaN LED structure having a Mg-doped p-type GaN layer similar to the structure used in Example 1 was divided into two pieces. The first piece of the GaN LED was heated to a fixed temperature of 400° C. in an ambient atmosphere, and an electric field was applied to the LED for 2.5 hours at a fixed voltage of 2100 volts using the apparatus depicted in FIG. 1 . The second piece of the GaN LED was untreated and used as a control. The current/voltage measurements were carried out on the electric-field-treated InGaN/GaN LED and the control by placing one indium perform on the top surface of the Mg-doped p-type GaN layer and another indium perform on the n-type GaN layer. The results shown in FIG. 7 indicate that in the forward bias mode a higher voltage is necessary to obtain a given current in the LED in the control than in the LED treated with an electric field. This provides evidence that the LED treated with an electric field has a higher concentration of active carriers than the control LED.
VII. Electroluminescence of an InGaN/GaN LED Treated with the Method of the Invention
The electroluminescence of the control InGaN/GaN LED and the electric field treated InGaN/GaN LED prepared in Example VI were measured by placing one indium perform on the top surface of the Mg-doped p-type GaN layer and another indium perform on the n-type GaN layer. An electric current of 20 mA was applied and the electroluminescence was measured. The results shown in FIG. 8 indicate that treatment with the method of the invention dramatically increased the light output of the LED as compared to the untreated control.
Equivalents
While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims. | The resistivity of a p-doped III-V or a p-doped II-VI semiconductor material is reduced. The reduction of resistivity of the p-type III-V or a II-VI semiconductor material is achieved by applying an electric field to the semiconductor material. III-V nitride-based light emitting diodes are prepared. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method of producing microstructures having, for example, a different structural height. In particular, the invention relates to a method of producing microstructures having regions of different structural height using a mask, positive x-ray sensitive resist material, and a developer.
2. Background Information
Such a method is disclosed in German Patent No. 3,623,637. In this process, a layer of a positive resist material is partially irradiated with X-ray radiation, with an X-ray mask being employed which is provided with a structured absorber layer that substantially completely absorbs the synchrotron radiation and with at least one further structured absorber layer which absorbs synchrotron radiation preferably only in one part of the spectrum.
A polymer having a sharply defined lower limit dose is employed as the positive resist material.
In the regions not shaded by the structured absorber layer, the resist material, when irradiated, receives a dose higher than the lower limit dose of the resist material along its entire thickness. In the regions shaded by the structured absorber layer, the resist material, when irradiated, receives a dose below the limit dose of the resist material over its entire thickness. In the regions shaded by the structured, partially absorbent absorber layer, a dose greater than the lower limit dose of the resist material is deposited during the irradiation only in the upper portion of the resist material; the lower portion receives a lower dose.
Since the resist material becomes soluble only at the locations that were previously exposed to a dose above the lower limit dose, microstructures are obtained which have regions of different structural height.
This method requires a resist material which has a precisely defined limit dose. On the other hand, the absorber characteristics of the X-ray mask must be carefully adjusted to the resist material.
German Patent No. 3,440,110 discloses another method of the above-mentioned type for the special case of columnar structures having a thin, longer section and a thicker, short section.
In this process, a resist plate of a thickness of about 0.5 mm is partially irradiated through an X-ray mask with high energy X-ray radiation from a synchrotron in such a manner that cylindrical regions result which have a diameter of about 30 μm at a predetermined grid spacing r and whose solubility is much greater than that of the non-irradiated regions of the resist plate. Then the resist plate is again partially irradiated from one side with the same grid spacing r, with, however, the penetration depth of the radiation being less than the thickness of the resist plate and the diameter of the irradiated regions being about 70 μm so that a thicker and shorter cylindrical irradiated region results. The thus irradiated and solubilized regions are removed by means of a liquid developer as disclosed, for example, in German Unexamined Published Patent Application DE-OS 3,039,110. This results in a configuration of columnar structures each having a thinner and a thicker section.
In principle, this method can be transferred to the production of microstructures having other lateral contours and also more than two different structural heights.
One basic problem in the two mentioned methods is that, although in the presently known resist systems there will be no removal during developing if doses below the limit dose are deposited, the mechanical characteristics and the resistance to solvents of these regions are noticeably worse. The height of the structures cannot be predetermined with sufficient accuracy because the weakening of the radiation and thus the dose deposited, is difficult to predetermine with increasing penetration depth.
SUMMARY OF THE INVENTION
It is the object of the invention to propose a method of producing stepped microstructures of the above-mentioned type in which the drawbacks of the prior art methods are avoided. The method is intended to permit tolerances in the step height within the micrometer range. Moreover, high solvent resistance and good mechanical characteristics for the microstructures are to be attained.
This is accomplished by the invention by providing the layer of resist material with microstructures on its side facing the radiation prior to performing a conventional method of producing microstructures using a mask, positive X-ray sensitive resist material, and a developer, as described in the Background section above. Further advantageous embodiments and modifications of the method according to the invention will become apparent from the detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The method according to the invention will be described in an exemplary manner with reference to FIGS. 1 to 10.
FIGS. 1 2a to 2c, 3a to 3c, and 4a to 4e depict three different process variations with which the layer of a resist material can be provided with microstructures.
FIGS. 5 to 7 depict the production of microstructures that have regions of different structural height.
FIGS. 8 to 10 illustrate the possibilities for further processing of the microstructures produced according to the method of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The layer of a resist material can be provided with microstructures according to three different variations of the method.
The first variation is illustrated in FIGS. 1, 2a, 3a and 4a and is presently described.
With the aid of a micromolding tool 3, a plastic microstructure is formed by way of reaction or injection molding on a resist layer 2 that is connected with a base plate 1. During the molding process, the mold nests 3A of the molding tool 3 are filled with a reaction resin or molding substance 7. The filled mold insert is then pressed onto the resist layer 2 as shown in FIG. 3a. In the course of the process, that is, during hardening or solidification of the plastic, a well adhering connection is established between the plastic of the microstructures and the resist layer 2. The microstructures are unmolded by way of a separating movement between molding tool 3 and base plate 1. The result is a resist layer 2 on which are disposed microstructures of plastic with a defined structural height (FIG. 4a). Since it can be ensured that molding substance 7 for the microstructures will not penetrate into the connecting plane between resist material 2 and plastic, the structured plastic 7a need not necessarily have resist characteristics.
The second variation is illustrated in FIGS. 1, 2b, 3b and 4b.
This variation for the production of microstructures on the surface of a resist layer 2 resides in that a further layer 5 having a fixed predetermined thickness from a few micrometers to several hundred micrometers is applied over the entire surface area of resist layer 2. In the course of a molding process, this layer is then structured in a stamping process (FIG. 3b) with the aid of a molding tool 6. The volume and thus the thickness of the stampable layer 5 must here be adapted to the volume of mold nests 6A. After solidification of the plastic, the microstructures are unmolded by way of a separating movement between molding tool 6 and base plate 1. A resist layer 2 is obtained in this way on which plastic microstructures are disposed that have a defined structural height (FIG. 4b).
The second variation is preferably selected if the layer 5 to be stamped has no resist characteristics or the resist material 2 cannot be structured by stamping.
The third variation is illustrated in FIGS. 1, 2c, 3c and 4c.
If layer 2 can be structured by stamping and if it exhibits sufficient resist characteristics, layer 5 of variation 2 is not required.
In this case, layer 2 is selected to be correspondingly thicker and is stamped directly with the aid of molding tool 6 and mold nests 6A.
Preferably a suitable base plate 1 is employed.
The production of the microstructures on the resist material 2 by stamping (variations 2 and 3) has the advantage compared to the reaction or injection molding process according to variation I, that, whenever necessary, an additional electrically conductive cover layer can be applied simultaneously to the end faces of the microstructures. The details of this particularly advantageous stamping process can be found in Patent Application P 4,010,669.1.
Such a conductive cover layer improves, in particular, the molding result in a subsequent metal deposition by electroplating.
In all three process variations, a sample is available after unmolding from the molding or stamping tool in which microstructures 2A, 5A, 7A are disposed on a continuous resist layer 2. This resist layer 2 is here preferably connected with a base plate 1.
The method of producing the microstructures with regions of different structural height will now be described with reference to the stamped resist layer according to FIG. 4c which is obtained according to variation 3.
According to FIG. 5, the sample structured by stamping and disposed on a base plate I includes resist material 2 with microstructures 2A. The sample is almost irradiated through a mask with perpendicularly directed synchrotron radiation. The mask includes regions 8 in which the synchrotron radiation is almost completely absorbed.
The mask having the radiation impermeable regions 8 is now aligned above structures 2A to correspond to the desired step shapes.
If structures 2A are not composed of resist material, for example, if they were produced according to variation 1, structures 2A may be shielded by regions 8.
If, however, structures 2A are composed of resist material, for example, if they were produced according to variation 3, a suitable arrangement of mask regions 8 also makes it possible to change the shape of structures 2A. In this way, structures produced with an existing stamping tool 6 can be changed subsequently, thus providing for the realization of a uniform shape that is independent of adjustment over the entire height of the structure.
Portions 9 of resist material 2 and 2A, respectively, which are not shaded by mask regions 8 are now irradiated by X-ray or synchrotron radiation (FIG. 6) and are thus changed radiation-chemically.
These regions 9 can be removed in a suitable solvent. Thus, after this process step, stepped plastic microstructures 10 exist whose step height is defined precisely by the thickness of the resistive layer (FIG. 7). The height of the structures on the lithographically produced base is predetermined by the depth of the mold nests in the molding tool.
If the thus produced plastic structure is filled with metal 11, for example by electroplating (FIG. 8) and the resist structure is dissolved away after the electroplating step, a step-shaped metal structure results (FIG. 9). If the produced metal structures remain on the base plate, it is possible to produce with the method according to the invention overhanging or also bridge shaped structures.
Moreover, by electroplating over the stepped resist structures (FIG. 8) it is possible to produce stepped molding tools (FIG. 10) with which the described steps can be performed again. This then results not only in two-step structures but, after repeating the method according to the invention n times, in n-step structures.
The technical details of the method steps of X-ray lithography and molding can be found in the two in-house reports, KfK-Bericht No. 3995 "Herstellung von Microstrukturen und grossem Aspektverhaltnis und grosser Strukturhohe mit Synchrotronstrahlung, Galvanoformung und Kunststoffabformung (LIGA-Verfahren)" (translation: Production of Microstructures Having a High Aspect Ratio And a High Structural Height by Means of Synchrotron Radiation, Shaping by Electroplating and Plastic Molding (LIGA Method)), by E. W. Becker, W. Ehrfeld, P. Hagmann, A. Maner, D. Munchmeyer, Kernforschungszentrum Karlsruhe, November, 1985, and No. 4267 "Untersuchungen zur Herstellung von galvanisierbaren Mikrostrukturen mit extremer Strukturhohe durch Abformen mit Kunststoff im Reaktionsgiessverfahren" (translation: Examinations Regarding the Production of Electroplatable Microstructures Having Extreme Structural Height by Molding Plastic Material in a Reaction Casting Process), Kernforschungszentrum Karlsruhe, May, 1987.
With the method according to the invention, it is possible to produce multi-step microstructures having structural heights of several hundred micrometers with lateral dimensions in the micrometer range and step heights from a few micrometers up to several hundred micrometers. A significant advantage of the method according to the invention is that the tolerances of the step height lie in the micrometer range and are thus significantly less than those of the prior art methods.
If necessary, base plate 1 (FIGS. 1 to 9) mechanically reinforces the resist layer so that the various steps according to the invention can be performed with greater precision. After completion of the microstructured bodies, the base plate 1 in this case is separated. Preferably, the base plate is fixed to the resist layer 2. However, the base plate 1 may also be a part of the microstructured bodies to be produced.
In the selection of the base plate 1, the intended use of the stepped microstructures will have to be considered. A ceramic material or a semiconductor material are also suitable in addition to a metal. However, the base plate 1 may also be made of plastic.
Examples for preferred uses of the microstructures produced according to the invention are valve reeds for the production of microvalves, capacitive acceleration sensors, which are optimized with respect to their space requirement as well as gears or toothed rods having two different, superposed rings of teeth for the production of micro drive assemblies. | A method of producing microstructures having regions of different structural height includes providing a layer of positive resist material that is sensitive to X-ray radiation with microstructures on a side facing a source of X-rays. Using a mask, the layer of a positive resist material is partially irradiated with the X-rays. The irradiated regions are removed with the aid of a developer. | 8 |
CLAIM OF PRIORITY
[0001] The present application claims priority from Japanese application JP2004-303648, filed on Oct. 19, 2004, the content of which is hereby incorporated by reference into this application.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to semiconductor integrated circuits, and more particularly to a circuit for converting (down-converting) a frequency of a system clock (high-speed internal clock of LSI) to a lower frequency to control a storage circuit (more specifically, a content addressable memory (CAM) circuit). In addition, it relates to an image processing system using the same.
[0004] 2. Description of the Related Arts
[0005] Heretofore, system LSIs (large-scale semiconductor integrated circuits) each having a built-in content addressable memory have been provided. One of such system LSIs is configured to generate a CAM control timing signal from a system clock. For example, refer to Japanese Patent
SUMMARY OF THE INVENTION
[0006] Heretofore, since the frequency of a system clock has been at the same level as the internal operating frequency of a content addressable memory (about from 125 to 250 MHz), it has been possible to control input/output signals of the content addressable memory by use of the system clock without causing problems.
[0007] However, in recent years, the frequency of a system clock is made higher (500 MHz) with the objective of improving the throughput and performance. On the other hand, a search control signal is still kept at 125 MHz. Because the operating frequency of search control largely depends on an electric current of a memory cell, it is not easy to speed up the operating frequency in question relative to surrounding logic parts.
[0008] In the configuration disclosed in FIG. 2 of Japanese Patent Laid-open No. 6-349284 described above, if a system clock is speeded up, it becomes impossible to load a coincidence line node ( 24 ) into a latch circuit ( 22 ) by a clock signal ( 26 ). This is because a response to the fall time of the coincidence line node ( 24 ) is slow, making it impossible to follow the system clock.
[0009] FIG. 5 is a diagram illustrating a configuration of an image processing LSI examined by the inventor prior to the proposal of the present invention. FIG. 6 illustrates a timing chart of the image processing LSI. A LSI clock Φ 1 whose frequency is 500 MHz is divided into four to generate a clock Φ 2 whose frequency is 125 MHz. A CAM macro is controlled by use of the clock F 2 . The table search ( 111 ) is started on the rising edge of the clock Φ 1 ( 1 ). At this time, a SEARCH enable signal for controlling the CAM macro is loaded by use of the divided clock. On the rising edge of the clock Φ 1 ( 5 ), more specifically, on the rising edge of the second cycle of the divided clock, an address output control signal is generated. The judgment/processing ( 112 ) are started at this point of time. Although the judgment/processing ( 112 ) ends in two cycles, the next control of the CAM macro can be started on the rising edge of the clock Φ 1 ( 9 ), more specifically, on the rising edge of the third cycle of the divided clock. Here, the SEARCH enable signal is inputted again to perform table update ( 113 ). As a result, the number of cycles required for the search processing becomes 12 cycles. In this configuration, because the system clock is simply divided into four to use the divided clock as the internal clock, the internal clock is subject to constraints by the system clock. As a result, for example, in a case where the number of cycles required for the processing from the table search to the table update is given by a request from the system side, the number of times of obtaining enable signals per unit cycle cannot be sufficiently achieved. This poses a problem in that it is not possible to sufficiently achieve the speedup.
[0010] A typical example of the present invention will be described below.
[0011] To be more specific, according to one aspect of the present invention, there is provided a semiconductor integrated circuit comprising: a content addressable memory circuit; and a control circuit for, if an operating frequency of a control signal for controlling input/output signals of the content addressable memory circuit differs from an operating frequency of a LSI internal clock, adjusting the timing thereof.
[0012] According to the means described above, in the semiconductor integrated circuit that operates with a high-speed system clock, it is possible to achieve the speedup without constraints by the system clock by controlling the content addressable memory circuit that operates at a lower speed, using the clock that is down-converted by the control circuit for adjusting the timing.
[0013] One of the typical effects of the present invention including the above means is an improvement in throughput and performance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a diagram illustrating a configuration of a system LSI to which the present invention is applied;
[0015] FIG. 2 is a diagram illustrating a configuration of a system LSI in which a plurality of content addressable memory macros are controlled;
[0016] FIG. 3 is a diagram illustrating as an example a configuration of a clock control circuit shown in FIG. 1 ;
[0017] FIG. 4 is a diagram illustrating a configuration of a content addressable memory macro shown in FIG. 1 ;
[0018] FIG. 5 is a block diagram schematically illustrating a configuration of an image processing LSI to be controlled with a divided clock;
[0019] FIG. 6 is a timing chart of FIG. 5 ;
[0020] FIG. 7 is a block diagram schematically illustrating a configuration of an image processing LSI to which the present invention is applied, and which uses a clock control circuit; and
[0021] FIG. 8 is a timing chart of FIG. 7 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Preferred embodiments of the present invention will be described in detail with reference to drawings below.
First Embodiment
[0023] FIG. 1 illustrates a system LSI according to a first embodiment, which is an example of a semiconductor integrated circuit device to which the present invention is applied. One CAM macro 102 is placed on the system LSI 101 on which a clock control circuit according to this embodiment is placed. This embodiment is applied to, for example, LSIs for image processing.
[0024] In FIG. 1 , reference numeral 103 denotes a clock control circuit for controlling a content addressable memory macro 102 a . The clock control circuit 103 is built into the CAM macro 102 . This configuration produces effects of reducing man-hours required for mounting on LSI, and also facilitating the timing alignment between the content addressable memory macro 102 a and the clock control circuit 103 . Signals inputted from external pins clock Φ 0 , 104 , 105 , 106 are connected to the clock control circuit 103 . A buffer may also be added between each of the external pins and the clock control circuit 103 . The clock control circuit 103 receives signals from the external pins 104 , 105 , 106 in synchronization with the clock Φ 1 so as to generate a control signal for controlling the content addressable memory macro 102 a . In this case, a frequency of the generated signal is converted from a frequency (500 MHz) of LSI internal clock Φ 1 to a lower frequency (250 MHz/125 MHz). Each signal of address input control, data input control, address output control, and data output control is directed from the clock control circuit 103 to the content addressable memory macro 102 a . Further, an address input pin, an address output pin, a data input pin, and a data output pin are connected to the content addressable memory macro 102 a.
[0025] FIG. 4 is a diagram illustrating a configuration of the content addressable memory macro 102 a . An address input end is connected to a FF 10 through a buffer. The FF 10 is controlled by address input control; and an output end of the FF 10 is connected to a decoder circuit. A data input end is connected to a FF 11 through a buffer. The FF 11 is controlled by data input control; and an output end of the FF 11 is connected to an input control circuit. The decoder circuit and the input control circuit are connected to a CAM array. The CAM array is connected to an output control circuit and an encoder circuit. An output end of the output control circuit is connected to a FF 12 ; and the FF 12 is controlled by data output control. An output of the FF 12 is output through a buffer to data output. An output end of the encoder circuit is connected to a FF 13 ; and the FF 13 is controlled by address output control. An output of the FF 13 is output through a buffer to address output.
[0026] Next, operation will be specifically described. In the case of read operation, when an address is inputted, the address is loaded into the FF 10 by an address input control signal. From the loaded address, the decoder generates a signal used to select a desired memory cell of the CAM array. Next, the output control circuit reads out information stored in the selected memory cell. The information is then loaded into the FF 12 by a data output control signal. The data loaded into the FF 12 is output from the data output.
[0027] In the case of write operation, an address is loaded in a manner similar to that of the read operation. Write data is loaded in parallel with the loading of the address. The write data is inputted from the data input end, and is then loaded into the FF 11 by a data input control signal. Through the input control circuit, the data is written to a memory cell selected by the address input.
[0028] In the case of search operation, inputted search data is compared with information stored in the CAM array. The search data is inputted from the data input end, and is then loaded into the FF 11 by a data input control signal. The loaded data is transferred through the input control circuit to the CAM array. The transferred search data is compared with all pieces of information stored in the CAM array. The result of comparison is inputted into the encoder circuit. After that, the result of encoding is loaded into the FF 13 by an address output control signal, and is then output as an address output.
[0029] FIG. 3 is a configuration diagram illustrating as an example a configuration of the clock control circuit 103 . Input signals include a READ enable signal, a WRITE enable signal, a SEARCH enable signal, and a clock Φ 1 . Output signals include an address input control signal, an address output control signal, a data input control signal, and a data output control signal. Flip-flops FF 1 , FF 2 , FF 3 are serially connected between the READ enable signal end and the data output control signal end. A flip-flop FF 4 is connected to the WRITE enable signal end. Flip-flops FF 5 , FF 6 , FF 7 , FF 8 , FF 9 are serially connected between the SEARCH enable signal end and the address output control signal end. A signal that is obtained by ORing RE 1 with WE 1 is equivalent to the address input control signal. A signal that is obtained by ORing WE 1 with SE 1 is equivalent to the data input control signal.
[0030] Operation performed when each of the enable signals is inputted will be specifically described below. In principle, exclusive control must be performed for each enable signal. When it is inputted, the READ enable signal is loaded into the FF 1 by the clock Φ 1 . The READ enable signal is usually kept in a “0” state. At the time of read operation, “1” is inputted. A period of time during which “1” is inputted corresponds to a length of time during which the FF 1 is allowed to input using one cycle of the clock Φ 1 . In addition, because the read operation is performed at a frequency of 250 MHz, the READ enable signal must be inputted at intervals of at least two cycles of the clock F 1 . An output signal RE 1 of the FF 1 becomes a signal having a width of about 200 ps, which is calculated from the frequency of the clock Φ 1 (500 MHz). The output signal RE 1 is then output as an address input control signal. Moreover, the output signal RE 1 is successively loaded into the flip-flops FF 2 , FF 3 that are serially connected to each other. Then, the output signal RE 1 is output as the data output control signal after a lapse of two cycles from the rising edge of the address input control signal. This signal also has a width of about 200 ps.
[0031] When the WRITE enable signal is inputted, the WRITE enable signal is loaded into the flip-flop FF 4 by the clock Φ 1 . The WRITE enable signal is usually kept in the “0” state. At the time of write operation, “1” is inputted. A period of time during which “1” is inputted corresponds to a length of time during which the FF 4 is allowed to input using one cycle of the clock Φ 1 . In addition, because the write operation is performed at a frequency of 250 MHz, the WRITE enable signal must be inputted at intervals of at least two cycles of the clock Φ 1 . An output signal WE 1 of the FF 4 becomes a signal having a width of about 200 ps, which is calculated from the frequency of the clock Φ 1 (500 MHz). The output signal WE 1 is then output as an address input control signal and a data input control signal.
[0032] When it is inputted, the SEARCH enable signal is loaded into the flip-flop FF 5 by the clock F 1 . The SEARCH enable signal is usually kept in the “0” state. At the time of search operation, “1” is inputted. A period of time during which “1” is inputted corresponds to a length of time during which the FF 5 is allowed to input using one cycle of the clock Φ 1 . In addition, because the search operation is performed at a frequency of 125 MHz, the SEARCH enable signal must be inputted at intervals of at least four cycles of the clock Φ 1 . An output signal SE 1 of the FF 5 becomes a signal having a width of about 200 ps, which is calculated from the frequency of the clock Φ 1 (500 MHz). The output signal SE 1 is then output as a data input control signal. Moreover, the output signal SE 1 is successively loaded into the flip-flops FF 6 , FF 7 , FF 8 , FF 9 that are serially connected to each other. Then, the output signal SE 1 is output as the address output control signal after a lapse of four cycles from the rising edge of the data input control signal. This signal also has a width of about 200 ps.
[0033] The clock control circuit 103 ensures the desired timing of each control signal by serially connecting the flip-flops (FF). In this method, centralizing locations at which the flip-flops are placed makes it possible to ensure the desired timing relatively easily. Additionally, even if the operating frequency of a storage circuit to be controlled is changed, it is possible to easily cope with the change by adjusting the number of stages of flip-flops to be serially connected. Moreover, each control signal is a control signal used to control the loading into the flip-flops. Accordingly, it is necessary to ensure the setup time and the hold time that enable the loading. An adjustment circuit for ensuring the setup time and the hold time is obtained by inserting a delay circuit thereto. The delay circuit may be configured with the even number of inverter circuits that are serially connected to each other.
[0034] FIG. 7 is a diagram schematically illustrating a configuration of an image processing LSI that is controlled by the clock control circuit. The LSI 101 includes a CAM macro 102 , and an image processing logic for controlling the CAM macro 102 . In addition, the LSI 102 includes a built-in clock control circuit 103 . The clock control circuit 103 and the image processing logic are controlled by an internal clock Φ 1 . Next, a control example in which a CAM macro of an image processing system is used will be described. First of all, table search ( 111 ) is performed in four cycles by use of the CAM macro, and then the result of the table search is judged/processed ( 112 ) in the image processing logic. Further, table update ( 113 ) is performed in four cycles by use of the CAM macro. It is to be noted that although the judgment/processing are performed at least in two cycles, the number of cycles can be arbitrarily increased depending on a kind of system.
[0035] FIG. 8 is a time chart illustrating signals observed when the clock control circuit included in the LSI shown in FIG. 7 is used. The table search ( 111 ) is started on the rising edge of the clock Φ 1 ( 1 ). At this time, a SEARCH enable signal for controlling the CAM macro is inputted on the rising edge of the clock Φ 1 ( 1 ). Next, in response to the rising ( 5 ) of the clock Φ 1 , an address output control signal is generated. The judgment/processing ( 112 ) are started at this point of time. The judgment/processing ( 112 ) end in two cycles. Accordingly, on the rising edge of the clock Φ 1 ( 7 ), a SEARCH enable signal is inputted to start the table update ( 113 ). As a result, the number of cycles required for the search processing becomes 10 cycles. Accordingly, as compared with the method shown in FIG. 5 , it is possible to decrease the number of cycles by two cycles, which enables an improvement in throughput.
Second Embodiment
[0036] FIG. 2 illustrates a second embodiment. A plurality of CAM macros 102 are placed on a system LSI 101 on which a clock control circuit according to this embodiment is placed. This embodiment is applied to LSIs used for a network whose search bit width is large. The LSIs include, for example, IPv6. In this case, one clock control circuit 103 is used to control a plurality of CAM macros. This makes it possible to achieve an improvement in throughput, and also to reduce the chip area.
[0037] In FIG. 2 , reference numeral 103 denotes a clock control circuit for controlling a CAM macro 102 . The clock control circuit 103 is located on the LSI. With the increase in the number of CAM macros 102 to be controlled, the area efficiency increases. Signals inputted from external pins (clock F 0 , 104 , 105 , 106 ) are connected to the clock control circuit 103 . A buffer may also be added between each of the external pins and the clock control circuit 103 . The clock control circuit 103 receives signals from the external pins 104 , 105 , 106 in synchronization with the clock F 1 so as to generate a control signal for controlling a content addressable memory macro 102 a . An address input control signal, an address output control signal, a data input control signal, and a data output control signal, which are generated, are directed from the clock control circuit 103 to the content addressable memory macro 102 a through bus wiring on the LSI. Further, an address input pin, an address output pin, a data input pin, and a data output pin are connected to the content addressable memory macro 102 a.
[0038] The invention made by the present inventor has been specifically described as above on the basis of the embodiments. However, the present invention is not limited to the above embodiments. As a matter of course, the present invention can be changed in various ways within the range without departing from the gist thereof. For example, how to configure the clock control circuit shown in FIG. 1 is not limited to the configuration shown in FIG. 3 . Any configuration may also be used so long as the clock control circuit has the same function.
[0039] In addition, it is also possible to adopt a configuration that uses in combination the method according to the first embodiment in which the CAM macro 102 including the built-in clock control circuit is used, and the method according to the second embodiment in which the clock control circuit is located on a chip to control a plurality of content addressable memories. As a result, the present invention can also be applied even in a case where CAM macros whose operating frequencies differ from each other are placed on the same LSI.
[0040] In the above description, the invention made by the present inventor has been mainly applied to the semiconductor integrated circuit having the built-in content addressable memory that is included in a field relating to the background on which the present invention is made. However, the present invention is not limited to this. The present invention can also be applied to a semiconductor integrated circuit having other kinds of built-in memories, for example, RAM or ROM.
[0041] Incidentally, the reference numerals used in the diagrams of the application concerned will be listed as below.
101 . . . System LSI 102 . . . CAM macro 102 a . . . Content addressable memory macro 103 . . . Clock control circuit 104 . . . READ enable signal 105 . . . WRITE enable signal 106 . . . SEARCH enable signal | A circuit system is provided capable of improving the throughput thereof by eliminating the operational constraint that if the operating frequency of a content addressable memory is lower than the operating frequency of a system LSI, two system clocks should be provided, or the higher frequency should be synchronized with the slower system clock. A clock control circuit ( 103 ) for down-converting an internal clock (Φ 1 ) of a LSI ( 101 ) is provided, and a control signal whose frequency is made lower is used to operate a content addressable memory circuit ( 102 ). | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
This is a division of U.S. patent application Ser. No. 08/703,441, filed Sep. 17, 1996 and claims benefit of U.S. Provisional Application No. 60/004,706, filed Oct. 3, 1995.
TECHNICAL FIELD
This invention relates to compounds having activity to inhibit leukotriene biosynthesis, to pharmaceutical compositions comprising these compounds, and to a medical method of treatment. More particularly, this invention concerns a class of symmetrical bis-heteroarylmethoxyphenylalkyl carboxylate compounds which inhibit leukotriene biosynthesis, to pharmaceutical compositions comprising these compounds and to a method of inhibiting leukotriene biosynthesis.
BACKGROUND OF THE INVENTION
The leukotrienes are extremely potent substances which produce a wide variety of biological effects, often even when present only in nanomolar to picomalar concentrations. Leukotrienes are important pathological mediators in a variety of diseases. Alterations in leukotriene metabolism have been demonstrated in a number of disease states including asthma, allergic rhinitis, rheumatoid arthritis and gout, psoriasis, adult respiratory distress syndrome, inflammatory bowel disease, endotoxin shock syndrome, atherosclerosis, ischemia induced myocardial injury, and central nervous system pathology resulting from the formation of leukotrienes following stroke or subarachnoid hemorrhage.
Compounds which prevent leukotriene biosynthesis are thus useful in the treatment of disease states such as those listed above in which the leukotrienes play an important pathophysiological role.
U.S. Pat. No. 5,358,955 (Oct. 25, 1994) discloses aryl and heteroarylmethoxyphenyl compounds which inhibit leukotriene biosynthesis.
U.S. Pat. No. 4,970,215 (Nov. 13, 1990) discloses quinolylmethoxyphenyl acetic acid derivatives which inhibit leukotriene biosynthesis.
U.S. Pat. No. 5,512,581 discloses iminoxycarboxylate derivatives which inhibit leukotriene biosynthesis. U.S. Pat. No. 5,326,883 (Jul. 5, 1994) discloses oxime ether derivatives having lipoxygenase inhibitory activity.
European Patent Application Number 349 062 (Jan. 3, 1990) discloses quinolylmethoxyphenyl alkanoic acid derivatives which inhibit leukotriene biosynthesis.
PCT Application Number WO 94/27968 (Dec. 8, 1994) discloses quinoline derivatives as leukotriene antagonists.
Prasit, et al., Bioorganic and Medicinal Chemistry Letters, 1 (11), 645 (1991) describe ((4-(4-chlorophenyl)-1-(4-(2-quinolylmethoxy)phenyl)butyl)thio)acetic acid as an orally active leukotriene biosynthesis inhibitor, and Musser and Kraft, Journal of Medicinal Chemistry, 35 (14), 1, (1992) review quinoline containing leukotriene biosynthesis inhibitors.
SUMMARY OF THE INVENTION
In its principal embodiment, the present invention provides a class of novel symmetrical bis-heteroarylmethoxyphenylalkyl carboxylate compounds and their derivatives and pharmaceutically acceptable salts. The compounds have the formula: ##STR2## wherein W is the same at each occurrence and is selected from the group consisting of (a) quinolyl; (b) quinolyl substituted with a substituent selected from the group consisting of (b-1) halogen, (b-2) alkyl of one to six carbon atoms, (b-3) phenyl, (b-4) phenyl substituted with a substituent selected from the group consisting of (b-4-a) halogen, (b-4b) alkyl of one to six carbon atoms, (b-4-c) haloalkyl of one to six carbon atoms, and (b-4-d) alkoxy of one to six carbon atoms, (b-5) pyridyl, and (b-6) pyridyl substituted with a substituent selected from the group consisting of (b-6-a) halogen, (b-6-b) alkyl of one to six carbon atoms, and (b-6-c) alkoxy of one to six carbon atoms; (c) benzothiazolyl; (d) benzothiazolyl substituted with a substituent selected from the group consisting of (d-1) halogen, (d-2) alkyl ol one to six carbon atoms, (d-3) phenyl, (d-4) phenyl substituted with a substituent selected from the group consisting of (d-4-a) halogen, (d-4-b) alkyl of one to six carbon atoms, (d-4-c) haloalkyl of one to six carbon atoms, and (d-4-d) alkoxy of one to six carbon atoms, (d-5) pyridyl, and (d-6) pyridyl substituted with a substituent selected from the group consisting of (d-6-a) halogen, (d-6-b) alkyl of one to six carbon atoms, and (d-6-c) alkoxy of one to six carbon atoms; (e) benzoxazolyl; (f) benzoxazolyl substituted with a substituent selected from the group consisting of (f-1) halogen, (f-2) alkyl of one to six carbon atoms, (f-3) phenyl, (f-4) phenyl substituted with a substituent selected from the group consisting of (f-4-a) halogen, (f-4-b) alkyl of one to six carbon atoms, (f-4-c) haloalkyl of one to six carbon atoms, and (f-4-d) alkoxy of one to six carbon atoms, (f-5) pyridyl, and (f-6) pyridyl substituted with a substituent selected from the group consisting of (f-6-a) halogen, (f-6-b) alkyl of one to six carbon atoms, and (f-6-c) alkoxy of one to six carbon atoms; (g) benzimidazolyl; (h) benzimidazolyl substituted with a substituent selected from the group consisting of (h-1) halogen, (h-2) alkyl of one to six carbon atoms, (h-3) phenyl, (h-4) phenyl substituted with a substituent selected from the group consisting of (h-4-a) halogen, (h-4-b) alkyl of one to six carbon atoms, (h-4-c) haloalkyl of one to six carbon atoms, and (h-4-d) alkoxy of one to six carbon atoms, (h-5) pyridyl, and (h-6) pyridyl substituted with a substituent selected from the group consisting of (h-6-a) halogen, (h-6-b) alkyl of one to six carbon atoms, and (h-6-c) alkoxy of one to six carbon atoms; (i) quinoxalyl; (j) quinoxalyl substituted with a substituent selected from the group consisting of (j-1) halogen, (j-2) alkyl of one to six carbon atoms, (j-3) phenyl, (j-4) phenyl substituted with a substituent selected from the group consisting of (j-4-a) halogen, (j-4-b) alkyl of one to six carbon atoms, (j-4-c) haloalkyl of one to six carbon atoms, and (j-4-d) alkoxy of one to six carbon atoms, (j-5) pyridyl, and (j-6) pyridyl substituted with a substituent selected from the group consisting of (j-6-a) halogen, (j-6-b) alkyl of one to six carbon atoms, and (j-6-c) alkoxy of one to six carbon atoms; (k) pyridyl; (l) pyridyl substituted with a substituent selected from the group consisting of (l-1) phenyl, (l-2) phenyl substituted with a substituent selected from the group consisting of (l-2-a) halogen, (l-2-b) alkyl of one to six carbon atoms, (l-2-c) haloalkyl of one to six carbon atoms, and (l-2-d) alkoxy of one to six carbon atoms, (l-3) pyridyl, and (l-4) pyridyl substituted with a substituent selected from the group consisting of (l-4-a) halogen, (l-4-b) alkyl of one to six carbon atoms, and (l-4-c) alkoxy of one to six carbon atoms; (m) pyrimidyl; (n) pyrimidyl substituted with a substituent selected from the group consisting of (n-1) phenyl, (n-2) phenyl substituted with a substituent selected from the group consisting of (n-2-a) halogen, (n-2-b) alkyl of one to six carbon atoms, (n-2-c) haloalkyl of one to six carbon atoms, and (n-2-d) alkoxy of one to six carbon atoms, (n-3) pyridyl, and (n-4) pyridyl substituted with a substituent selected from the group consisting of (n-4-a) halogen, (n-4-b) alkyl of one to six carbon atoms, and (n-4-c) alkoxy of one to six carbon atoms; (o) thiazolyl, and (p) thiazolyl substituted with a substituent selected from the group consisting of (p-1) phenyl, (p-2) phenyl substituted with a substituent selected from the group consisting of (p-2-a) halogen, (p-2-b) alkyl of one to six carbon atoms, (p-2-c) haloalkyl of one to six carbon atoms, and (p-2-d) alkoxy of one to six carbon atoms, (p-3) pyridyl, and (p-4) pyridyl substituted with a substituent selected from the group consisting of (p-4-a) halogen, (p-4-b) alkyl of one to six carbon atoms, and (p-4-c) alkoxy of one to six carbon atoms.
R 1 and R 2 are independently selected from the group consisting of (a) hydrogen, (b) alkyl of one to six carbon atoms, (c) halolalkyl of one to six carbon atoms, (d) alkoxy of one to six carbon atoms, and (e) halogen.
R 3 is selected from the group consisting of (a) hydrogen and (b) alkyl of one six carbon atoms.
X is absent or is selected from the group consisting of (a) alkylene of one to six carbon atoms, (b) alkenylene of one to six carbon atoms, and (c) alkynylene of one to six carbon atoms.
Z is selected from the group consisting of (a) COM, (b) CH═N--O--A--COM, (c) CH 2 --O--N═A--COM, and (d) OR 3 where R 3 is hydrogen or alkyl of one to six carbon atoms.
A is selected from the group consisting of (a) alkylene of one to six carbon atoms, and (b) cycloalkylene of three to eight carbon atoms.
M is selected from the group consisting of (a) a pharmaceutically acceptable metabolically cleavable group, (b) --OR 3 where R 3 is selected from the group consisting of hydrogen and alkyl of one to six carbon atoms, and (c) --NR 7 R 8 where R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl of one to six carbon atoms, hydroxy, and alkoxy of one to six carbon atoms, or R 7 and R 8 taken together define a five- to eight-membered ring, with the proviso that R 7 and R 8 may not simultaneously be hydroxyl, (d) --NR 3 SO 2 R 9 wherein R 3 is as defined above and R 9 is alkyl of one to six carbon atoms, (e) --NH-tetrazolyl, and (f) glycinyl.
The present invention also provides pharmaceutical compositions which comprise a therapeutically effective amount of compound as defined above in combination with a pharmaceutically acceptable carrier.
The invention further relates to a method of inhibiting leukotriene biosynthesis in a host mammal in need of such treatment comprising administering to a mammal in need of such treatment a therapeutically effective amount of a compound as defined above.
DETAILED DESCRIPTION
As used throughout this specification and the appended claims, the following terms have the meanings specified.
The term alkyl refers to a monovalent group derived from a straight or branched chain saturated hydrocarbon by the removal of a single hydrogen atom. Alkyl groups are exemplified by methyl, ethyl, n- and iso-propyl, n-, sec-, iso- and tert-butyl, and the like.
The terms alkoxy and alkoxyl denote an alkyl group, as defined above, attached to the parent molecular moiety through an oxygen atom. Representative alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and the like.
The term alkenyl as used herein refers to monovalent straight or branched chain groups of 2 to 6 carbon atoms containing a carbon-carbon double bond, derived from an alkene by the removal of one hydrogen atom and include, but are not limited to groups such as ethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl and the like.
The term alkylene denotes a divalent group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms, for example --CH 2 --, --CH 2 CH 2 --, --CH(CH 3 )CH 2 -- and the like.
The term alkenylene denotes a divalent group derived from a straight or branched chain hydrocarbon containing at least one carbon-carbon double bond. Examples of alkenylene include --CH═CH--, --CH 2 CH═CH--, --C(CH 3 )═CH--, --CH 2 CH═CHCH 2 --, and the like.
The term alkynylene refers to a divalent group derived by the removal of two hydrogen atoms from a straight or branched chain acyclic hydrocarbon group containing at least one carbon-carbon triple bond. Examples of alkynylene include --CH.tbd.CH--, --CH.tbd.CH--CH 2 --, --CH.tbd.CH--CH(CH 3 )--, and the like.
The term aryl as used herein refers to a monovalent carbocyclic group containing one or more fused or non-fused phenyl rings and includes, for example, phenyl, 1- or 2-naphthyl, 1,2-dihydronaphthyl, 1,2,3,4-tetrahydronaphthyl, and the like.
The term cycloalkyl as used herein refers to a monovalent saturated cyclic hydrocarbon group. Representative cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo 2.2.1!heptane and the like.
Cycloalkylene denotes a divalent radical derived from a cycloalkane by the removal of two hydrogen atoms.
The term haloalkyl denotes an alkyl group, as defined above, having one, two, or three halogen atoms attached thereto and is exemplified by such groups as chloromethyl, bromoethyl, trifluoromethyl, and the like.
As used throughout this specification and the appended claims, the term "metabolically cleavable group" denotes a moiety which is readily cleaved in vivo from the compound bearing it, which compound after cleavage remains or becomes pharmacologically active. Metabolically cleavable groups form a class of groups reactive with the carboxyl group of the compounds of this invention (where M is --OH) well known to practitioners of the art. They include, but are not limited to such groups as alkanoyl (such as acetyl, propionyl, butyryl, and the like), unsubstituted and substituted aroyl (such as benzoyl and substituted benzoyl), alkoxycarbonyl (such as ethoxycarbonyl), trialkylsilyl (such as trimethyl- and triethysilyl), monoesters formed with dicarboxylic acids (such as succinyl), and the like. Because of the ease with which the metabolically cleavable groups of the compounds of this invention are cleaved in vivo, the compounds bearing such groups act as pro-drugs of other leukotriene biosynthesis inhibitors. The compounds bearing the metabolically cleavable groups have the advantage that they may exhibit improved bioavailability as a result of enhanced solubility and/or rate of absorption conferred upon the parent compound by virtue of the presence of the metabolically cleavable group.
In those instances where M═OH, the compounds of the present invention are capable of forming base addition salts. In such instances, the term "pharmaceutically acceptable salts" refers to the relatively nontoxic inorganic and organic base addition salts of compounds of the present invention. These salts can be prepared in situ during the final isolation and purification of the compounds, or by separately reacting the purified carboxyl compound with a suitable base such as the hydroxide, carbonate, or bicarbonate of a pharmaceutically acceptable metal cation or with ammonia, or an organic primary, secondary, or tertiary amine of sufficient basicity to form a salt with the carboxyl functional group of the compounds of this invention.
Representative alkali or alkaline earth metal salts include sodium, lithium, potassium, calcium, magnesium, and the like. Representative organic amines useful for the formation of base addition salts include ethylamine, diethylamine, ethylenediamine, ethanolamine, diethanolamine, piperazine, and the like. (See, for example, S. M. Berge, et al., J. Pharmaceutical Sciences, 1977, 66: 1-19, which is incorporated herein by reference).
Similarly, in those instances where the compounds of the present invention possess a heterocyclic ring moiety containing a basic nitrogen atom, the compounds are capable of forming acid addition salts. In such cases, the term "pharmaceutically acceptable salts" also refers to the nontoxic inorganic and organic acid addition salts of compounds of the present invention. These salts can be prepared in situ during the final isolation and purification of the compounds, or by separately reacting the purified compound in its free-base form with a suitable inorganic or organic acid and isolating the salt thus formed. Representative acid addition salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphersulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, fumarate, glucoheptonate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, 2-hydroxy-ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, parnoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, toluenesulfonate, undecanoate, valerate salts, and the like. (See, for example, S. M. Berge, et al., J. Pharmaceutical Sciences, 1977, 66: 1-19), which is incorporated herein by reference). Said pharmaceutically acceptable acid and base addition salts are also contemplated as falling within the scope of the present invention.
Asymmetric centers may exist in the compounds of the present invention. The present invention contemplates the various stereoisomers and mixtures thereof. Individual stereoisomers of compounds of the present invention are made by synthesis from starting materials containing the chiral centers or by preparation of mixtures of enantiomeric products followed by separation as, for example, by conversion to a mixture of diastereomers followed by separation by recrystallization, or chromatographic techniques, or by direct separation of the optical enantiomers on chiral chromatographic columns. Starting compounds of particular stereochemistry are either commercially available or are made by the methods detailed below and resolved by techniques well known in the organic chemical arts.
Examples of compounds contemplated as falling within the scope of the present invention include, but are not limited to:
4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(2-quinolylmethyl)phenyl)pentanoic acid methyl ester,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(4-(2-quinolylmethoxy)phenyl) pentanoic acid magnesium salt,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!iminoxyacetic acid,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid, methyl ester,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!oximinoacetic acid,
4,4-bis(4-(2-benzothiazoylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(2-benzothiazoylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(4-(7-chloro-2-quinolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(6-fluoro-2-quinolylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(4-(6-fluoro-2-quinolylmethoxy)phenyl)pentanoic acid,
2,2-bis(4-(2-quinolylmethoxy)phenyl)propionic acid,
3,3-bis(4-(2-quinolylmethoxy)phenyl)butanoic acid,
5,5-bis(4-(2-quinolylmethoxy)phenyl)hexanoic acid,
5,5-bis(4-(2-quinolylmethoxy)phenyl)hexanoic acid sodium salt,
4,4-bis-(4-(2-pyridylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis-(4-(2-pyridylmethoxy)phenyl)pentanoic acid,
4,4-bis-(4-(2-quinoxylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(4-(1-methyl-2-benzimdazolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(1-methyl-2-benzimidazolylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid methyl ester,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid sodium salt,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentan-1-ol,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid N,N-diethylhydroxylamine ester,
2,2-bis(4-(2-quinolylmethoxy)phenyl)butyric acid,
1,1-bis(4-(2-quinolylmethoxy)phenyl)ethanol,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid methyl ester,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)prop-1-yl!oximinoacetic acid sodium salt,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propan-1-ol,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)prop-1-yl!oximinoacetic acid,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)-1-propyliminoxyacetic acid,
2,2-bis(4-(2-quinolymethoxy)phenyl)acetic acid,
2,2-bis(4-(6-fluoro-2-quinolymethoxy)phenyl)acetic acid,
2,2-bis(4-(2-quinolylmethoxy)phenyl)eth-1-yloximinoacetic acid,
2,2-bis(4-(2-quinolymethoxy)phenyl)acetic acid methyl ester,
2,2-bis(4-(2-quinolylmethoxy)phenyl)eth-1-yloximinoacetic acid sodium salt,
3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid,
3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt,
4,4-bis(4-(2-quinolylmethoxy)phenyl)acetic acid-N-carboxymethyl amide,
3,3-bis-(2-quinolylmethoxyphenyl)but-1-yl!-2-iminoxypropionic acid,
3,3-bis(4-(2-quinolylmethoxy)phenyl)butan-1-ol,
4,4-bis(4-(2-quinolylmethoxy)phenyl)-4-hydroxy-2-butynoic acid,
4,4-bis(2-quinolylmethoxy)phenyl)-4-hydroxy-2-butynoic acid methyl ester,
5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-pentyn-1-yl!-2-iminoxypropionic acid sodium salt,
5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-pentyn-1-yl!-2-iminoxypropionic acid,
4,4-bis(4-(2-benzoxazolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(2-pyrimidylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(4-phenyl-2-thiazolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(4-(pyrid-2-yl)-2-thiazolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(6-phenyl-2-pyridylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(5-phenyl-2-pyridylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(6-(pyrid-2-yl)-2-pyridylmethoxy)phenyl)pentanoic acid, and
4,4-bis(4-(4-phenyl-2-pyrimidylmethoxy)phenyl)pentanoic acid.
Preferred compounds of the present invention have the structure defined above wherein Z is selected from the group consisting of (a) COM, (b) CH═N--O--A--COM, (c) CH 2 --O--N═A--COM, and (d) OH wherein A is alkylene of one to six carbon atoms, and M is --OH.
More preferred compounds of the present invention have the structure defined immediately above wherein W is selected from the group consisting of (a) quinolyl; (b) quinolyl substituted with a substituent selected from the group consisting of (b-1) halogen, (b-2) alkyl of one to six carbon atoms, (b-3) phenyl, (b-4) phenyl substituted with a substituent selected from the group consisting of (b-4-a) halogen, (b-4-b) alkyl of one to six carbon atoms, (b-4-c) haloalkyl of one to six carbon atoms, and (b-4-d) alkoxy of one to six carbon atoms, (b-5) pyridyl, and (b-6) pyridyl substituted with a substituent selected from the group consisting of (b-6-a) halogen, (b-6-b) alkyl of one to six carbon atoms, and (b-6-c) alkoxy of one to six carbon atoms; (c) benzothiazolyl; and (d) benzothiazolyl substituted with a substituent selected from the group consisting of (d-1) halogen, (d-2) alkyl of one to six carbon atoms, (d-3) phenyl, (d-4) phenyl substituted with a substituent selected from the group consisting of (d-4-a) halogen, (d-4-b) alkyl of one to six carbon atoms, (d-4-c) haloalkyl of one to six carbon atoms, and (d-4-d) alkoxy of one to six carbon atoms, (d-5) pyridyl, and (d-6) pyridyl substituted with a substituent selected from the group consisting of (d-6-a) halogen, (d-6-b) alkyl of one to six carbon atoms, and (d-6-c) alkoxy of one to six carbon atoms.
Still more preferred compounds have the structure defined immediately above wherein X is alkylene of one to six carbon atoms, and Z is COOH.
The most preferred compounds of the present invention have the structure defined immediately above wherein W is the same at each occurrence and is selected from the group consisting of (a) quinolyl; and (b) quinolyl substituted with a substituent selected from the group consisting of (b-1) halogen, (b-2) alkyl of one to six carbon atoms, (b-3) phenyl, (b-4) phenyl substituted with a substituent selected from the group consisting of (b-4-a) halogen, (b-4-b) alkyl of one to six carbon atoms, (b-4-c) haloalkyl of one to six carbon atoms, and (b-4-d) alkoxy of one to six (carbon atoms, (b-5) pyridyl, and (b-6) pyridyl substituted with a substituent selected from the group consisting of (b-6-a) halogen, (b-6-b) alkyl of one to six carbon atoms, and (b-6-c) alkoxy of one to six carbon atoms.
Compounds representative of the most preferred embodiment include, but are not limited to
4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(4-(2-quinolylmethoxy)phenyl) pentanoic acid magnesium salt,
4,4-bis(4-(2-benzothiazoylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(2-benzothiazoylmethoxy)phenyl)pentanoic acid sodium salt,
4,4-bis(4-(7-chloro-2-quinolylmethoxy)phenyl)pentanoic acid,
4,4-bis(4-(7-fluoro-2-quinolylmethoxy)phenyl)pentanoic acid sodium salt,
2,2-bis(4-(2-quinolylmethoxy)phenyl)propionic acid,
3,3-bis(4-(2-quinolylmethoxy)phenyl)butanoic acid,
5,5-bis(4-(2-quinolylmethoxy)phenyl)hexanoic acid,
5,5-bis(4-(2-quinolylmethoxy)phenyl)hexanoic acid sodium salt,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid,
4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt,
2,2-bis(4-(2-quinolylmethoxy)phenyl)butyric acid,
2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt,
2,2-bis(4-(2-quinolymethoxy)phenyl)acetic acid,
2,2-bis(4-(6-fluoro-2-quinolymethoxy)phenyl)acetic acid,
2,2-bis(4-(2-quinolylmethoxy)phenyl)propionic acid, and
2,2-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt.
Lipoxygenase Inhibition Determination
Inhibition of leukotriene biosynthesis was evaluated in vitro using an assay involving calcium ionophore-induced LTB 4 expressed in human polymorphornuclear leukocytes (PMNL). Human PMNL isolated from heparinized (20 USP units/mL) venous blood (25 mL) obtained from healthy volunteers was layered over an equal volume of Ficoll-Hypaque Mono-Poly Resolving Medium (ICN Flow, Costa Mesa, Calif.) and centrifugated at 400×g for 40 minutes at 20° C. The PMNL was collected, erythrocytes lysed and washed 2× and suspended at 1.0×10 7 cells/mL in Earle's balanced salt solution with 17 mM Earle's HEPES. Aliquots of the cell suspension were preincubated with test compounds dissolved in DMSO (final concentration <2%) for 15 minutes and stimulated with calcium ionophore (final concentration 8.3, μM) for 10 minutes at 37° C. Incubations were stopped with the addition of two volumes of ice-cold methanol followed by centrifuging the cell suspensions at 4° C. for 10 minutes at ˜450×g. The amount of LTB 4 in the methanol extract was analyzed by enzyme-linked immunoassay or by HPLC analysis.
The compounds of this invention inhibit leukotriene biosynthesis as shown by the data for representative examples in Table 1.
TABLE 1______________________________________In Vitro Inhibitory Potencies Against 5-Lipoxygenase FromStimulated LTB.sub.4 Formation in Human Polymorphonuclear______________________________________Leukocytes Example IC.sub.50 (μM)______________________________________ 1 0.040 2 0.069 5 0.030 6 0.035 7 0.040 8 0.046 9 0.050 11 0.040 12 0.032 14 0.043 20 0.026 25 0.050 26 0.080 27 0.028 28 0.034 30 0.050 31 0.035 34 0.070 36 0.025 38 0.060______________________________________
Inhibition of leukotriene biosynthesis in vivo was evaluated using the Ionophore A32187-Induced Rat Plueral Inflammation Model. Pleural inflammation was induced in male rats following the method of Rao et al (Rao, T. S., Currie, J. L., Shaffer, A. F., Isakson, P. C., (1993) Evaluation of 5-lipoxygenase Inhibitors, Zileuton, A-78773 and ICI D-2138 in an lonophore (A-23187) Induced Pleural Inflammation Model in the Rat, Life Sciences, 53: 147 (1993)). Rats were dosed with experimental compounds in 0.2% methocel one hour prior to the intrapleural injection of the calcium ionophore, A23187. The rats where lightly anesthetized with Pentrane (Abbott Laboratories) and injected intrapleurally with 0.5 ml of 2% ethanol in injectable saline (Abbott Laboratories) containing 20 μg of A23187 (Cal BioChem-Novabiochem). Thirty minutes later the animals were euthanised and the pleural cavities lavaged with ice cold saline (Abbott Laboratories). The lavage fluid was then added to ice cold methanol (final methanol concentration 30%) to lyse cells and precipitate protein. Eicosanoids were determined by enzyme immunoassay by standard methods.
TABLE 2______________________________________In Vivo Leukotriene Inhibition in Rat Pleural Inflammation % Inhibition atExample 3 mg/kg______________________________________ 2 53%11 42%14 32%24 38%26 50%27 42%34 30%38 40%______________________________________
Pharmaceutical Compositions
The present invention also provides pharmaceutical compositions which comprise compounds of the present invention formulated together with one or more non-toxic pharmaceutically acceptable carriers. The pharmaceutical compositions may be specially formulated for oral administration in solid or liquid form, for parenteral injection, or for rectal administration.
The pharmaceutical compositions of this invention can be administered to humans and other animals orally, rectally, parenterally, intracisternally, intravaginally, intraperitoneally, topically (as by powders, ointments, or drops), bucally, or as an oral or nasal spray. The term "parenteral" administration as used herein refers to modes of administration which include intravenous, intramuscular, intraperitoneal, intrasternal, subcutaneous and intraarticular injection and infusion.
Pharmaceutical compositions of this invention for parenteral injection comprise pharmaceutically acceptable sterile aqueous or nonaqueous solutions, dispersions, suspensions or emulsions as well as sterile powders for reconstitution into sterile injectable solutions or dispersions just prior to use. Examples of suitable aqueous and nonaqueous carriers, diluents, solvents or vehicles include water, ethanol, polyols (such as glycerol, propylene glycol, polyethylene glycol, and the like), and suitable mixtures thereof, vegetable oils (such as olive oil), and injectable organic esters such as ethyl oleate. Proper fluidity can be maintained, for example, by the use of coating materials such as lecithin, by the maintenance of the required particle size in the case of dispersions, and by the use of surfactants.
These compositions may also contain adjuvants such as preservative, wetting agents, emulsifying agents, and dispersing agents. Prevention of the action of microorganisms may be ensured by the inclusion of various antibacterial and antifungal agents, for example, paraben, chlorobutanol, phenol sorbic acid, and the like. It may also be desirable to include isotonic agents such as sugars, sodium chloride, and the like. Prolonged absorption of the injectable pharmaceutical form may be brought about by the inclusion of agents which delay absorption such as aluminum monostearate and gelatin.
In some cases, in order to prolong the effect of the drug, it is desirable to slow the absorption of the drug from subcutaneous or intramuscular injection. This may be accomplished by the use of a liquid suspension of crystalline or amorphous material with poor water solubility. The rate of absorption of the drug then depends upon its rate of dissolution which, in turn, may depend upon crystal size and crystalline form. Alternatively, delayed absorption of a parenterally administered drug form is accomplished by dissolving or suspending the drug in all oil vehicle.
Injectable depot forms are made by forming microencapsule matrices of the drug in biodegradable polymers such as polylactide-polyglycolide. Depending upon the ratio of drug to polymer and the nature of the particular polymer employed, the rate of drug release can be controlled. Examples of other biodegradable polymers include poly(orthoesters) and poly(anhydrides). Depot injectable formulations are also prepared by entrapping the drug in liposomes or microemulsions which are compatible with body tissues.
The injectable formulations can be sterilized, for example, by filtration through a bacterial-retaining filter, or by incorporating sterilizing agents in the form of sterile solid compositions which can be dissolved or dispersed in sterile water or other sterile injectable medium just prior to use.
Solid dosage forms for oral administration include capsules, tablets, pills, powders, and granules. In such solid dosage forms, the active compound is mixed with at least one inert, pharmaceutically acceptable excipient or carrier such as sodium citrate or dicalcium phosphate and/or
a) fillers or extenders such as starches, lactose, sucrose, glucose, mannitol, and silicic acid,
b) binders such as, for example, carboxymethylcellulose, alginates, gelatin, polyvinylpyrrolidone, sucrose, and acacia,
c) humectants such as glycerol,
d) disintegrating agents such as agar-agar, calcium carbonate, potato or tapioca starch, alginic acid, certain silicates, and sodium carbonate,
e) solution retarding agents such as paraffin,
f) absorption accelerators such as quaternary ammonium compounds,
g) wetting agents such as, for example, cetyl alcohol and glycerol monostearate,
h) absorbents such as kaolin and bentonite clay, and i) lubricants such as talc, calcium stearate, magnesium stearate, solid polyethylene glycols, sodium lauryl sulfate, and mixtures thereof. In the case of capsules, tablets and pills, the dosage form may also comprise buffering agents.
Solid compositions of a similar type may also be employed as fillers in soft and hard-filled gelatin capsules using such excipients as lactose or milk sugar as well as high molecular weight polyethylene glycols and the like.
The solid dosage forms of tablets, dragees, capsules, pills, and granules can be prepared with coatings and shells such as enteric coatings and other coatings well known in the pharmaceutical formulating art. They may optionally contain opacifying agents and can also be of a composition that they release the active ingredient(s) only, or preferentially, in a certain part of the intestinal tract, optionally, in a delayed manner. Examples of embedding compositions which can be used include polymeric substances and waxes.
The active compounds can also be in micro-encapsulated form, if appropriate, with one or more of the above-mentioned excipients.
Liquid dosage forms for oral administration include pharmaceutically acceptable emulsions, solutions, suspensions, syrups and elixirs. In addition to the active compounds, the liquid dosage forms may contain inert diluents commonly used in the art such as, for example, water or other solvents, solubilizing agents and emulsifiers such as ethyl alcohol, isopropyl alcohol, ethyl carbonate, ethyl acetate benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylene glycol, dimethyl formamide, oils (in particular, cottonseed, groundnut, corn, germ, olive, castor, and sesame oils), glycerol, tetrahydrofurfuryl alcohol, polyethylene glycols and fatty acid esters of sorbitan, and mixtures thereof.
Besides inert diluents, the oral compositions can also include adjuvants such as wetting agents, emulsifying and suspending agents, sweetening, flavoring, and perfuming agents.
Suspensions, in addition to the active compounds, may contain suspending agents as, for example, ethoxylated isostearyl alcohols, polyoxyethlylene sorbitol, and sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, aparagar, and tragacanth, and mixtures thereof.
Compositions for rectal or vaginal administration are preferably suppositories which can be prepared by mixing the compounds of this invention with suitable non irritating excipients or carriers such as cocoa butter, polyethylene glycol or a suppository wax which are solid at room temperature but liquid at body temperature and therefore melt in the rectum or vaginal cavity and release the active compound.
Compounds of the present invention can also be administered in the form of liposomes. As is known in the art, liposomes are generally derived from phospholipids or other lipid substances. Liposomes are formed by mono- or multilamellar hydrated liquid crystals that are dispersed in an aqueous medium. Any nontoxic, physiologically acceptable and metabolizable lipid capable of forming liposomes can be used. The present compositions in liposome form can contain, in addition to a compound of the present invention, stabilizers, preservatives, excipients, and the like. The preferred lipids are the phospholipids and the phosphatidyl cholines (lecithins), both natural and synthetic.
Methods to form liposomes are known in the art. See, for example, Prescott, Ed., Methods in Cell Biology, Volume XIV, Academic Press, New York, N.Y. (1976), p. 33, et seq.
Dosage forms for topical administration of a compound of this invention include powders, sprays, ointments and inhalants. The active compound is mixed under sterile conditions with a pharmaceutically acceptable carrier and any needed preservatives, buffers, or propellants which may be required. Opthalmic formulations, eye ointments, powders and solutions are also contemplated as being within the scope of this invention.
Actual dosage levels of active ingredients in the pharmaceutical compositions of this invention may be varied so as to obtain an amount of the active compound(s) that is effective to achieve the desired therapeutic response for a particular patient, compositions, and mode of administration. The selected dosage level will depend upon the activity of the particular compound, the route of administration, the severity of the condition being treated, and the condition and prior medical history of the patient being treated. However, it is within the skill of the art to start doses of the compound at levels lower than required to achieve the desired therapeutic effect and to gradually increase the dosage until the desired effect is achieved.
Generally dosage levels of about 1 to about 50, more preferably of about 5 to about 20 mg of active compound per kilogram of body weight per day are administered orally to a mammalian patient. If desired, the effective daily dose may be divided into multiple doses for purposes of administration, e.g., two to four separate doses per day.
Preparation Of Compounds Of This Invention
In general, the compounds of this invention are synthesized by reaction schemes 1-3 as illustrated below. The preparation of compounds of this invention wherein Z is CO 2 R 6 , wherein R 6 is H or alkyl is outlined in Scheme 1. Reaction of two equivalents of phenol with the requisite carbonyl (keto or aldehyde) ester in the presence of acid gives adducts of formula I (see U.S. Pat. No. 2,933,520). Intermediates of formula I wherein R 6 is H are esterified, for example by reaction with an alcohol in the presence of acid, to give an ester of formula II, which is then reacted with a heteroarylmethyl halide of formula W--CH 2 X where X is Cl, Br, or I, and W is defined above in the presence of a suitable base such as K 2 CO 3 to provide the desired compound III in which R 6 is alkyl. Hydrolysis of the ester, for example using aqueous alkali, provides compounds of formula IV wherein R 6 is H. ##STR3##
A general procedure for the synthesis of compounds of this invention wherein Z is OR 4 or CH═N--O--A--COM is described in Scheme 2. Reduction of ester III, for example using lithium aluminum hydride or sodium borohydride, or acid IV, for example using lithium aluminum hydride or using sodium borohydride to reduce the mixed anhydride made from the acid and ethyl chloroformate, provides alcohol V. Compounds of this invention wherein R 4 is alkyl are then prepared from V using methods well-known in the art such as reaction with alkyl iodide in the presence of base. Alcohol V is converted to compounds of this invention wherein CH═N--O--A--COM by oxidation to the aldehyde, for example using Swern oxidation conditions (Swern, et al., J. Org. Chem., 1978, 43, 2480), followed by reaction with the requisite hydroxylamine derivative H 2 N--O--A--COM. ##STR4##
The preparation of compound of this invention wherein Z is CH 2 --O--N═A--COM is described in Scheme 3. The hydroxy intermediate V, prepared in Scheme 2 above, is converted to hydroxylamine derivative VIII by known methods such as coupling with N-hydroxyphthalimide under Mitsunobu conditions (triphenyl-phosphine, diethyl or diisopropylazodicarboxylate; see Mitsunobu, O., Synthesis, 1981, 1), followed by treatment with hydrazine. The hydroxylamine derivative VIII is then reacted with the requisite carbonyl unit, O═A--COM to provide the compounds of this invention represented by the general structure IX. ##STR5##
The foregoing may be better understood by reference to the following examples which are provided for illustration and are not intended to limit the scope of the invention as it is defined by the appended claims.
EXAMPLE 1
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid ##STR6## Step 1: 4,4-bis(4-hydroxyphenyl)pentanoic acid methyl ester
To a solution in methanol (120 mL) of 4,4-bis(4-hydroxyphenyl)pentanoic acid (Aldrich Chemical Co., 12 g, 42 mmol) was added concentrated H 2 SO 4 (0.5 mL) and the mixture was heated to reflux for 3 hours. After cooling to room temperature the mixture was concentrated in vacuo and dissolved in ether (300 mL). The organic layer was washed with saturated aqueous NaHCO 3 (2×150 mL) and brine, dried over MgSO 4 , filtered, and concentrated in vacuo to provide a thick oil which was crystallized from ether/hexane to give 4,4-bis(4-hydroxyphenyl)pentanoic acid methyl ester as an off-white color solid (11.8 g, 94%), mp 130° C.
Step 2: 4,4-bis(4-(2-quinolylmethyl)phenyl)pentanoic acid methyl ester
To a solution in dry DMF under N 2 of 4,4-bis(4-hydroxyphenyl)pentanoic acid methyl ester (6.0 g, 20 mmol), prepared as in step 1, was added powdered K 2 CO 3 (11.0 g, 80 mmol) and the reaction was stirred for 10 minutes after which 2-chloromethylquinoline hydrochloride (8.5 g, 40 mmol) was added. The mixture was heated at 60° C. for 18 hours and then cooled to room temperature, diluted with EtOAc (200 mL), washed with water and brine, dried over MgSO 4 , filtered and concentrated in vacuo to provide a residue which was purified by chromatography on silica gel (9:1 CH 2 Cl 2 /EtOAc) to provide 10.8 (92%) of 4,4-bis(4-(2-quinolylmethyl)phenyl)pentanoic acid methyl ester.
Step 3: 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid
To a solution in 1:1 dioxane/methanol (100 mL) of 4,4-bis(4-(2-quinolylmethyl)phenyl)pentanoic acid methyl ester (3.3 g, 5.7 mmol), prepared as in step 2, was added aqueous 1N NaOH (10 mL) and the mixture was heated at reflux for 3 hours, cooled to room temperature, concentrated in vacuo, diluted with water and neutralized with 10% aqueous citric acid. The solid precipitate was collected by filtration, dried in vacuo, and purified by chromatography on silica gel (9:1 CH 2 Cl 2 /EtOAc, followed by 20:1 CH 2 Cl 2 /CH 3 OH) to provide 2.53 g (70%) of the desired product. Crystallization from methylene chloride-hexanes gave 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: mp 105°-106° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 1.50 (s, 3H), 1.95 (m, 2H), 2.27 (m, 2H), 5.34 (s, 4H), 6.98 (d, 4H, J=8 Hz), 7.10 (d, 4H, J=8 Hz), 7.65 (m, 4H), 7.80 (m, 2H), 8.00 (m, 4H), 8.42 (d, 2H, J=9 Hz), 12.00 (s, 1H); MS (DCl--NH 3 ) m/e 569 (M+H) + . Anal. Calc'd. for C 37 H 32 N 2 O 4 : C, 78.15; H, 5.67; N, 4.93. Found: C, 77.52; H, 5.88; N, 4.60.
EXAMPLE 2
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt
To a solution in dioxane (10 mL) and methanol (10 mL) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid (320 mg, 0.56 mmol), prepared as in step 1, was added aqueous 1N sodium hydroxide (0.55 ml, 0.55 mmol). The mixture was then concentrated in vacuo. The product was crystallized by dissolving in CH 2 Cl 2 and precipitation by dropwise addition of a mixture of ethyl acetate-ethyl ether (1:2): 1 H NMR (300 MHz, DMSO-d 6 ) d 1.47 (s, 3H), 1.63 (m, 2H), 2.18 (m, 2H), 5.31 (s, 4H), 6.95 (d, 4H, J=9 Hz), 7.08 (d, 4H, J=9 Hz), 7.64 (m, 4H), 7.78 (m, 2H), 8.00 (m, 4H), 8.40 (d, 2H, J=8 Hz); MS (FAB + ) m/e 591 (M+H) + ; (FAB - ) 589 (M-H) - . Anal. Calc'd. for C 37 H 31 N 2 O 4 Na.0.25 H 2 O:C, 74.67; H, 5.34; N, 4.71; Found: C, 74.57; H, 5.32; N, 4.52.
EXAMPLE 3
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid magnesium salt
To a stirred room temperature THF solution of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid (0.6 g, 1.06 mmol), prepared as in Example 1, was added MgO (0.021 g, 0.528 mmol). Water was added until the mixture became homogeneous. The reaction was allowed to stir for 24 hours. The solvent was removed in vacuo and the residue triturated with hexanes. The precipitate was vacuum filtered and washed with hexanes. The solid was dried in vacuo at 55° C. for 48 hours to give 0.510 g (83%) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid magnesium salt as a cream-colored powder: mp 96°-110° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 1.42 (s, 6H), 1.76 (m, 4H), 2.21 (m, 4H), 5.27 (s, 8H), 6.91 (d, 8H, J=7.5 Hz), 7.03 (d, 8H, J=7.5 Hz), 7.58 (m, 8H), 7.74 (t, 4H, J=7.5 Hz), 7.96 (m, 8H), 8.34 (m, 4H). Anal. Calc'd. for C 74 H 62 N 4 O 8 Mg.1.50 H 2 O: C, 74.90; H 5.52; N, 4.72. Found: C, 74.81; H, 5.64; N, 4.68.
EXAMPLE 4
Preparation of 4.4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol ##STR7##
To a mixture in THF (50 mL) of 4.4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid 2-quinolylmethyl ester (2.1 g, 3 mmol), prepared as in Example 1, and sodium borohydride (380 mg, 10 mmol) was added dropwise methanol at 50°-55° C. and the mixture was stirred for 30 minutes. The mixture was cooled to room temperature, poured into water (50 mL) and acidified to pH 4. The resulting mixture was extracted with ethyl acetate, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was purified by chromatography on silica gel (methylene chloride-ethyl acetate 3:1) to afford 1.46 g (88%) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol: 1 H NMR (300 MHz, DMSO-d 6 ) d 1.18 (m, 2H), 1.48 (s, 3H), 2.00 (m, 2H), 3.34 (m, 2H), 4.34 (t, 1H, J=6 Hz), 5.30 (s, 4H), 6.96 (d, 4H, J=9 Hz), 7.09 (d, 4H, J=9 Hz), 7.64 (m, 4H), 7.79 (m, 2H), 8.00 (t, 4H, J=8 Hz), 8.41 (d, 2H, J=8 Hz); MS (DCl--NH 3 ) m/e 555 (M+H) + . Anal. Calc'd. for C 37 H 34 N 2 O 3 .0.5 H 2 O: C, 78.84; H, 6.44; N, 4.97. Found: C, 78.67; H, 5.95; N, 4.70.
EXAMPLE 5
Preparation of 4,4bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!iminoxyacetic acid ##STR8## Step 1: N-phthaloyl-O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine
To a solution in THF (35 mL) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol (1.11 g, 2 mmol), prepared as in Example 4, N-hydroxyphthalimide (326 mg, 2 mmol) and triphenylphosphine (786 mg, 3 mmol) was added a solution of DIAD (0.6 ml, 3 mmol) in THF (5 mL), and the resulting mixture was stirred at room temperature for 10 hours. The reaction mixture was concentrated in vacuo and purified by chromatography on silica gel (methylene chloride-ethyl acetate 12:1) to provide 1.33 g of N-phthaloyl-O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine
Step 2: O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine
To a solution in dioxane (15 mL) and ethanol (15 mL) of the N-phthaloyl-O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine prepared in step 1 was added hydrazine hydrate (0.25 mL, 4 mmol) and the mixture was heated at reflux for 30 minutes. The mixture was then treated with aqueous 10% sodium carbonate (20 mL) and extracted with ethyl acetate. The organic extract was washed with water and brine, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was purified by chromatography on silica gel (ethyl acetate) to afford 420 mg of O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine.
Step 3: 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!iminoxyacetic acid
A solution in dioxane (10 mL), methanol (5 mL) and water (2 mL) of O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine (114 mg, 0.2 mmol), prepared as in step 2, glyoxylic acid (19 mg, 0.2 mmol) and acetic acid (0.012 mL, 0.2 mmol) was stirred at ambient temperature for 16 hours. The mixture was then concentrated in vacuo and the residue was dissolved in ethyl acetate (50 mL). The resulting solution was washed with water and brine, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was crystallized from methylene chloride-hexane to afford 108 mg (86%) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!iminoxyacetic acid: mp 80°-82° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 1.40 (m, 2H), 1.53 (s, 3H), 2.04 (m, 2H), 4.10 (t, 2H, J=7 Hz), 5.31 (s, 4H), 6.95 (d, 4H, J=9 Hz), 7.08 (d, 4H, J=9 Hz), 7.52 (s, 1H), 7.63 (m, 4H), 7.78 (m, 2H), 8.00 (m, 4H), 8.40 (d, 2H, J=8 Hz); MS (DCl--NH 3 ) m/e: 626 (M+H) + . Anal. Calc'd. for C 39 H 35 N 3 O 5 : C, 74.86; H, 5.64; N, 6.72; Found: C, 74.89; H, 6.03; N 6.42.
EXAMPLE 6
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid ##STR9## Step 1: 4,4-bis(4-(2-(quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid methyl ester
A mixture in dioxane (20 mL) and methanol (20 mL) of O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine (306 mg, 0.54 mmol), prepared as in Example 5, step 2, methyl pyruvate (0.055 mL, 0.55 mmol) and acetic acid (0.033 mL, 0.55 mmol) was stirred at room temperature for 12 hours. The mixture was then partitioned between aqueous 10% sodium bicarbonate and ethyl acetate. The ethyl acetate extract was washed with water and brine, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was purified by chromatography on silica gel (methylene chloride-ethyl acetate 4:1) to afford 320 mg of 4,4-bis(4-(2-quinolyl-methoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid methyl ester.
Step 2: 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid
The desired compound was prepared according to the method of Example 1, step 3, except substituting 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid methyl ester, prepared as in step 1, for 4,4-bis(4-(2-quinolylmethyl)phenyl)pentanoic acid methyl ester: mp 80°-82° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 1.42 (m, 2H), 1.53 (s, 3H), 1.90 (s, 3H), 2.05 (m, 2H), 4.11 (t, 2H, J=7 Hz), 5.33 (s, 4H), 6.95 (d, 4H, J=9 Hz), 7.09 (d, 4H, J=9 Hz), 7.64 (m, 4H), 7.78 (m, 2H), 8.00 (m, 4H), 8.41 (d, 2H, J=8 Hz); MS (DCl--NH 3 ) m/e 640 (M+H) + . Anal. Calc'd. for C 40 H 37 N 3 O 5 : C, 75.10; H, 5.83; N, 6.57. Found: C, 74.86; H, 6.11; N, 6.27.
EXAMPLE 7
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!oximinoacetic acid ##STR10## Step 1: 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanal
To a solution in DMSO (20 mL) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol (410 mg, 0.74 mmol), prepared as in Example 4, and 1,3-dicyclohexylcarbodiimide (515 mg, 2.5 mmol) was added aqueous 1M phosophoric acid (0.5 mL) and the resulting mixture was stirred at room temperature for 4 hours. Ethyl acetate (80 mL) was added and dicyclohexylurea was filtered off. The filtrate was washed with water and brine dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was purified by chromatography on silica gel (methylene chloride-ethyl acetate 9:1) to afford 280 mg of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanal.
Step 2: 4,4-bis(4-(2-quinolylmethoxy)phenylpent-1-yl!oximinoacetic acid
A mixture in dioxane (10 mL), methanol (10 mL) and water (5 mL) of the 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanal (280 mg, 0.5 mmol) prepared in step 1, carboxymethoxylamine hemihydrochloride (110 mg, 0.5 mmol), and sodium acetate trihydrate (69 mg, 0.5 mmol) was stirred at ambient temperature for 12 hours. The mixture was diluted with water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and brine, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was recrystallized from methylene chloridehexane to afford 250 mg (80 %) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!oximinoacetic acid: mp 78°-80° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 1.53 (s, 3H), 1.88 (m 1H), 2.05 (m, 1H), 2.22 (m, 2H), 4.40 and 4.45 (two s, 1:1, 2H), 5.34 (s, 4H), 6.75 and 7.45 (two t, 1:1, 1H), 6.96 (d, 4H, J=9 Hz), 7.10 (dd, 4H, J=9, 7 Hz), 7.64 (m, 4H), 7.78 (m, 2H), 8.00 (m, 4H), 8.41 (d, 2H, J=8 Hz), 12.62 (bs, 1H); MS (DCl--NH 3 ) m/e 626 (M+H) + . Anal. Calc'd. for C 39 H 35 N 3 O 5 .0.5 H 2 O: C, 73.79; H, 5.72; N, 6.62. Found: C, 73.94; H, 6.13; N, 6.68.
EXAMPLE 8
Preparation of 4,4-bis(4-(2-benzothiazoylmethoxy)phenyl)pentanoic acid ##STR11##
The desired product was prepared according to the procedure of Example 1, except substituting 2-chloromethylbenzothiazole for 2-chloromethylquinoline: mp 185°-186° C.; 1 H NMR (300 mHz, DMSO-d 6 ) d 1.60 (s, 3H), 1.94 (m, 2H), 2.29 (m, 2H), 5.05 (s, 4H), 7.01 (d, 4H, J=9 Hz), 7.13 (d, 4H, J=9 Hz), 7.50 (m, 4H), 8.03 (d, 2H, J=9 Hz), 8.13 (m, 2H), 12.04 (bs, 1H); MS (DCl--NH 3 ) m/e 598 (M+NH 4 ) + , 581 (M+H) + . Anal. Calc'd. for C 33 H 28 N 2 O 4 S 2 : C, 68.27; H, 4.86; N, 4.83. Found C, 68.06; H, 4.70; N, 4.64.
EXAMPLE 9
Preparation of 4,4bis(4-(2-benzothiazoylmethoxy)phenyl)pentanoic acid sodium salt
The desired salt was prepared according to the procedure of Example 2, except substituting 4,4-bis(4-(2-benzothiazoylmethoxy)phenyl)pentanoic acid, prepared as in Example 8, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid; mp 105°-108° C.; 1 H NMR (300 mHz, DMSO-d 6 ) d 1.48 (s, 3H), 1.58 (m, 2H), 2.19 (m, 2H), 5.54 (s, 4H), 6.98 (d, 4H, J=9 Hz), 7.10 (d, 4H, J=9 Hz), 7.5 (m, 4H), 8.01 (d, 2H, J=9 Hz), 8.11 (d, 2H, J=9 Hz). MS (FAB) m/e 625 (M+Na) + 603 (M+H) + . Anal. Calc'd. for C 33 H 27 N 2 O 4 SNa.1.5 H 2 O: C, 62.95; H, 4.80; N, 4.45. Found: C, 63.11; H, 4.72; N, 4.26.
EXAMPLE 10
Preparation of 4,4-bis(4-(7-chloro-2-quinolylmethoxy)phenyl)pentanoic acid ##STR12##
The desired compound was prepared according to the procedure of Example 1, except substituting 2 chloromethyl-7-chloroquinoline for 2-chloromethylquinoline: mp 88°-90° C.; 1 H NMR (300 mHz, DMSO-d 6 ) d 1.51 (s, 3H), 1.95 (m, 2H), 2.28 (m, 2H), 5.33 (s, 4H), 6.97 (d, 4H, J=9 Hz), 7.09 (d, 4H, J=9 Hz), 7.66 (dd, 2H, J=9, 2 Hz), 7.71 (d, 2H, J=9 Hz), 8.06 (m, 4H), 8.47 (d, 2H, J=9 Hz), 12.03 (bs, 1H); MS (DCl--NH 3 ) m/e 637 (M+H) + . Anal. Calc'd. for C 37 H 30 C 12 N 2 O 4 : C, 69.81; H, 4.75; N, 4.40. Found: C, 69.77; H, 5.05; N, 4.17.
EXAMPLE 11
Preparation of 4,4-bis(4-(6-fluoro-2-quinolylmethoxy)phenyl)pentanoic acid sodium salt ##STR13## Step 1: 4,4-bis(4-(6-fluoro-2-quinolylmethoxy)phenyl)pentanoic acid
The desired compound was prepared according to the procedure of Example 1, except substituting 2 chloromethyl-6-fluoroquinoline for 2-chloromethylquinoline.
Step 2: 4,4-bis(4-(6-fluoro-2-quinolylmethoxy)phenyl)pentanoic acid sodium salt
The desired salt was prepared according to the procedure of Example 2, except substituting 4,4-bis(4-(6-fluoro-2-quinolylmethoxy)phenyl)pentanoic acid, prepared as in step 1, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: mp 97°-99° C.; 1 H NMR (300 mHz, DMSO-d 6 ) d 1.48 (s, 3H), 1.70 (m, 2H), 2.1 (m, 2H), 5.31 (S, 4H), 6.95 (d, 4H, J=9 Hz), 7.08 (d, 4H, J=9 Hz), 7.68 (m, 4H), 7.80 (dd, 2H, J=9, 3 Hz), 8.08 (dd, 2H, J=9, 6 Hz), 8.41 (d, 2H); MS (FAB) m/e 627 (M+Na) + , 605 (M+H) + . Anal. Calc'd. for: C 37 H 29 F 2 N 2 O 4 Na: C, 70.92; H, 4.76; N 4.47. Found: C, 70.79; H, 4.84; N, 4.30.
EXAMPLE 12
Preparation of 2,2-bis(4-(2-quinolylmethoxy)phenyl)propionic acid ##STR14## Step 1: 2,2-bis(4-hydroxyphenylpropionic acid
To a cooled mixture of phenol (9.4 g, 0.1 mol), pyruvic acid (4.4 g, 0.05 mol), and water was added concentrated H 2 SO 4 (4.5 mL, 18.0 g) dropwise with stirring. After 15 minutes the ice bath was removed and the reaction was warmed to room temperature and stirred for 18 hours. The reaction mixture was diluted with ethyl ether/water (200 ml 1:1) and the layers were separated. The organic layer was extracted with saturated aqueous NaHCO 3 . The aqueous extract was then acidified, extracted with ethyl ether, dried over MgSO 4 , filtered, and concentrated in vacuo to give 2,2-bis(4-hydroxyphenyl)propionic acid (6.2 g) as a colorless sticky oil.
Step 2: 2,2-bis(4-(2-quinolylmethoxy)phenyl)propionic acid
The desired compound was prepared according to the method of Example 1, except substituting 2,2-bis(4-hydroxyphenyl)propionic acid, prepared as in step 1, for 4,4-bis(4-hydroxyphenyl)pentanoic acid: mp 208°-210° C.; 1 H NMR (300 mHz, DMSO-d 6 ) d 1.75 (s, 31H), 5.33 (s, 4H), 7.01 (d, 4H, J=9 Hz), 7.12 (d, 4H, J=9 Hz), 7.63 (m, 4H), 7.78 (m, 2H), 8.01 (t, 4H, J=8 Hz), 8.42 (d, 2H, J=8 Hz), 12.65 (bs, 1H); MS (DCl--NH 3 ) m/e 541 (M+H) + . Anal. Calc'd. for C 35 H 28 N 2 O 4 .H 2 O: C, 75.19; H, 5.28; N, 5.02. Found: C, 74.85; H, 4.89; N, 4.92.
EXAMPLE 13
Preparation of 3,3-bis(4-(2-quinolylmethoxy)phenyl)butanoic acid ##STR15##
The desired product was prepared according to the procedure of Example 12, except substituting ethyl acetoacetate for pyruvic acid and hydrolysis of the intermediate ethyl ester as described in Example 1, step 3: mp 94°-96° C.; 1 H NMR (300 mHz, DMSO-d 6 ) d 1.75 (s, 3H), 3.02 (s, 2H), 5.32 (s, 4H), 6.95 (d, 4H, J=9 Hz), 7.11 (d, 4H, J=9 Hz), 7.65 (m, 4H), 7.78 (m, 2H), 8.01 (t, 4H, J=8 Hz), 8.41 (d, 2H, J=8 Hz), 11.83 (bs, 1H); MS (DCl--NH 3 ) m/e 555 (M+H) + . Anal. Calc'd. for C 36 H 30 N 2 O 4 .0.5H 2 O: C, 76.71; H, 5.54; N, 4.95. Found: C, 76.23; H 5.43; N, 4.66.
EXAMPLE 14
Preparation of 5,5-bis(4-(2-quinolylmethoxy)phenyl)hexanoic acid ##STR16##
The desired compound was prepared according to the procedure of Example 12, except substituting 4-acetyl butyric acid for pyruvic acid: mp 87°-89° C.; 1 H NMR (300 mHz, DMSO-d 6 ) d 1.25 (m, 2H), 1.51 (s, 3H), 2.0 (m, 2H), 2.17 (t, 2H, J=8 Hz), 5.32 (s, 4H), 6.96 (d, 4H, J=9 Hz), 7.09 (d, 4H, J=9 Hz), 7.62 (m, 4H), 7.68 (d, 2H, J=9 Hz), 7.78 (m, 2H), 8.02 (t, 2H, J=8 Hz), 8.41 (d, 2H, J=8 Hz), 11.97 (bs, 1H); MS (FAB) m/e 583 (M+H) + . Anal. Calc'd. for C 38 H 34 N 2 O 4 : C, 78.34; H, 5.87; N, 4.81. Found: C, 77.97; H, 6.0; N, 4.63.
EXAMPLE 15
Preparation of 5,5-bis(4-(2-quinolylmethoxy)phenyl)hexanoic acid sodium salt
The desired compound was prepared according to the method of Example 2, except substituting 5,5-bis(4-(2-quinolylmethoxy)phenyl)hexanoic acid, prepared as in Example 14, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: 1 H NMR (300 mHz, DMSO-d 6 ) d 1.20 (m, 2H), 1.51 (s, 3H), 1.81 (t, 2H, J=8 Hz), 1.95 (m, 2H), 5.32 (s, 4H), 6.94 (d, 4H, J=9 Hz), 7.09 (d, 4H, J=9 Hz), 7.61 (t, 2H, J=8 Hz), 7.68 (d, 2H, J=8 Hz), 7.80 (m, 2H), 8.01 (t, 4H, J=8 Hz), 8.42 (d, 2H, J=8 Hz). MS (FAB) m/e 605 (M+Na) + , 583 (M+H) + . Anal. Calc'd. for C 38 H 33 N 2 O 4 Na.0.5 H 2 O: C, 74.39; H, 5.55; N, 4.57. Found: C, 74.64; H, 5.64; N, 4.36.
EXAMPLE 16
Preparation of 4,4-bis-(4-(2-pyridylmethoxy)phenyl)pentanoic acid sodium salt ##STR17## Step 1: 4,4-bis-(4-(2-pyridylmethoxy)phenyl)pentanoic acid
The desired compound was prepared according to the procedure of Example 1, except substituting 2-picolyl chloride for 2-chloromethylquinoline.
Step 2: 4,4-bis-(4-(2-pyridylmethoxy)phenyl)pentanoic acid sodium salt
The desired compound was prepared according to Example 2, except substituting 4,4bis-(4-(2-pyridylmethoxy)phenyl)pentanoic acid, prepared as in step 1, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: 1 H NMR (300 mHz, DMSO-d 6 ) d 1.49 (s, 3H), 1.53 (m, 2H), 2.21 (m, 2H), 5.13 (s, 4H), 6.92 (d, 4H, J=9 Hz), 7.08 (d, 4H, J=9 Hz), 7.34 (m, 2H), 7.51 (d, 2H, J=9 Hz), 7.34 (m, 2H), 7.51 (d, 2H, J=9 Hz), 7.84 (dt, 2H, J=9, 2 Hz), 8.56 (d, 2H, J=4.5 Hz); MS (FAB) m/e 491 (M+Na) + , 469 (M+H) + . Anal. Calc'd. for C 29 H 27 N 2 O 4 Na.0.5H 2 O: C, 69.72; H, 5.57; N, 5.57. Found: C, 69.45; H, 5.59; N, 5.29.
EXAMPLE 17
Preparation of 4,4-bis-(4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt ##STR18##
The desired compound was prepared according to Example 16, except substituting 2-chloromethylquinoxaline for 2-picolyl chloride: 1 H NMR (300 mHz, DMSO-d 6 ) d 1.49 (s, 3H), 1.66 (m, 2H), 2.22 (m, 2H), 5.42 (s, 4H), 6.99 (d, 4H, J=9 Hz), 7.11 (d, 4H, J=9 Hz), 7.88 (m, 4H), 8.11 (m, 4H), 9.11 (s, 2H); MS (FAB) m/e 593 (M+Na) + , 571 (M+H) + . Anal. Calc'd. for C 35 H 29 N 4 O 4 Na.H 2 O: C, 68.91; H, 5.11; N, 9.19. Found: C, 68.58, H, 5.15, N, 8.99.
EXAMPLE 18
Preparation of 4,4-bis(4-(1-methyl-2-benzimidazolylmethoxy)phenyl)pentanoic acid ##STR19##
The desired product was prepared according to the procedure of Example 1, except substituting 1-methyl-2-chloromethylbenzimidazole for 2-chloromethylquinoline: mp 110°-112° C.; 1 H NMR (300 MHz; DMSO-d 6 ) d 1.52 (s, 3H), 1.95 (m, 2H), 2.28 (m, 2H), 3.85 (s, 6H), 5.37 (s, 4H), 7.02 (d, 4H, J=9 Hz), 7.10 (d, 4H, J=9 Hz), 7.35 (m, 4H), 7.56 (m, 2H), 7.64 (m, 2H), 12.00 (bs, 1H); MS (FAB+) m/e 575 (M+H) + ; (FAB-) m/e 573 (M-H) - . Anal. Calc'd. for C 35 H 34 N 4 O 4 .H 2 O: C, 70.93; H, 6.12; N, 9.45. Found: C, 70.79; H, 6.11; N 8.87.
EXAMPLE 19
Preparation of 4,4-bis(4-(1-methyl-2-benzimidazolylmethoxy)phenyl)pentanoic acid sodium salt
The desired product was prepared according to the method of Example 2, except substituting 4,4-bis(4-(1-methyl-2-benzimidazolylmethoxy)phenyl)pentanoic acid, prepared as in Example 18, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: 1 H NMR (300 MHz, DMSO-d 6 ) d 1.48 (s, 3H), 1.60 (m, 2H), 2.20 (m, 2H), 3.85 (s, 6H), 5.35 (s, 4H), 7.00 (d, 4H, J=9 Hz), 7.09 (d, 4H, J=9 Hz), 7.35 (m, 4H), 7.56 (m, 2H), 7.64 (m, 2H); MS (FAB+) m/e 597 (M+Na) + , 575 (M+H) + , (FAB-) m/e 573 (M-H) - . Anal. Calc'd. for C 35 H 33 N 4 O 4 Na.1.5H 2 O: C, 67.53; H, 5.81; N, 9.00. Found: C, 67.50; H, 5.85; N, 8.56.
EXAMPLE 20
Preparation of 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid ##STR20## Step 1: 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid methyl ester
A mixture of 4,4-bis(4-hydroxyphenyl)pentanoic acid (5.72 g, 20 mmol), and N-chlorosuccinimide (5.84 g, 44 mmol) in chloroform (120 mL) and dioxane (30 mL) was heated at reflux for 5 hours. The reaction mixture was concentrated in vacuo and the residue was dissolved in methanol (100 mL). The methanol solution was cooled to -70° C., thionyl chloride (3 mL) was added, and the mixture was left at ambient temperature for 16 hours. The methanol was removed in vacuo and DMF (150 mL), potassium carbonate (13.8 g, 100 mmol) and 2-chloromethyl-quinoline hydrochloride (9 g, 42 mmol) were added to the residue. The resulting mixture was stirred at room temperature for 10 hours. The mixture was diluted with water (400 mL) and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was purified by chromatography on silica gel (methylene chloride-ethyl acetate 15:1) to afford 8 g of 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid methyl ester and 1.2 g of 4-(3-chloro-4-(2-quinolylmethoxy)phenyl)-4-(3,5-dichloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid methyl ester.
Step 2: 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid
The desired compound was prepared according to the method of Example 1, step 3, except substituting 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid methyl ester, prepared as in step 1, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid methyl ester: mp 91°-94° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 1.53 (s, 3H), 1.96 (m, 2H), 2,30 (m, 2H), 5.44 (s, 4H), 7.09 (dd, 2H, J=3, 9 Hz), 7.20 (d, 2H, J=9 Hz), 7.24 (d, 2H, J=3Hz), 7.62 (m, 2H), 7.71 (d, 2H, J=9 Hz), 7.80 (m, 2H), 8.00 (m, 4H), 8.44 (d, 2H, J=9 Hz), 12.08 (bs, 1H); MS (DCl--NH 3 ) m/e 637 (M+H) + . Anal. Calc'd. for C 37 H 30 Cl 2 N 2 O 4 ×H 2 O: C, 67.79; H, 4.92; N, 4.27. Found: C, 68.02; H, 4.85; N, 3.94.
EXAMPLE 21
Preparation of 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid sodium salt
The desired product was prepared according to the method of Example 2, except substituting 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentanoic acid, prepared as in Example 20, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: 1 H NMR (300 MHz, DMSO-d 6 ) d 1.47 (s, 3H), 1.85 (m, 2H), 2.25 (m, 2H), 5.43 (s, 4H), 7.06 (dd, 2H, J=3, J=9 Hz), 7.18 (d, 2H, J=9 Hz), 7.22 (d, 2H, J=3 Hz), 7.61 (m, 2H), 7.71 (d, 2H, J=9 Hz), 7.79 (m, 2H), 8.00 (m, 4H), 8.42 (d, 2H, J=9 Hz); MS (FAB+) m/e 659 (M+Na) + , 637 (M+H) + , MS (FAB-) m/e 635 (M-H) - . Anal. Calc'd. for C 37 H 29 Cl 2 N 2 O 4 Na: C, 67.38; H, 4.43; N, 4.25. Found: C, 67.74; H, 4.89; N, 3.96.
EXAMPLE 22
Preparation of 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid sodium salt ##STR21## Step 1: 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentan-1-ol
The desired compound was prepared according to the method of Example 4, except substituting 4,4-Bis(3-chloro-4-hydroxyphenyl)pentanoic acid, prepared as in Example 20, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid.
Step 2: O- 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine
The desired compound was prepared according to the method of Example 5, steps 1 and 2, except substituting 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pentan-1-ol, prepared as in step 1, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol.
Step 3: 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid
The desired compound was prepared according to the method of Example 6, except substituting O- 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine, prepared as in step 2, for O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine.
Step 4: 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid sodium salt
The desired compound was prepared according to the method of Example 2, except substituting 4,4-bis(3-chloro-4-(2-quinolylmethoxy)phenyl)pent-1-yl!-2-iminoxypropionic acid, prepared as in step 3, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: 1 H NMR (300 MHz, DMSO-d 6 ) d 1.31 (m, 2H), 1.54 (s, 3H), 1.79 (s, 3H), 2.04 (m, 2H), 3.93 (t, 2H, J=7 Hz), 5.42 (s, 4H), 7.09 (dd, 2H, J=3, 9 Hz), 7.20 (m, 4H), 7.62 (m, 2H), 7.71 (d, 2H, J=8 Hz), 7.80 (m, 2H), 8.00 (m, 4H), 8.44 (d, 2H, J=8 Hz); MS (FAB+) m/e 730 (M+Na) + , 708 (M+H) + , (FAB-) m/e 706 (M-H) - . Anal. Calc'd. for C 40 H 34 N 3 Cl 2 O5Na.H 2 O: C, 64.17; H, 4.84; N, 5.61. Found: C, 64.40; H, 4.87; N, 5.37.
EXAMPLE 23
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid N,N-diethylhydroxylamine ester ##STR22##
To a solution in methylene chloride (10 mL) of 4,4-bis-(4-(2-quinolylmethoxy)phenyl) pentanoic acid (570 mg, 1 mmol), prepared as in Example 1, was added 1,1'-carbonyldiimidazole (162 mg, 1.1 mmol) and the resulting mixture was stirred at room temperature for 25 minutes. N,N-Diethylhydroxylamine (0.14 mL, 1.2 mmol) was then added and stirring was continued for additional 30 minutes. The solution was concentrated in vacuo and the residue was purified by chromatography on silica gel (methylene chloride-ethyl acetate 4:1) to afford 420 mg (66%) of 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid N,N-diethylhydroxylamine ester: 1 H NMR (300 MHz, DMSO-d 6 ) d 0.92 (t, 6H, J=7 Hz), 1.51 (s, 3H), 2.03 (m, 2H), 2.30 (m, 2H), 2.75 (q, 4H, J=7 Hz), 5.32 (s, 4H), 6.98 (d, 4H, J=9 Hz), 7.09 (d, 4H, J=9 Hz), 7.65 (m, 4H), 7.78 (m, 2H), 8.00 (m, 4H), 8.41 (d, 2H, J=9 Hz); MS (DCl--NH 3 ) m/e 640 (M+H) + . Anal. Calc'd. for C 41 H 41 N 3 O 4 : C, 76.97; H, 6.46; N, 6.57. Found: C, 76.82; H, 6.49; N, 6.50.
EXAMPLE 24
Preparation of 2,2-bis(4-(2-quinolylmethoxy)phenyl)butyric acid ##STR23##
The desired product was prepared according to the procedure of Example 12, except substituting 2-ketobutyric acid for pyruvic acid: mp 83°-92° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 0.65 (m, 3H), 2.25 (m, 2H), 5.35 (s, 4H), 7.00 (d, 4H, J=9 Hz), 7.16 (d, 4H, J=9 Hz), 7.63 (m, 2H), 7.68 (d, 2H, J=9 Hz), 7.79 (m, 2H), 8.01 (m, 4H), 8.42 (d, 2H, J=9 Hz), 12.54 (br s, 1H); MS (DCl--NH 3 ) m/e 555 (M+H) + . Anal. Calc'd. for C 36 H 30 N 2 O 4 .0.55 H 2 O: C, 76.59; H, 5.55; N, 4.96. Found: C, 76.90; H, 5.78; N, 4.57.
EXAMPLE 25
Preparation of 1,1-bis(4-(2-quinolylmethoxy)phenyl)ethanol ##STR24## Step 1: bis(4-(2-quinolylmethoxy)phenyl) ketone
To a solution of 4-4'-dihydroxybenzophenone (4.22 g, 20 mmol) and K 2 CO 3 (16.5 g, 120 mmol) in DMF (75 mL) was added 2-chloromethylquinoline hydrochloride (8.56 g, 40 mmol) and the resulting solution was stirred at 60° C. or 16 hours. The reaction mixture was then poured into ice water (100 mL and the resulting solid was collected by filtration, slurried in 20% ether/hexane, filtered, and dried in vacuo to afford bis(4-(2-quinolylmethoxy)phenyl) ketone (9.3 g, 94%) as white solid.
Step 2: 1,1-bis(4-(2-quinolylmethoxy)phenyl)ethanol
To a -78° C. solution in THF (20 mL) of bis(4-(2-quinolylmethoxy)phenyl) ketone (992 mg, 2 mmol), prepared as in step 1, was added methylmagnesium bromide (3M solution in ethyl ether, 0.8 mL, 2.4 mmol) and the resulting mixture was stirred at room temperature for 12 hours. The mixture was then quenched with saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was washed with water and brine, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was purified by chromatography on silica gel (methylene chloride-ethyl acetate 4:1) to afford 920 mg (90%) of 1,1-bis(4-(2-quinolylmethoxy)phenyl)ethanol: mp 129°-131° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 1.74 (s, 3H), 5.32 (s, 4H), 5.48 (s, 1H), 6.95 (d, 4H, J=9 Hz), 7.30 (d, 4H, J=9 Hz), 7.63 (m, 4H), 7.78 (m, 2H), 8.01 (m, 4H), 8.39 (d, 2H, J=8 Hz); MS (DCl--NH 3 ) m/e 513 (M+H) + . Anal. Calc'd. for C 34 H 28 N 2 O 3 : C, 79.67; H, 5.51; N, 5.46. Found: C, 79.48; H, 5.62; N, 5.25.
EXAMPLE 26
Preparation of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt ##STR25## Step 1: 2,2-dimethyl-3,3-bis(4-hydroxyphenyl)propionic acid methyl ester
To a stirred 0° C. solution in methanol (2 mL) of phenol (3.76 g, 40 mmol) and methyl-3-carboxaldehyde-2,2-dimethyl propionate (2.6 g, 20 mmol) was added dropwise 10 g of sulfuric acid. The deep red solution was stirred in the ice bath for 0.5 hours and at room temperature for an additional 3 hours. The mixture was poured into 300 mL water and extracted with ether (2×300 mL). The combined ether extracts were washed twice with saturated aqueous NaHCO 3 , twice with waters and once with brine. The organic layer was dried over MgSO 4 , filtered, and concentrated in vacuo. The residue purified by column chromatography on silica gel (35% ethyl acetate/hexanes) to give 1.1 g (18%) of methyl ester intermediate as a white semisolid.
Step 2: 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid methyl ester
To a stirred solution in DMF (50 mL) of 2,2-dimethyl-3,3-bis(4-hydroxyphenyl)propionic acid methyl ester (1.1 g, 3.7 mmol), prepared as in step 1, was added Cs 2 CO 3 (2.5 g, 7.7 mmol) and the mixture stirred 0.5 hours at room temperature. 2-Chloromethyquinoline (1.37 g, 7.7 mmol) was added as a solid in small portions. The reaction mixture was stirred overnight at room temperature. The mixture was poured into 300 mL of water and extracted with ether (2×200 mL). Brine was added to the aqueous layer and it was extracted twice with ether. The combined ether extracts were washed with brine, dried over MgSO 4 , filtered, and concentrated in vacuo to give a light yellow oil. Chromatography on silica gel (40% ethyl acetate/hexanes) gave 1.68 g (78%) of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid methyl ester as a white foam.
Step 3: 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid
To a solution in methanol (8 mL) and THF (4 mL) of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid methyl ester (0.4 g, 0.69 mmol), prepared as in step 2, was added LiOH.H 2 O (4 ml, 4 mmole, 1M solution) dropwise, and the mixture was stirred overnight after which an additional 2 mL of the LiOH solution was added and the mixture was stirred an additional 24 hours. The mixture was concentrated to dryness, acidified with excess 0.5M citric acid, diluted with water and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine, dried over MgSO 4 , filtered, and concentrated in vacuo. Purification by chromatography on silica gel (7% MeOH/CH 2 Cl 2 ) provided 0.16 g (40%) of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid as a white solid: mp 124°-127° C. Anal. Calc'd. for C 37 H 32 N 2 O 4 : C, 78.14; H, 5.67; N 4.92. Found C, 77.45; H, 5.74; N, 4.67.
Step 4: 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt
To a solution in THF (10 mL) and ethanol (8 mL) of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid (0.128 g, 0.225 mmol), prepared as in step 3, was added one equivalent of NaOH (2.3 mL, 0.1N NaOH). The reaction was stirred for 1 hour at room temperature, concentrated, and dried under high vacuum to provide 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt as a white powder 0.13 g (99%): mp 250°-255° C. (dec); 1 H NMR (300 MHz, DMSO-d 6 ) d 0.91 (s, 6H), 4.46 (s, 1H), 5.29 (s, 4H), 6.87 (d, 4H, J=9 Hz), 7.15 (d, 4H, J=9 Hz), 7.61 (m, 2H), 7.67 (d, 4H, J=9 Hz), 7.78 (m, 2H), 8.00 (t, 4H, J=9 Hz), 8.40 (d, 2H, J=9 Hz); MS m/e (FAB+) 569 (M+H) + , (FAB-) 567 (M-H) - . Anal. Calc'd. for C 37 H 31 N 2 O 4 Na.0.5 H 2 O: C, 74.10; H, 5.37; N 4.67. Found C, 74.02; H, 5.24; N, 4.50.
EXAMPLE 27
Preparation of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)prop-1-yl!oximinoacetic acid sodium salt ##STR26## Step 1: 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propan-1-ol
To a stirred solution in THF (50 mL) at ambient temperature of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid methyl ester (1.33 g, 2.28 mmole), prepared as in Example 26, step 2, was added LiAlH 4 (0.09 g, 2.5 mmol) in a single portion. The mixture was stirred 3 hours at ambient temperature. Water (0.1 mL) was added followed by aqueous 1N NaOH (0.1 ml) and water (0.5 mL). The mixture was then concentrated to dryness and partitioned between water and ethyl acetate. The organic layer was washed with brine, dried over MgSO 4 , filtered, and concentrated in vacuo. Purification by chromatography on silica gel (60% ethylacetate/hexanes) gave 1.01 g (80%) of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)-propan-1-ol as a yellow foam.
Step 2: 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propanal
To a -78° C. solution in methylene chloride (15 mL) of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propan-1-ol (0.4 g, 0.72 mmol), prepared as in step 1, and DMSO (0.17 g, 2.17 mmol) was added oxalyl chloride (0.14 g, 1.08 mmol) and the reaction mixture was stirred for 0.5 hours. Triethylamine (0.37 g, 3.6 mmol) was added via syringe, the ice bath was removed, and the reaction was allowed to warm to room temperature. The mixture was concentrated in vacuo and triturated with dry THF. The THF solution was filtered and washed with additional THF. The THF solution and washings were combined and concentrated in vacuo to give crude 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propanal which was used without further purification for oxime formation.
Step 3: 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)prop-1-yl!oximinoacetic acid
The desired compound was prepared according to the method of Example 7, step 2, except substituting 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propanal, prepared as in step 2, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanal.
Step 4: 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)prop-1-yl!oximinoacetic acid sodium salt
The desired compound was prepared according to the method of Example 2, except substituting 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)prop-1-yl!oximinoacetic acid, prepared as in step 2, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: 1 H NMR (300 MHz, DMSO-d 6 ) d 1.03 (s, 6H), 3.89 (s, 1H), 4.06 (s, 2H), 5.32 (s, 4H), 6.97 (d, 4H, J=9 Hz), 7.31 (d, 4H, J=9 Hz), 7.46 (s, 1H), 7.65 (m, 4H), 7.78 (m, 2H), 8.01 (t, 4H, J=9 Hz), 8.40 (d, 2H, J=9 Hz); MS (FAB+) m/e 648 (M+Na) 30 , 626 (M+H) + .
EXAMPLE 28
Preparation of 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)-1-propyliminoxyacetic acid ##STR27##
The desired compound was prepared according to the method of Example 5, except substituting 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)propan-1-ol prepared as in Example 27, step 1, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol: Amorphous white solid, softens at 125° C. (decompose over next 40° C. range); 1 H NMR (300 MHz, DMSO-d 6 ) d 0.94 (s, 6H), 3.68 (s, 2H), 3.90 (s, 1H), 5.41 (s, 4H), 6.96 (d, 4H, J=9 Hz), 7.36 (d, 4H, J=9 Hz), 7.41 (m, 2H) 7.63 (m, 4H), 7.78 (m, 2H), 8.00 (t, 4H, J=9 Hz), 8.39 (d, 2H, J=9 Hz). Anal. Calc'd. for C 39 H 35 N 3 O 5 N.2.0 H 2 O: C, 70.78; H, 5.94; N 6.34. Found C, 71.25; H, 5.28; N 6.39.
EXAMPLE 29
Preparation of 2,2-bis(4-(2-quinolymethoxy)phenyl)acetic acid ##STR28##
The title compound was prepared according to the procedure of Example 12, except substituting glyoxylic acid for pyruvic acid: mp 119°-128° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 4.91 (s, 1H), 5.34 (s, 4H), 7.01 (d, 4H, J=7.5 Hz), 7.23 (d, 4H, J=7.5 Hz), 7.62 (t, 2H, J=7.5 Hz), 7.66 (d, 2H, J=7.5 Hz), 7.79 (t, 2H, J=7.5 Hz), 8.01 (t, 4H, J=7.5 Hz), 8.40 (d, 2H, J=7.5 Hz). MS (DCl--NH 3 ) m/e 527 (M+H) + . Anal. Calc'd. for C 34 H 26 N 2 O 4 .H 2 O: C, 74.98; H, 5.18; N, 5.14. Found: C, 74.97; H, 4.75; N, 5.02.
EXAMPLE 30
Preparation of 2,2-bis(4-(6-fluoro-2-quinolymethoxy)phenyl)acetic acid ##STR29##
The title compound was prepared according to the procedure of Example 12, except substituting glyoxylic acid for pyruvic acid, and substituting 2-chloromethyl-6-fluoroquinoline for 2-chloromethylquinoline: mp 221°-223° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 4.92 (s, 1H), 5.33 (s, 4H), 7.01 (d, 4H, J=7.5 Hz), 7.23 (d, 4H, J=7.5 Hz), 7.70 (m, 4H), 7.82 (dd, 2H, J=2.5, 9.0 Hz), 8.08 (m, 2H), 8.40 (d, 2H, J=7.5 Hz); MS (DCl--NH 3 ) m/e 563(M+H) + . Anal. Calc'd. for C 34 H 26 N 2 O 4 : C, 72.59; H, 4.30; N, 4.97. Found: C, 72.36; H, 4.22; N, 4.76.
EXAMPLE 31
Preparation of 2,2-bis(4-(2-quinolylmethoxy)phenyl)eth-1-yloximinoacetic acid ##STR30## Step 1: 2,2-bis(4-(2-quinolymethoxy)phenyl)acetic acid methyl ester
The desired compound was prepared according to the method of Example 1; steps 1 and 2, except substituting 2,2-bis(4-hydroxyphenyl)acetic acid, prepared as in Example 29, for 4,4-bis(4-hydroxyphenyl)pentanoic acid.
Step 2: 2,2-bis(4-(2-quinolylmethoxy)phenyl)eth-1-yloximinoacetic acid
The title compound was prepared according to the procedure of Example 27, steps 1-3, except substituting 2,2-bis(4hydroxyphenyl)acetic acid methyl ester, prepared as in step 1, for methyl 2,2-dimethyl-3,3-bis(4-(2-quinolylmethoxy)phenyl)-propionate: mp 104°-108° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 4.18 (s, 2H), 4.72 (d, 1H, J=7.5 Hz), 5.33 (s, 4H), 7.01 (d, 4H, J=7.5 Hz), 7.28 (d, 4H, J=7.5 Hz), 7.64 (m, 4H), 7.78 (t, 2H, J=7.5 Hz), 7.98 (m, 5H), 8.40 (d, 2H, J=7.5 Hz); MS (FAB+) m/e 584 (M+H) + , (FAB-) m/e 582 (M-H) - . Anal. Calc'd. for C 36 H 29 N 3 O 5 .1.5 H 2 O: C, 70.80; H, 5.28; N, 6.88. Found: C, 71.07; H, 5.03; N, 6.61.
EXAMPLE 32
Preparation of 2,2-bis(4-(2-quinolylmethoxy)phenyl)eth-1-yloximinoacetic acid sodium salt
The desired compound was prepared according to the method of Example 2, except substituting 2,2-bis(4-(2-quinolylmethoxy)phenyl)-1-ethyloximinoacetic acid, prepared as in Example 31, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: mp 138°-145° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 4.04 (s, 2H), 4.12 (s, 1H), 4.72 (d, 1H, J=7.5 Hz), 5.33 (s, 4H), 7.01 (d, 4H, J=7.5 Hz), 7.28 (d, 4H, J=7.5 Hz), 7.64 (m, 4H), 7.78 (t, 2H, J=7.5 Hz), 8.00 (m, 4H), 8.40 (d, 2H, J=7.5 Hz). MS (DCl--NH 3 ) m/e 606 (M+Na) + , 584 (M+H) + .
EXAMPLE 33
Preparation of 3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid ##STR31##
The desired compound was prepared according to the procedure of Example 26, except substituting ethyl 3,3-diethoxypropionate in ethanol for methyl 3-carboxaldehyde-2,2-dimethyl propionate in methanol: mp 94°-111° C; 1 H NMR (300 MHz, DMSO-d 6 ) d 2.93 (d, 2H, J=7.5 Hz), 4.31 (t, 1H, J=7.5 Hz), 5.31 (s, 4H), 6.95 (d, 4H, J=8.0 Hz), 7.23 (d, 4H, J=8.0 Hz), 7.62 (m, 4H), 7.78 (t, 2H, J=7.5 Hz), 8.00 (t, 4H, J=7.5 Hz), 8.40 (d, 2H, J=7.5 Hz); MS (DCl--NH 3 ) m/e 541 (M+H) + . Anal. Calc'd. for C 35 H 28 N 2 O 4 .H 2 O: C, 75.25; H, 5.41; N, 5.01. Found: C, 75.09; H, 5.19; N, 4.93.
EXAMPLE 34
Preparation of 3,3-bis(4-(2-quinolylmethoxy)phenyl)propionic acid sodium salt
The desired compound was prepared according to the method of Example 2, except substituting 3,3-bis( 4 -(2-quinolylmethoxy)phenyl)propionic acid, prepared as in Example 33, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: mp 224°-232° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 2.44 (d, 2H, J=7.5 Hz), 4.31 (t, 1H, J=7.5 Hz), 5.29 (s, 4H), 6.89 (d, 4H, J=9.0 Hz), 7.12 (d, 4H, J=9.0 Hz), 7.62 (m, 4H), 7.78 (t, 2H, J=7.5 Hz), 8.00 (t, 4H, J=7.5 Hz), 8.40 (d, 2H, J=7.5 Hz); MS (DCl--NH 3 ) m/e 541 (M+H) + .
EXAMPLE 35
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)acetic acid-N-carboxymethyl amide ##STR32## Step 1: 2,2-bis(4-hydroxyphenyl)acetic acid-N-carboxymethyl amide
To a stirred solution in CH 2 Cl 2 (0.5 mL), THF (20 mL), and pyridine (20 mL) of 2,2-bis(4-hydroxyphenyl)acetic acid (0.94 g, 3.85 mmol), prepared as in Example 31, was added 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (1.10 g, 5.76 mmol), glycine methyl ester hydrochloride (0.723 g, 5.76 mmol), and N-methylmorpholine (0.63 mL, 5,76 mmol) and the mixture was stirred overnight at room temperature. The reaction mixture was then diluted with ethyl acetate and aqueous 0.5N HCl. The organic layer was washed with 0.5N HCl (3×), saturated aqueous NaHCO 3 (3×), and brine, dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was dried to constant weight on high vacuum to give 1.05 g (87%) of 2,2-bis(4-hydroxyphenyl)acetic acid-N-carboxymethyl amide.
Step 2: 4,4-bis(4-(2-quinolylmethoxy)phenyl)acetic acid-N-carboxymethyl amide
The desired compound was prepared according to the method of Example 1, steps 1-3, except substituting 2,2-bis(4-hydroxyphenyl)acetic acid-N-carboxymethyl amide, prepared as in step 1, for 4,4-bis(4-hydroxyphenyl)pentanoic acid: mp 228°-231° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 3.79 (d, 2H, J=6.5 Hz), 4.93 (s, 1H), 5.34 (s, 4H), 7.00 (d, 4H, J=7.5 Hz), 7.22 (d, 4H, J=7.5), 7.63 (m, 4H), 7.79 (t, 2H, J=7.5 Hz), 8.01 (m, 4H), 8.44 (m, 3H), 12.52 (s, 1H); MS (DCl--NH 3 ) m/e 584 (M+H) + . Anal. Calc'd. for C 36 H 29 N 3 O 5 : C, 74.08; H,5.01; N, 7.20. Found: C, 73.81; H, 5.20; N, 6.90.
EXAMPLE 36
Preparation of 3,3-bis-(2-quinolylmethoxyphenyl)but-1-yl!-2-iminoxypropionic acid ##STR33## Step 1: 3,3-bis(4-(2-quinolylmethoxy)phenyl)butan-1-ol
To a 0° C. solution in THF (40 mL) of 3,3-bis(4-(2-quinolylmethoxy)phenyl)butanoic acid ethyl ester (3.2 g, 5.5 mmol), prepared as in Example 13, was added slowly a solution of LiAlH 4 (1.0M, 6 mL, 6.0 mmol). The mixture was stirred for 2 hours and water (15 mL) was added slowly followed by aqueous 1N NaOH. The reaction mixture was diluted with THF (20 mL) and the mixture was filtered through a celite pad. The filtrate was extracted with ether and the organic extract was washed with water and brine, dried over MgSO 4 , filtered, and concentrated in vacuo to provide 3,3-bis(4-(2-quinolylmethoxy)phenyl)butan-1-ol (2.4 g) as a pale yellow foam.
Step 2: O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)but-1-yl!hydroxylamine
The desired compound was prepared according to the method of Example 5, steps 1 and 2, except substituting 3,3-bis(4-(2-quinolylmethoxy)phenyl)butan-1-ol, prepared as in step 1, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentan-1-ol.
Step 3: 3,3-bis-(2-quinolylmethoxyphenyl)but-1-yl!-2-iminoxypropionic acid
The desired compound was prepared according to the method of Example 6, except substituting O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)but-1-yl!hydroxylamine for O- 4,4-bis(4-(2-quinolylmethoxy)phenyl)pent-1-yl!hydroxylamine: mp 94°-96° C.; 1 H NMR (300 MHz, DMSO-d 6 ), d 1.58 (s, 3H), 1.80 (s, 3H), 2.39 (m, 2H), 3.85 (m, 2H), 5.32 (s, 4H), 6.97 (d, 4H, J=9Hz), 7.11 (d, 4H, J=9Hz), 7.64 (m, 4H), 7.78 (m, 2H), 7.99 (t, 4H, J=9 Hz), 8.41 (d, 2H, J=9 Hz). MS (FAB) m/e 626 (M+H) + . Anal. Calc'd. for: C 39 H 35 N 3 O 5 .H 2 O: C, 72.71; H, 5.47; N, 6.53. Found: C, 72.35; H, 5.42; N, 6.40.
EXAMPLE 37
Preparation of 4,4-bis(4-(2-quinolylmethoxy)phenyl)-4-hydroxy-2-butynoic acid ##STR34## Step 1: 4,4-bis(2-quinolylmethoxy)phenyl)-4-hydroxy-2-butynoic acid methyl ester
To a -78° C. solution in THF (40 mL) of bis(4-(2-quinolylmethoxy)phenyl) ketone (980 mg, 2 mmol), prepared as in Example 25, step 1, and propiolic acid (0.19 ml, 3 mmol) was added LDA (1.5M solution in THF, 4 mL, 6 mmol) and the mixture was left at room temperature for 24 hours. The reaction mixture was diluted with water, acidified to pH 5, and extracted with ethyl acetate. The organic phase was dried over MgSO 4 , filtered, and concentrated in vacuo. The residue was dissolved in DMF (40 mL) and treated with methyl iodide (2 mL) and sodium bicarbonate (170 mg, 2 mmol). The reaction mixture was stirred for 24 hours and then was poured into water. The layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with brine, dried over MgSO 4 , filtered, and concentrated in vacuo. Chromatography on silica gel (methylene chloride-ethyl acetate 4:1) provided 730 mg (63%) of 4,4-bis(2-quinolylmethoxy)phenyl)-4-hydroxy-2-butynoic acid methyl ester.
Step 2: 4,4-bis(4-(2-quinolylmethoxy)phenyl)-4-hydroxy-2-butynoic acid
The desired compound was prepared according to the method of Example 1, step 3, except substituting 4,4-bis(2-quinolylmethoxy)phenyl)-4-hydroxy-2-butynoic acid methyl ester, prepared as in step 1, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: mp 169°-172° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d 5.35 (s, 4H), 7.04 (d, 4H, J=9 Hz), 7.37 (d, 4H, J=9 Hz), 7.63 (m, 4H), 7.78 (m, 2H), 8.00 (m, 4H), 8.40 (d, 2H, J=8 Hz), 13.75 (bs, 1H); MS (DCl--NH 3 ) m/e: 567 (M+H) + . Anal. Calc'd. for C 36 H 26 N 2 O 4 .0.5 H 2 O: C, 75.12; H, 4.73; N, 4.89. Found: 75.19; H, 4.80; N, 4.60.
EXAMPLE 38
Preparation of 5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-pentyn-1-yl!-2-iminoxypropionic acid sodium salt ##STR35## Step 1: 5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-butyn-1-ol
To a -50° C. solution in THF (25 mL) of bis(4-(2-quinolylmethoxy)phenyl) ketone (496 mg, 1 mmol), prepared as in Example 25 was added a solution of dilithium salt of 3-butyn-1-ol (prepared by addition of 1.5M LDA (3 mL) to 3-butyn-1-ol (0.15 mL, 2 mmol) at -50° C.) and the reaction mixture was allowed to warm to room temperature. The mixture was stirred for 12 hours at room temperature and then was quenched with saturated aqueous ammonium chloride. The layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with brine, dried over MgSO 4 , filtered, and concentrated in vacuo. Chromatography on silica gel (silica gel, ethyl acetate) provided 400 mg of 5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-butyn-1-ol.
Step 2: 5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-pentyn-1-yl!-2-iminoxypropionic acid
The desired compound was prepared according to the method of Example 36, steps 2, and 3, except substituting 5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-butyn-1-ol, prepared as in step 1, for 3,3-bis(4-(2-quinolylmethoxy)phenyl)butan-1-ol.
Step 3: 5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-pentyn-1-yl!-2-iminoxypropionic acid sodium salt
The desired compound was prepared according to the method of Example 2, except substituting 5,5-bis(4-(2-quinolylmethoxy)phenyl)-5-hydroxy-3-pentyn-1-yl!-2-iminoxypropionic acid, prepared as in Step 2, for 4,4-bis(4-(2-quinolylmethoxy)phenyl)pentanoic acid: mp 108°-111° C.; 1 H NMR (300 MHz, DMSO-d 6 ) d: 1.83 (s, 3H), 2.61 (t, 2H, J=7 Hz), 4.10 (t, 2H, J=7 Hz), 5.32 (s, 4H), 6.96 (d, 4H, J=9 Hz), 7.40 (d, 4H, J=9 Hz), 7.62 (m, 4H), 7.78 (m, 2H), 8.00 (m, 4H), 8.40 (d, 2H, J=8 Hz); MS (FAB+) m/e 674 (M+Na) + , 652 (M+H) + , (FAB-) m/e 651 (M-H)-. Anal. Calc'd. for C 40 H 32 N 3 O 6 Na.H 2 O: C, 69.46; H, 4.95; N, 6.07. Found: C, 69.62; H, 5.10; N, 5.61.
The following additional examples are prepared according to the method described in Example 1, except substituting the requisite heteroarylmethylhalide W--CH 2 X where X is Cl, Br, or I for 2-chloromethylquinoline hydrochloride.
EXAMPLE 39
4,4-bis(4-(2-benzoxazolylmethoxy)phenyl)pentanoic acid ##STR36##
EXAMPLE 40
4,4-bis(4-(2-pyrimidylmethoxy)phenyl pentanoic acid ##STR37##
EXAMPLE 41
4,4-bis(4-(4-phenyl-2-thiazolylmethoxy)phenyl)pentanoic acid ##STR38##
EXAMPLE 42
4,4-bis(4-(4-(pyrid-2-yl)-2-thiazolylmethoxy)phenyl)pentanoic acid ##STR39##
EXAMPLE 43
4,4-bis(4-(6-phenyl-2-pyridylmethoxy)phenyl)pentanoic acid ##STR40##
EXAMPLE 44
4,4-bis(4-(5-phenyl-2-pyridylmethoxy)phenyl)pentanoic acid ##STR41##
EXAMPLE 45
4,4-bis(4-(6-(pyrid-2-yl)-2-pyridylmethoxy)phenyl)pentanoic acid ##STR42##
EXAMPLE 46
4,4-bis(4-(4-phenyl-2-pyrimidylmethoxy)phenyl)pentanoic acid ##STR43## | Compounds having the formula: ##STR1## wherein W is the same at each occurrence and is selected from optionally substituted quinolyl, optionally substituted benzothiazolyl, optionally substituted benzoxazolyl, optionally substituted benzimidazolyl, optionally substituted quinoxalyl, optionally substituted pyridyl, optionally substituted pyrimidyl, and optionally substituted thiazolyl; R 1 and R 2 are independently selected from hydrogen, alkyl, halolalkyl, alkoxy, halogen; R 3 is a valence bond or is selected from hydrogen and alkyl; X is a valence bond or is selected from alkylene, alkenylen, and alkynylene; and Z is selected from (a) COM, (b) CH═N--O--A--COM, (c) CH 2 --O--N═A--COM wherein A is selected from alkylene and cycloalkylene, and M is selected from (a) a pharmaceutically acceptable metabolically cleavable group, (b) --OR 6 , (c) --NR 7 R 8 , (d) --NR 6 SO 2 R 9 , (e) --NH-Tetrazolyl, and (f) glycinyl inhibit leukotriene biosynthesis and are useful in the treatment of allergic and inflammatory disease states. Also disclosed are leukotriene biosynthesis inhibiting compositions and a method of inhibiting leukotriene biosynthesis. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application Ser. No. 60/676,697, filed in of the United States Patent and Trademark Office on Apr. 29, 2005, the disclosure of which is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] This invention relates to variable air volume (VAV) ceiling diffusers and more particularly to a thermally powered VAV ceiling diffuser.
BACKGROUND OF THE INVENTION
[0003] Thermal powered VAV ceiling diffusers are widely used in HVAC systems to control the temperature within an occupied space. The VAV ceiling diffuser is connected to a heating and cooling duct of the HVAC system. The heating and cooling duct supplies either warm or cool air to the diffuser. The diffuser has thermal sensors/actuators that sense the temperature of the air supplied in the duct and the temperature of the occupied space. Based on the sensed temperatures, the thermal sensors/actuators drive a linkage that opens and closes a damper to increase or decrease the amount of heating or cooling air supplied to the occupied space in order to maintain a relatively constant temperature in the occupied space.
[0004] The prior art discloses a number of thermal powered VAV ceiling diffusers that employ various linkages for controlling the movement of the damper in response to the duct temperature and the room temperature. Because the sensors/actuators provide limited movement, the linkages must be able to translate that limited movement into accurate positioning for the damper in order to control the temperature in the occupied space.
SUMMARY OF THE INVENTION
[0005] In order to control the temperature within the occupied space accurately, the thermal powered VAV ceiling diffuser of the present invention incorporates a number of features that enhance the accuracy of the temperature control. The ceiling diffuser of the present invention is mounted in the ceiling of the occupied space and is connected to an HVAC duct that supplies warm or cool air to the inlet of the diffuser. The diffuser controls the temperature within the occupied space by controlling the amount of heating or cooling air passing through the inlet and into the occupied space from the HVAC duct. The diffuser includes a diffuser hood from which a base plate is suspended. The diffuser has a circular damper stack mounted on the base plate of the diffuser and a damper with a circular opening that slides vertically on the damper stack between an upper closed inlet position and a lower open inlet position. The damper is raised and lowered by a linkage that is controlled by a duct temperature sensor/actuator and one or more room temperature sensors/actuators.
[0006] The linkage includes two horizontal slides, a heating slide movable for the heating mode and a cooling slide movable for the cooling mode. The horizontal movements of the heating and cooling slides are controlled by the duct temperature sensor/actuator and the one or more room temperature sensors/actuators. The differential movement between the heating and cooling slides moves a roller that engages a profiled cam surface attached to two lever arms. One end of each of the lever arms is pivotally mounted at one end of the base plate for rotation about an axis, and the other end of each of the lever arms engages the bottom of the damper. As the roller moves along the cam surface, the lever arms pivot about their axis of rotation so that the damper moves upward to close the air inlet and downward to open the air inlet.
[0007] By reducing the friction in the linkage and the loading on the linkage, temperature control accuracy is enhanced. In order to reduce the load on the linkage required to move the damper up and down, the lever arms are spring loaded to offset the weight of the damper. In addition, in one embodiment of the invention, the damper stack and the opening in the damper are circular so that the damper can rotate about the damper stack thereby reducing binding between the damper stack and the damper. Temperature control accuracy is further enhanced by means of the roller and profiled cam surface that together accurately translate the differential sliding movement of the heating and cooling slides into an accurate rotational movement of the lever arms.
[0008] In operation, the duct temperature sensor/actuator senses the temperature of the air in the duct and activates the heating mode slide when the duct temperature is warm and activates the cooling mode slide when the duct temperature is cool. In the heating mode, the duct temperature sensor/actuator holds the cooling slide stationery while the two room temperature sensors/actuators control the movement of the heating slide by means of a heating set point knob attached to the two room temperature sensors/actuators. The differential movement between the stationary cooling slide and the movable heating slide controls the roller that engages the profiled cam surface attached to the two lever arms. The movement of the two lever arms raises and lowers the damper to control the flow of warm air through the diffuser.
[0009] In the cooling mode, the duct temperature sensor/actuator holds the heating slide stationery while the two room temperature sensors/actuators control the movement of the cooling slide by means of a cooling set point knob attached to the two room temperature sensors/actuators. The differential movement between the stationary heating slide and the movable cooling slide controls the roller that engages the profiled cam surface attached to the two lever arms. The movement of the two lever arms raises and lowers the damper to control the flow of cool air through the diffuser. The set point knobs are independently adjustable to set the heating temperature and the cooling temperature in the occupied space.
[0010] The diffuser of the present invention further has a single means for setting the minimum flow rate as well as setting the fully open damper position for HVAC system balancing. Raising and lowering the axis of rotation of the lever arms controls the minimum flow rate and the fully opened position of the damper.
[0011] In order to gain access to adjust the minimum flow rate, the fully open damper position, and the heating and cooling set points, the diffuser has a plaque that is hinged on one side to the base plate so that the plaque can swing away from the base plate of the diffuser. The other side of the plaque is latched to the base plate by means of rare earth magnets that hold the plaque in its closed position.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a top plan view of the variable air volume ceiling diffuser with a movable damper in accordance with the present invention.
[0013] FIG. 2 is a top plan view of the diffuser backing hood of the variable air volume ceiling diffuser in accordance with the present invention.
[0014] FIG. 3 is a side elevation view of the variable air volume ceiling diffuser with a movable damper in accordance with the present invention.
[0015] FIG. 4 is a detailed view of the base plate hangers and hanger locks of the variable air volume ceiling diffuser in accordance with the present invention.
[0016] FIG. 5 is an end elevation view of the variable air volume ceiling diffuser and showing the fully open and minimum air adjustment mechanism in accordance with the present invention.
[0017] FIG. 6 a is a plan view of the linkage of the variable air volume ceiling diffuser in the heating mode with the damper closed in accordance with the present invention.
[0018] FIG. 6 b is a plan view of the linkage of the variable air volume ceiling diffuser in the cooling mode with the damper closed in accordance with the present invention.
[0019] FIG. 7 a is a section view of the ceiling diffuser taken along section line 7 - 7 of FIG. 1 and showing the linkage for controlling movement of the damper (heating mode, damper closed) in accordance with the present invention.
[0020] FIG. 7 b is a section view of the ceiling diffuser taken along section line 7 - 7 of FIG. 1 and showing the linkage for controlling movement of the damper (cooling mode, damper closed) in accordance with the present invention.
[0021] FIG. 8 a is a detailed plan view of the linkage of the variable air volume ceiling diffuser in the heating mode with the damper closed in accordance with the present invention.
[0022] FIG. 8 b is a detailed plan view of the linkage of the variable air volume ceiling diffuser in the cooling mode with the damper closed in accordance with the present invention.
[0023] FIG. 9 a is a detailed plan view of the linkage of the variable air volume ceiling diffuser in the heating mode with the damper open in accordance with the present invention.
[0024] FIG. 9 b is a detailed plan view of the linkage of the variable air volume ceiling diffuser in the cooling mode with the damper open in accordance with the present invention.
[0025] FIG. 10 is a detailed plan view of the temperature set point linkage of the variable air volume ceiling diffuser in the heating mode with the damper closed in accordance with the present invention.
[0026] FIG. 11 is a bottom plan view of the variable air volume ceiling diffuser with a movable damper in accordance with the present invention.
[0027] FIG. 12 is a perspective view of the variable air volume ceiling diffuser with a movable damper having a contoured profile in accordance with the present invention.
[0028] FIG. 13 is end elevation view of the variable air volume ceiling diffuser and showing the contoured damper profile in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0029] Referring now to the drawings, in which like reference numerals represent like parts throughout the several views, FIG. 1 shows a variable air volume (VAV) ceiling diffuser 10 . The diffuser 10 comprises a diffuser hood 12 , a base plate 20 hung from the hood 12 by means of base plate hangers 22 ( FIG. 3 ) and hanger slots 23 ( FIG. 2 ), a cylindrical damper stack 32 supported by the base plate 20 , a damper 42 slideably and rotatably supported on the damper stack 32 , a supply temperature actuator 46 , a first room temperature actuator 60 , a second room temperature actuator 70 , and a damper control linkage 44 ( FIGS. 3, 7 a , and 7 b ) for controlling the movement of the damper 42 along the height of the damper stack 32 .
[0030] As shown in FIG. 4 , the base plate hanger 22 has a hanger lock 24 that, when closed, locks the base plate hanger 22 into the hanger slot 23 of the diffuser hood 12 . As shown in FIGS. 3 and 5 , a plaque 26 is connected to the base plate 20 by means of a plaque hinge 28 at one end and a plaque latch 30 at the opposite end. The plaque latch 30 comprises two rare earth magnets.
[0031] As best shown in FIG. 3 , the diffuser hood 12 includes a short air inlet 14 and a flared air outlet 16 . The air inlet 14 is connected to an air duct for receiving warm or cool air supplied by an HVAC system. The diffuser hood 12 also has a relief 13 at the flared air outlet 16 that interfaces with a ceiling system of an occupied space.
[0032] The damper 42 , shown in FIGS. 3, 5 , 7 a , and 7 b , is slidably mounted on the damper stack 32 by means of a damper bushing 41 . The damper stack 32 and the damper bushing 41 are circular in cross-section so that the damper 42 can rotate freely about the damper stack 32 as the damper 42 slides up and down, thereby reducing the chances of the damper 42 binding as it slides on the damper stack 32 . The damper 42 slides vertically along the damper stack 32 in response to changes in room air temperature and supply air temperature as will be more fully explained below. When the damper 42 is in the upper position and in contact with air inlet 14 , the damper 42 shuts off the flow of air through the diffuser 10 to the occupied space except for a small amount of air flowing through the damper stack 32 . As the damper 42 travels downwardly and away from contact with the air inlet 14 , the damper 42 allows proportionately more air through the diffuser 10 into the occupied space.
[0033] With continuing reference to FIGS. 3, 7 a , and 7 b , the cylindrical damper stack 32 is mounted on the base plate 20 and protrudes upwardly into the center of the air inlet section 14 . The damper stack 32 has an upper opening 33 that receives warm or cool air from the air duct and a lower end 35 that is covered by a converging deflector 18 ( FIG. 11 ) connected to the base plate 20 . The converging deflector 18 has a restricted discharge opening 19 ( FIGS. 3, 7 a , 7 b , and 11 ). The damper stack 32 further has a keyhole opening 36 adjacent the lower end 35 of the damper stack 32 . The supply temperature actuator 46 , which has a supply temperature actuator body 45 and a supply temperature actuator piston 47 ( FIGS. 7 a , 7 b , 8 a , 8 b , 9 a , and 9 b ), is mounted on the base plate 20 by means of a supply temperature bracket 48 connected to the body at 45 of supply temperature actuator 46 . The supply temperature actuator 46 extends through the keyhole opening 36 , and the body 45 of the supply temperature actuator 46 is exposed the warm or cool supply air that enters the damper stack 32 through the upper opening 33 .
[0034] The piston 47 of the supply temperature actuator 46 is biased to a retracted position by means of a compression supply temperature bias spring 52 . A first end 53 (left in FIGS. 8 a , 8 b , 9 a , and 9 b ) of the bias spring 52 is constrained by tab 55 fixed to the body 45 of the supply temperature actuator 46 . A second end 54 (right in FIGS. 8 a , 8 b , 9 a , and 9 b ) of the spring 52 engages a second end 51 of a spring keeper 49 . A first end 50 (left in FIGS. 8 a , 8 b , 9 a , and 9 b ) of the spring keeper 49 is connected to the piston 47 of the supply temperature actuator 46 . The compression bias spring 52 serves to return the piston 47 of the actuator 46 to its retracted position when cool supply air is present within the damper stack 32 . When warm air is present in the damper stack 32 , the piston 47 of the supply temperature actuator 46 extends against the spring force of the bias spring 52 and compresses the bias spring 52 .
[0035] With reference to FIGS. 7 a , 7 b , and 10 , the first room temperature actuator 60 includes a first room temperature actuator body 63 . The body 63 of the first room temperature actuator 60 is affixed to the base plate 20 by means of first room temperature actuator bracket 62 . The second room temperature actuator 70 includes a second room temperature actuator body 73 . The first room temperature actuator 60 and the second room temperature actuator 70 share a common piston 61 . The body 73 of the second room temperature actuator 70 is slidably mounted on the common piston 61 .
[0036] With reference to FIGS. 6 a , 6 b , 7 a , 7 b , and 10 , a set point mechanism 102 is part of the damper control linkage 44 and comprises a slide activator bar 104 , a threaded heating rod 110 with a heating set point knob 112 , and a threaded cooling rod 106 with a cooling set point knob 108 . The threaded heating rod 110 is connected to one end of the slide activator bar 104 , and the threaded cooling rod 106 is connected to the other end of the slide activator bar 104 . The slide activator bar 104 is connected to the body 73 of the second room temperature actuator 70 . Room temperature bias springs 114 and 116 are connected to each end of the slide activator bar 104 . The other ends of the bias springs 114 and 116 are connected to the base plate 20 by means of anchor posts 118 and 120 . The bias springs 114 and 116 cause the common piston 61 to retract into both the first room temperature actuator body 63 and the second room temperature actuator body 73 .
[0037] With reference to FIGS. 1, 3 , 7 a , and 7 b , a room temperature actuator cover 38 is supported by the base plate 20 and extents over and around the first room temperature actuator 60 and the second room temperature actuator 70 . The room temperature actuator cover 38 has a room temperature air inlet 40 in communication with the occupied space. As warm or cool air enters the upper opening 33 of the damper stack 32 under pressure, the air passes across the supply temperature actuator 46 and exits through the restricted discharge opening 19 of the converging deflector 18 . As the air exits through the restricted discharge opening 19 of the converging deflector 18 , the restricted discharged opening 19 creates a jet of air moving from right to left in FIGS. 7 a and 7 b . The jet creates low pressure at the inlet 40 of the actuator cover 38 thereby pulling room temperature air into the air inlet 40 and across the first room temperature actuator 60 and the second room temperature actuator 70 .
[0038] With reference to FIGS. 6 a , 6 b , 7 a , and 7 b , the damper control linkage 44 further includes a heating mode slide 74 , a cooling mode slide 80 , a slide inverter mechanism 130 , a cam actuator or roller 131 , a cam lift profile 132 , a lever mounting bracket 92 , and lever arms 90 and 91 for rotation about a lever axis 94 . A pair of lever bias springs 95 biases the levers 90 and 91 in a counterclockwise direction about the lever axis 94 ( FIGS. 7 a and 7 b ) tending to raise the damper 42 toward its upper closed position. Consequently, the lever bias springs 95 help to offset the weight of the damper 42 . The mounting bracket 92 has bracket slots 96 ( FIG. 3 ) which allowed the lever axis 94 to be raised and lowered with respect to the base plate 20 . The lever axis 94 is raised and lowered by means of a minimum air adjustment mechanism 98 ( FIG. 5 ). The minimum air adjustment mechanism 98 comprises a bushing 99 engaging the lever axis 94 and a minimum air adjustment screw 100 that threads into the adjustment bushing 99 and is captured by the base plate 20 . By turning the minimum air adjustment screw 100 , the adjustment bushing 99 and the lever axis 94 are raised or lowered in the bracket slots 96 with respect to the base plate 20 .
[0039] Turning to FIGS. 3 and 7 a , the heating mode slide 74 has a body portion 75 that extents along the length of the diffuser 10 . The body portion 75 of the heating mode slide 74 has a generally inverted U-shaped cross-section with cutouts to accommodate, for example, the damper stack 32 and the dual set point mechanism 102 . The heating mode slide 74 has a downwardly extending control tab 76 ( FIGS. 3 and 10 ) with a hole adjacent the dual set point mechanism 102 that engages the threaded heating rod 110 . The heating mode slide 74 also has a first inverter mechanism pivot 136 and a second inverter mechanism pivot 139 (left side of FIGS. 7 a and 7 b ) and a downwardly extending stop tab 78 midway between the ends of the heating mode slide 74 .
[0040] The cooling mode slide 80 has a body portion 81 that extents along the length of the diffuser 10 . The body portion 81 of the cooling mode slide 80 has a generally inverted U-shaped cross-section with cutouts to accommodate, for example, the damper stack 32 and the dual set point mechanism 102 . The cooling mode slide 80 has a downwardly extending control tab 82 ( FIGS. 7 a , 7 b , and 10 ) with a hole adjacent the dual set point mechanism 102 (right side of FIGS. 7 a and 7 b ) that engages the threaded heating rod 106 . The cooling mode slide 80 also has a pair of horizontal slots 83 ( FIG. 3 , left side of FIGS. 7 a and 7 b ) and a downwardly extending stop tab 84 midway between the ends of the cooling mode slide 80 .
[0041] The heating mode slide 74 is nested within and underneath the cooling mode slide 80 so that the heating mode slide 74 and the cooling mode slide are free to slide with respect to each other and with respect to the base plate 20 . The base plate 20 has heating base plate tabs 79 and cooling base plate tabs 85 ( FIGS. 8 a , 8 b , 9 a , and 9 b ). The heating base plate tabs 79 engage the heating mode slide stop tab 78 to arrest the movement of the heating mode slide 74 from moving to the right in FIGS. 6 a , 6 b , 7 a , 7 b , 8 a , 8 b , 9 a , and 9 b . The cooling base plate tabs 85 engage the cooling mode slide stop tab 84 to arrest the movement of the cooling mode slide 80 to the left in FIGS. 6 a , 6 b , 7 a , 7 b , 8 a , 8 b , 9 a , and 9 b.
[0042] Turning to FIGS. 8 a , 8 b , 9 a , and 9 b , the slide inverter mechanism 130 includes an inverter mechanism base 133 attached to the base plate 20 of the diffuser 10 . The cam actuator or roller 131 is attached to an inverter mechanism slide 134 that is captured by the inverter mechanism base 133 and that is free to slide horizontally on the inverter mechanism base 133 . The inverter mechanism slide 134 has a vertical slide post 135 . The vertical slide post 135 is captured by a first lever slot 138 of a first inverter mechanism lever 137 and by a second lever slot 141 of a second inverter mechanism lever 140 . The first inverter mechanism lever 137 pivots about the first inverter mechanism pivot 136 , and the second inverter mechanism lever 140 pivots about the second inverter mechanism pivot 139 . As previously disclosed, the first inverter mechanism pivot 136 and the second inverter mechanism pivot 139 are fixed to the heating mode slide 74 . The cooling mode slide slot 83 on one side 145 of the cooling mode slide 80 captures an end 143 of the first inverter mechanism lever 137 . Likewise, the cooling mode slide slot 83 on the opposite side 146 of the cooling mode slide 80 captures an end 144 of the second inverter mechanism lever 140 .
[0043] The heating mode operation of the diffuser 10 is illustrated with reference to FIGS. 6 a , 7 a , and 8 a that show the diffuser 10 in the heating mode with the damper 42 closed, and the cooling mode operation of the diffuser 10 is illustrated with reference to FIGS. 6 b , 7 b , and 8 b that show the diffuser 10 in the cooling mode with the damper 42 closed. FIG. 9 a shows the diffuser 10 in the heating mode with the damper 42 open, and FIG. 9 b shows the diffuser 10 in the cooling mode with the damper 42 open.
[0044] In the heating mode, warm air enters the upper damper stack opening 33 from the air inlet 14 of the diffuser 10 . The warm air passes through the damper stack 32 and exits through the restricted discharge opening 19 thereby drawing room temperature air into the room air inlet 40 of the actuator cover 38 and across the first room temperature actuator 60 and the second room temperature actuator 70 . If the duct air is warm and the room air is warm, the damper 42 is closed as shown in FIGS. 6 a , 7 a , and 8 a . Specifically, the warm air inside the damper stack 32 impinges on the supply temperature actuator 46 and causes the supply temperature actuator piston 47 to extend against the resistance of the supply temperature bias spring 52 . The extended supply temperature actuator piston 47 engages the cooling mode slide stop tab 84 and pins the cooling mode slide stop tab 84 against the cooling mode base plate tabs 85 on the base plate 20 thereby holding the cooling mode slide 80 in the leftward position shown in FIGS. 6 a , 7 a , and 8 a.
[0045] Because the room temperature is warm, the common piston 61 of the first room temperature actuator 60 and the second temperature actuator 70 is extended from the first room temperature actuator body 63 and from the second room temperature actuator body 73 . The extension of the common piston 61 forces the body 73 of the second room temperature actuator 70 to the right most position shown in FIGS. 6 a and 7 a . Because the slide activator bar 104 is attached to the body 73 of the second room temperature actuator 70 , the slide activator bar 104 is positioned in the right most position shown in FIGS. 6 a and 7 a . As a result, the threaded cooling rod 106 and the threaded heating rod 110 are in the right most position as well. The heating knob 112 on the threaded heating rod 110 engages the heating mode slide control tab 76 so that the heating mode slide 74 is positioned toward the right in FIGS. 6 a and 7 a . With the heating mode slide 74 positioned toward the right, the first inverter mechanism lever 137 and the second inverter mechanism lever 140 are rotated as shown in FIG. 8 a . In that position, the inverter mechanism levers 137 and 140 pull the slide post 135 toward the right. As a result, the cam roller 131 engages the cam lift profiled 132 at its rightward most position as shown in FIG. 7 a . When of the cam roller 131 is in the rightward most position, the lever arms 90 and 91 are pivoted counterclockwise about the lever axis 94 to raise the damper 42 to its upper closed position.
[0046] As the temperature in the occupied space decreases, the cooler room temperature air is drawn into the inlet 40 of the actuator cover 38 . The cooler room temperature air causes the common piston 61 to retract into both the first room temperature actuator 60 and the second room temperature actuator 70 as a result of the spring tension from bias springs 114 and 116 . As the common piston 61 retracts, the body 73 of the second room temperature actuator 70 moves to the left ( FIGS. 6 a , 7 a , and 8 a ) carrying with it the slide activator bar 104 , the threaded cooling rod 106 , and the threaded heating rod 110 . As the threaded heating rod 110 moves left, the heating knob 112 also moves left allowing the heating mode slide 74 to move to the left under the influence of the force provided by the weight of the damper 42 transmitted through the lever arms 90 and 91 , the cam lift profile 132 , the cam roller 131 , and the slide inverter mechanism 130 . As the heating mode slide 74 moves left, the first inverter mechanism pivot 136 and the second inverter mechanism pivot 139 attached to the heating mode slide 74 also move to the left causing the first inverter mechanism lever 137 to rotate clockwise and the second inverter mechanism lever 140 to rotate counterclockwise. The rotation of the first inverter mechanism lever 137 and the second inverter mechanism lever 140 drives the cam roller 131 toward the left. As the cam roller 131 moves to the left, the lift profile 132 allows the lever arms 90 and 91 to rotate clockwise about the lever axis 94 thereby lowering the damper 42 to allow warm air to enter the occupied space below the diffuser 10 to raise the temperature in the occupied space. In the heating mode with the damper 42 open, the positioning of the first inverter mechanism lever 137 , the second inverter mechanism lever 140 , and the inverter mechanism slide 134 are shown in FIG. 9 a.
[0047] In the cooling mode, cool air enters the upper damper stack opening 33 from the air inlet 14 of the diffuser 10 . The cool air passes through the damper stack 32 and exits through the restricted discharge opening 19 thereby drawing room temperature air into the room air inlet 40 of the actuator cover 38 and across the first room temperature actuator 60 and the second room temperature actuator 70 . If the duct air is cool and the room temperature air is cool, the damper 42 is closed as shown in FIGS. 6 b , 7 b , and 8 b . Specifically, the cool air inside the damper stack 32 impinges on the supply temperature actuator 46 and causes the supply temperature actuator piston 47 to retract under the influence of the bias spring 52 . As the supply temperature actuator piston 47 retracts, the right end 54 of the spring 52 and the right end 51 of the spring keeper 49 move to the right and pin the heating mode slide stop tab 78 against the heating base plate tab 79 thereby holding the heating mode slide 74 in the rightward position shown in FIGS. 6 b , 7 b , and 8 b.
[0048] Because the room temperature is cool, the common piston 61 is retracted into the first room temperature actuator 60 and the second temperature actuator 70 as a result of the room temperature bias springs 114 and 116 . The retraction of the common piston 61 causes the body 73 of the second room temperature actuator 70 to the left most position shown in FIGS. 6 b and 7 b . Because the slide activator bar 104 is attached to the body 73 of the second room temperature actuator 70 , the slide activator bar 104 is positioned in the left most position shown in FIGS. 6 b and 7 b . As a result, the threaded cooling rod 106 and the threaded heating rod 110 are in the left most position as well. The cooling knob 108 on the threaded cooling rod 106 engages the cooling mode slide control tab 82 so that the cooling mode slide 80 is position toward the left in FIGS. 6 b and 7 b . With the cooling mode slide 80 positioned toward the left, the first inverter mechanism lever 137 and the second inverter mechanism lever 140 are rotated as shown in FIG. 8 b . In that position, the inverter mechanism levers 137 and 140 pull the slide post 135 toward the right. As a result, the cam roller 131 engages the cam lift profiled 132 at its rightward most position as shown in FIG. 7 b . When of the cam roller 131 is in the rightward most position, the lever arms 90 and 91 are pivoted counterclockwise about the lever axis 94 to raise the damper 42 to its upper closed position.
[0049] As the temperature in the room increases, the warmer room temperature air is drawn into the inlet 40 of the actuator cover 38 . The warmer room temperature air causes the common piston 61 to extend from both the first room temperature actuator 60 and the second room temperature actuator 70 against the spring tension of bias springs 114 and 116 . As the common piston 61 extents, the of body 73 of the second room temperature actuator 70 moves to the right ( FIGS. 6 b , 7 b , and 8 b ) carrying with it the slide activator bar 104 , the threaded cooling rod 106 , and the threaded heating rod 110 . As the threaded cooling rod 106 moves right, the cooling knob 108 also moves right allowing the cooling mode slide 80 to move to the right as a result of the force provided by the weight of the damper 42 transmitted through the lever arms 90 and 91 , the cam lift profile 132 , the cam roller 131 , and the slide inverter mechanism 130 . As the cooling mode slide 80 moves right, cooling mode slide slots 83 attached to the cooling mode slide 80 also move to the right causing the first inverter mechanism lever 137 to rotate clockwise and the second inverter mechanism lever 140 to rotate counterclockwise. The rotation of the first inverter mechanism lever 137 and the second inverter mechanism lever 140 drives the cam roller 131 toward the left. As the cam roller 131 moves to the left, the lift profile 132 allows the lever arms 90 and 91 to rotate clockwise thereby lowering the damper 42 to allow cool air to enter the occupied space below the diffuser 10 . In the cooling mode with the damper 42 open, the positioning of the first inverter mechanism lever 137 , the second inverter mechanism lever 140 , and the inverter mechanism slide 134 are shown in FIG. 9 b.
[0050] The engineered cam lift profile 132 allows the small differential horizontal motion of the heating mode slide 74 and the cooling mode slide 80 described above to be amplified and predictably converted into a vertical motion of the damper 42 .
[0051] With reference to FIG. 10 , the temperature in the occupied space is set in the heating mode by adjusting the heating knob 112 along the threaded heating rod 110 . Similarly, the temperature in the occupied space is set in the cooling mode by adjusting the cooling knob 108 along the threaded cooling rod 106 . Particularly, in the heating mode, moving the heating knob 112 toward the left in FIGS. 6 a , 7 a , 8 a , and 10 increases the temperature in the occupied space. Similarly, in the cooling mode, moving the cooling knob 108 toward the right in FIGS. 6 b , 7 b , 8 b , and 10 increases the temperature in the occupied space. Set point indices 113 ( FIG. 11 ) may be provided adjacent the set point knobs 108 and 112 to aid in the adjustment of the set point knobs 108 and 112 . The set point knobs 108 and 112 are accessible from the occupied space below the diffuser by simply opening the plaque 26 .
[0052] In connection with the installation of the diffuser 10 as part of a complete HVAC system, the damper 42 is set to its fully open position in order to balance the HVAC system to which the diffuser 10 is connected. In order to set the damper 42 is set to its fully open position, the adjustment screw 100 ( FIG. 5 ) is rotated in order to raise the lever axis 94 in the bracket slots 96 ( FIG. 3 ). Visible indices 115 ( FIG. 11 ) are provided around the head of the adjustment screw 100 in order to facilitate adjustment to the fully open position. The adjustment screw 100 in conjunction with the adjustment bushing 99 also controls the minimum air opening for the damper 42 . Again, by adjusting the lever axis 94 up or down, the minimum airflow is set for the damper 42 . Further, the indices 115 around the head of the adjustment screw 100 provide assistance in facilitating the adjustment of the minimum airflow for the damper 42 . The airflow adjustment screw 100 is accessible from the occupied space below the diffuser by simply opening the plaque 26 .
[0053] FIGS. 12 and 13 show an alternative embodiment of the ceiling diffuser 210 in accordance with the present invention. Particularly, the alternative embodiment has a profiled damper 242 having an upper section 154 , a transition section 156 , and a lower section 152 . The profiled damper 242 has a damper bushing 241 that is slidably mounted on a modified damper stack 232 . The modified damper stack 232 has splines 150 spaced about the outside circumference of the damper stack 232 and extending vertically along the outside of the damper stack 232 . The splines engage matching recesses 158 on the damper bushing 241 so that the bushing 241 cannot be angularly displaced about the damper stack 232 as the damper 242 is raised and lowered. The profiled damper 242 minimizes noise when the damper 242 is in its fully opened position as shown in FIGS. 12 and 13 .
[0054] While this invention has been described with reference to preferred embodiments thereof, it is to be understood that variations and modifications can be affected within the spirit and scope of the invention as described herein and as described in the appended claims. | A variable air volume ceiling diffuser includes a damper that is raised and lowered by a linkage that is controlled by a duct temperature sensor/actuator and one or more room temperature sensors/actuators. The linkage includes a heating slide movable for the heating mode and a cooling slide movable for the cooling mode. The duct temperature sensor/actuator selects the heating slide for movement by the room temperature sensors/actuators in the heating mode and selects the cooling slide for movement by the room temperature sensors/actuators in the cooling mode. The differential movement between the heating and cooling slides moves a roller that engages a profiled cam surface attached to two lever arms. As the roller moves along the cam surface, the lever arms pivot about their axis of rotation so that the damper moves upward to close the air inlet and downward to open the air inlet. | 5 |
This is a continuation of application Ser. No. 523,853, filed Nov. 14, 1974 and now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to devices for mounting lenses, particularly ophthalmic lenses, in edge grinding machines of the type in which the lens is gripped between a pair of pads at the ends of coaxial rotatable shafts in a movable head of the machine, so that the edge of the lens is presented to a grinding wheel. Fixed to one of the shafts so as to rotate with it is a template of the desired shape of the lens. By cooperating with a stationary stop or anvil, the template limits the extent to which the shaft axis can approach the grinding wheel. As the lens is slowly rotated against the surface of the rapidly rotating grinding wheel, the edge of the lens is progressively ground away until the lens has the same shape as the template.
It is necessary that the lens be accurately positioned in relation to the template so that it is optically correct when fitted into the spectacle frame. Not only must the optical centre of the lens be correctly located relative to the shaft axis (usually but not always, the centre will lie on this axis) but also, in the case of a lens having a cylindrical component of surface curvature, the cylinder axis must be orientated at the ophthalmically prescribed angle in relation to the horizontal.
A usual procedure is to place the already surfaceground and polished lens in an instrument which enables the power (magnification) of the lens to be checked, the lens centred, and cylindrical axis angularly oriented in relation to the horizontal as prescribed. The lens is then marked with removable marks to indicate its optical centre and its correct horizontal axis. These marks enable the lens to be mounted in the edge grinding machine in the correct position, both as regards optical centre and axis orientation, in relation to the template.
Various devices are used for mounting the lens in the machine in the correct position, but all have certain disadvantages which the present invention avoids.
SUMMARY OF THE INVENTION
According to the invention a device for mounting a lens in an edge grinding machine comprises a flexible base adapted to be adhesively secured to the lens surface, and a key projecting from the base.
The key is adapted to be received in a keyway in the friction pad of one of the lens-supporting shafts of the machine, which pad has a recess around the keyway to accommodate the base and which frictionally engages the said lens surface around the base.
Since the pad frictionally engages the lens surface directly, around the flexible base of the device, the force required to rotate the lens in the machine is transmitted to the lens directly via the friction pad, not via the keyway and key as is the case with certain prior locating devices which have an element adhesively affixed to the lens and through which the drive is transmitted to the lens.
Since the flexible element and the key do not have to transmit any rotational driving force but merely constitute a guide device for proper location of the lens blank, the device can be of very small size and simple construction, so that it is economically feasible to use it once and throw it away.
The device may comprise a base of elastomeric material such as rubber, synthetic rubber or flexible plastic, and the key extending from the base may be moulded in one piece with the base. To enhance the flexibility, the key may comprise two or more aligned projections with a gap or gaps between their adjacent edges.
The opposite face of the base may carry a layer of an adhesive. This layer may be protected by a peel-off strip, e.g. a strip of plastics film which adheres lightly to the adhesive layer. When the peel-off strip is removed, the exposed adhesive enables the device to be attached to the lens surface.
Owing to its flexibility the device can be applied to concave, plane or convex lens surfaces.
Because the device is surrounded by the pad during the edge grinding operation, the device is shielded from the cutting fluid used in the grinding.
DETAILED DESCRIPTION
The invention may be performed in various ways, and a specific embodiment will now be described by way of example with reference to the accompanying drawings, in which:
FIG. 1 is a side view of a device embodying the invention, showing a peel-off protective strip being peeled off to expose a layer of pressure-sensitive adhesive;
FIG. 2 is an end view of the device shown in FIG. 1;
FIG. 3 shows the device mounted on the convex surface of a lens;
FIG. 4 shows the device mounted on the concave surface of a lens;
FIG. 5 is a view of part of an edge grinding machine showing a lens gripped between a pair of friction pads;
FIG. 6 is an end view of a friction pad, showing the recess and keyway to accommodate a device as shown in FIGS. 1 and 2;
FIG. 7 is a sectional side view of the friction pad shown in FIG. 6;
FIG. 8 shows a lens blank prior to application thereto of a device as shown in FIGS. 1 and 2; and
FIG. 9 is a side view, partly in section, of a lens blank having affixed thereto a device as shown in FIGS. 1 and 2.
Referring to the drawings, FIGS. 1 and 2 show a device 10 embodying the invention. The device comprises a thin flexible base 11 and, projecting from the base, a key 12. The key comprises two parts 13 and 14 disposed in line with a gap 15 between them. On the underside of the base 11 there is an adhesive layer 16. This is normally protected by a peel-off strip 17 of plastics film. In FIG. 1 the strip 17 is shown in the process of being peeled off, to expose the adhesive layer 16. It will be observed that the peel-off strip is somewhat longer than the base 11 so that its extremity 18 will project beyond the base, to facilitate removal of the strip. By way of example, the adhesive layer 16 may be a piece of pressure-sensitive adhesive tape with adhesive material on both faces, one face being stuck to the base 11 and the opposite face being protected by the peel-off strip 17.
The base 11 and the key parts 13 and 14 may be a one-piece moulding of a suitable plastics material.
FIGS. 1 to 4 are enlarged to show the details of the device more clearly. A convenient practical size for the device is: base length -- 9 mm; base width -- 4.5 mm; base thickness -- 0.4 mm; key height -- 3 mm; key thickness -- 1.6 mm.
The base 11 is sufficiently flexible to enable the device 10 to be affixed to a convex lens surface 19 as shown in FIG. 3, or to a concave lens surface 20 as shown in FIG. 4, or of course to a flat surface. Making the key 12 in two parts 13 and 14 with a gap 15 between them enhances the flexibility of the base.
In use, the device is affixed to one surface of a lens blank in the correct position, as described below, and the lens blank with the device attached is mounted in an edge grinding machine for grinding the lens to the correct profile shape. As shown in FIG. 5, a lens 25 has had a device 10 (not visible in the drawing) fixed to its convex surface, i.e. the right-hand surface in the drawing, the lens is gripped between a left-hand friction pad 26 on the end of a rotatable shaft 27, and a right-hand friction pad 28 on the end of a rotatable shaft 29. The shafts 27 and 29 are coaxial and are rotatably mounted in a movable head of the machine (not shown) which can move towards and away from the edge of a grinding wheel 30 in the direction of the double arrow 31. The grinding wheel is rotated at high speed about a fixed axis. The extent to which the rotational axis of the shafts 27 and 29 can approach the grinding wheel 30 as the edge of the lens is ground away is limited by a template (not shown) fixed to the end of one of those shafts to rotate therewith, and which cooperates with a fixed anvil. Thus as the shafts 27 and 29, and the lens 25, are rotated, the grinding wheel 30 grinds away the edge of the lens until it has exactly the same profile shape as the template. During the grinding, the grinding region is liberally supplied with a suitable cutting fluid.
The lens edge grinding operation and the machine in which the operation is performed, as so far described, are conventional and need not be described further. However, for use with a device according to the invention, e.g. the device 10 as illustrated, one of the friction pads is modified as shown in FIGS. 6 and 7. The end 33 of the shaft 29 is provided with a deep rectangular recess or keyway 34 which will accommodate the key 12. The friction pad 28 surrounds the shaft end 33 and projects beyond it, leaving a shallow rectangular recess 35 to accommodate the base 11 of the device. When the lens 25 is gripped between the pads 26 and 28, the key 12 enters the keyway 34 and the face of the pad 28 engages the lens surface around the base 11 of the device, which base occupies the shallow recess 35. The key 12 and the keyway 34 cooperate to locate the lens 25 with its optical axis coincident with the axis of the shafts 27, 29 and with the centre of the template, and also to locate the lens in the correct angular position relative to the template, provided of course that the device 10 has been affixed to the lens 25 in the correct position. The positioning and application of the device 10 will now be described with reference to FIGS. 8 and 9.
FIG. 8 shows a circular lens blank 40 the optical surfaces of which have already been ground and finished. Shown in a broken line 41 is the desired outline of the finished lens, to fit the lens aperture of a spectacle frame. The optical centre 42 of the lens is required to be at a predetermined position in the frame, i.e. in line with the pupil of the wearer's eye. Also, in the case of an aspherical lens, e.g. a lens having a cylindrical component of surface curvature, the cylinder axis 43 must be oriented at the opthalmically prescribed angle a in relation to the horizontal 44. If the device 10 is affixed to the lens blank 40 with its centre coincident with the optical axis 42, and with its longitudinal axis correctly disposed at the angle a in relation to the cylinder axis 43, the lens blank will be correctly located relative to the axis of the shafts 27, 29 and of the template when the lens blank is fitted into the edge grinding machine. The template will have an outline shape corresponding to the desired outline 41 of the finished lens.
The device 10 may be positioned and affixed to the lens blank 40 with the aid of a jig which is not a part of the present invention and portions of which are illustrated in FIG. 9.
The jig has a platform 45 on which the lens blank 40 is supported so as to be movable laterally in any direction, and angularly, in relation to an axis 46. The lens blank has previously been marked with removable marks to indicate its optical centre 42 (FIG. 8) and its correct horizontal axis 44, e.g. by three spaced spots aligned on the horizontal axis 44, the centre spot being the optical centre 42. These marks are applied in a known type of instrument which forms no part of this invention and need not be further described. The jig has a rod 48 which is movable towards and away from the platform 45. In at least the last portion of its movement towards the lens blank 40, the rod 48 is constrained to move along the axis 46, in the direction of the double arrow 49. The rod 48 has at its lower end a head 50 in which there is a keyway 47 corresponding to the keyway 34 shown in FIGS. 6 and 7. The jig has means for projecting a light beam along the axis 46, to project a shadow of a graticule and of the markings on the lens blank 40 onto a translucent screen. This screen is disposed above the lens 40, when the rod 48 has been moved out of the way. Thus it is possible to adjust both the translational and angular positions of the lens blank 40 in relation to the graticule. The screen is then removed and the rod 48 carrying the device 10 with the key 12 in the keyway 47 is moved downwards so that the device 10 is brought into the correct position on the lens blank 10. The adhesive layer on the base 11 of the device secures the device firmly to the lens. | This application discloses a device for mounting a lens between friction pads on the inner ends of coaxial rotatable shafts of a lens edge grinding machine. The device comprises a base which can be adhesively secured to one face of the lens, after removal of a protective peel-off strip which lightly adheres to a layer of adhesive on said base, and a key projecting from the back of said base. Said key is received in a keyway in one of said friction pads to locate the lens angularly in relation to said shafts. This friction pad engages the lens surface around said base so that the rotational drive is transmitted from the shaft to the lens direct from the friction pad surface and not through the key. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a direct-current power supply device and particularly to a technique of reducing a rise in voltage of a smoothing capacitor of a PFC (Power Factor Correction: Power factor improvement) circuit at a time when a load is light in a direct-current power supply device designed to control a DC/DC converter and the PFC circuit by means of one switching element.
2. Description of the Related Art
A direct-current power supply device, which converts a commercial alternating-current power supply to a direct-current power supply using a rectification smoothing circuit and then converts the direct-current power supply to a desired direct-current voltage using a DC/DC converter to output the direct-current voltage, has been used. When the direct-current power supply is obtained by the rectification smoothing circuit from the commercial alternating-current power supply, current flows through a smoothing capacitor only around a peak of sine-wave alternating-current voltage. Accordingly, a power factor becomes worse; a higher harmonic wave is generated, which badly affects surrounding areas. To solve the above problem, a PFC circuit may be provided in the rectification smoothing circuit. In this case, a switch used by the PFC circuit can be shared as a switching element by the DC/DC converter; the sharing of the switch is effective in making the direct-current power supply device smaller and reducing costs. Those sharing the switching element between the PFC circuit and the DC/DC converter include, for example, the one disclosed in Jpn. Pat. Appln. Laid-Open Publication No. 2002-247843 (Patent Document 1) or U.S. Pat. No. 5,991,172 (Patent Document 2).
CITATION LIST
Patent Document
[Patent Document 1] Jpn. Pat. Appln. Laid-Open Publication No. 2002-247843
[Patent Document 2] U.S. Pat. No. 5,991,172
The above conventional techniques are effective in making devices smaller and reducing costs because the switching elements and controllers used in the PFC circuit and DC/DC converter are put into one. However, it is only output voltage of the DC/DC converter that can be controlled in a stable manner. Therefore, the problem is that when a load of the DC/DC converter is light, terminal voltage of the smoothing capacitor of the PFC circuit rises. FIG. 6 shows a characteristic, with the horizontal axis representing the output voltage (the state of the load) of the DC/DC converter and the vertical axis representing the terminal voltage of the smoothing capacitor of the PFC circuit. It is clear that as the output voltage of the DC/DC converter falls (or turns into a light-load state), the terminal voltage of the smoothing capacitor of the PFC circuit rises.
In general, an electrolytic capacitor is used for the smoothing capacitor with a unique absolute rated voltage; there is a limit to the voltage that can be applied to the smoothing capacitor. The reason why the terminal voltage of the smoothing capacitor of the PFC circuit rises at a time when the load of the DC/DC converter is light has been unclear. Therefore, the following has been required for the smoothing capacitor: a capacitor having a sufficient withstanding voltage rating, or an operation of connecting two or more capacitors in series or any other operation to secure a voltage-withstanding capability. Or alternatively, an overvoltage protection circuit has been provided to protect the capacitor against overvoltage. The measures described above, however, lead to an increase in costs and become a snag in terms of implementation when the device is made smaller.
The inventors of the present invention have found as a result of careful examination that the inefficiency in a process of transferring the energy released from a reactor of the PFC circuit to a secondary side of a transformer at a time when the load is light is a cause of the above problem. That is, when the load is light, the ON pulse width, which is used to switch the switching element ON/OFF, becomes narrower. Therefore, stray capacitance that exists on a primary winding of the transformer, or a capacitor of a snubber circuit that is connected to the primary winding of the transformer to absorb a surge voltage, is not fully charged. As a result, the voltage of the transformer is lowered. Thus, the energy released form the reactor of the PFC circuit cannot be transferred to the secondary side of the transformer in an efficient manner. The phenomenon will be described with reference to FIGS. 7 and 8 .
FIG. 7 shows the circuit configuration of a direct-current power supply device 100 of a conventional technique, which is so formed as to control a DC/DC converter and a PFC circuit with one switching element. FIG. 8 shows the operational waveform of each portion to explain an operation of the direct-current power supply device 100 when a load is light. Since the load is light, the direct-current power supply device 100 oscillates intermittently. What is shown is the rising terminal voltage of a smoothing capacitor C 1 of the PFC circuit.
As shown in FIG. 7 , the direct-current power supply device 100 includes the smoothing capacitor C 1 , which performs a DC/DC converter operation; a transformer T 1 ; a switching element Q 1 ; a diode D 2 ; a smoothing capacitor C 2 ; a reactor L 1 , which performs a PFC operation; a fast recovery diode D 1 , which serves as a backflow preventing diode; and a switching element Q 1 . In this case, the switching element Q 1 is shared by a DC/DC converter section and a PFC section. The DC/DC converter section works as a flyback converter. The voltage polarity of the transformer T 1 is set as indicated by ● in the diagram so as to work as a flyback converter.
As the switching element Q 1 is turned ON/OFF, a change in voltage of a high frequency wave occurs at a tap section where two windings N 1 a (first primary winding) and N 1 b (second primary winding) of the primary winding N 1 of the transformer T 1 are connected in response to the ON/OFF operation of the switching element Q 1 . As the voltage changes, high frequency current flows through the reactor L 1 . The amplitude of the current varies according to the voltage amplitude of a commercial alternating-current power supply Vs. Therefore, the PFC operation with improved power factors is achieved.
The circuit configuration of the direct-current power supply device 100 will be described with reference to FIG. 7 . To a rectification circuit RC 1 where diodes are so connected to form a bridge, a commercial alternating-current power supply Vs is connected. Between a positive electrode-side output terminal and negative electrode-side output terminal of the rectification circuit RC 1 , a bypass capacitor C 3 , whose capacitance is smaller than that of the smoothing capacitor C 1 , is connected. To a connection point where the positive electrode-side output terminal of the rectification circuit RC 1 and one terminal of the bypass capacitor C 3 are connected, one terminal of the reactor L 1 is connected. To the other terminal of the reactor L 1 , an anode terminal of the fast recovery diode D 1 is connected. A cathode terminal of the fast recovery diode D 1 is connected to the tap section of the primary winding N 1 of the transformer T 1 . The primary winding N 1 of the transformer T 1 is made up of two windings N 1 a (first primary winding) and N 1 b (second primary winding). A connection point where the other terminal of the first primary winding N 1 a and one terminal (at the side indicated by ● in the diagram) of the second primary winding N 1 b are connected together is the tap section described above. One terminal (at the side indicated by ● in the diagram) of the first primary winding N 1 a is connected to one terminal (at the positive electrode side) of the smoothing capacitor C 1 . The other terminal (at the negative electrode side) of the smoothing capacitor C 1 is connected to a connection point where the negative electrode-side output terminal of the rectification circuit RC 1 and the other terminal of the bypass capacitor C 3 are connected. The other terminal of the second primary winding N 1 b is connected to a drain terminal of the switching element Q 1 . A source terminal of the switching element Q 1 is connected to a connection point where the negative electrode output terminal of the rectification circuit RC 1 , the other terminal of the bypass capacitor C 3 and the other terminal of the smoothing capacitor C 1 are connected together.
The other terminal of the secondary winding N 2 of the transformer T 1 is connected to an anode terminal of the diode D 2 . A cathode terminal of the diode D 2 is connected to one terminal (at the positive electrode side) of the smoothing capacitor C 2 . One terminal (at the side indicated by ● in the diagram) of the secondary winding N 2 of the transformer T 1 is connected to the other terminal (at the negative electrode side) of the smoothing capacitor C 2 . One terminal and the other terminal of the smoothing capacitor C 2 serve as a positive electrode-side output terminal A and negative electrode-side output terminal B of the direct-current power supply device 100 , respectively. The voltage between the positive electrode-side output terminal A and negative electrode-side output terminal B of the direct-current power supply device 100 is input to a control circuit CTL 5 , which outputs a pulse signal to a gate terminal of the switching element Q 1 to turn the switching element Q 1 ON/OFF so that a target voltage is obtained.
The waveforms shown in FIG. 8 represent, from top to bottom, positive electrode-side output voltage Vin (=voltage Vc 3 of the bypass capacitor C 3 ) of the rectification circuit RC 1 , drain-to-source voltage Vds of the switching element Q 1 , voltage Vc 1 of the smoothing capacitor C 1 , current IL 1 of the reactor L 1 , current IC 1 of the smoothing capacitor C 1 , drain current IQ 1 of the switching element Q 1 , current ID 2 of the diode D 2 , and output voltage Vo of the direct-current power supply device 100 (=voltage VC 2 of the smoothing capacitor C 2 ), with t 1 to t 18 at the bottom representing time.
(Until t 0 )
The positive electrode-side output voltage Vin (=voltage Vc 3 of the bypass capacitor C 3 ) of the rectification circuit RC 1 is substantially at a constant level, as the DC/DC converter consumes less power because the load is light. At time t 0 , the output voltage Vo goes down to a switching operation restart voltage, which is lower than the rated voltage. The control circuit CTL 5 outputs a gate signal to the switching element Q 1 to prompt ON/OFF control.
(t 0 to t 1 )
After the switching element Q 1 is turned on at time t 0 , the voltage waveform of the drain-to-source voltage Vds of the switching element Q 1 becomes substantially 0V as shown in FIG. 8 , and the discharging of electricity of the smoothing capacitor C 1 takes place through the first and second primary windings N 1 a and N 1 b of the transformer T 1 (The discharge current is IC 1 ). Accordingly, the voltage VC 1 of the smoothing capacitor C 1 drops over time t 0 to t 1 . From t 0 to t 1 , the current IL 1 of the reactor L 1 flows through the second primary winding N 1 b of the transformer T 1 and the switching element Q 1 , rising from 0 A. At this time, the drain current IQ 1 of the switching element Q 1 is a flow of current that is the sum of the discharge current IC 1 of the smoothing capacitor C 1 and the current IL 1 from the reactor L 1 .
(t 1 to t 2 )
From time t 1 to t 2 , after the switching element Q 1 is turned off by OFF signal, the magnetic energy accumulated in the reactor L 1 charges the smoothing capacitor C 1 via the first primary winding N 1 a of the transformer T 1 . At this time, because of the voltage applied to the first primary winding N 1 a , the voltage of the secondary winding N 2 occurs in proportion to the turns ratio, but does not go above the output voltage Vo (=the voltage VC 2 of the smoothing capacitor C 2 ). Therefore, the diode D 2 remains off. Thus, the secondary-side smoothing capacitor C 2 is not charged with the voltage of the secondary winding N 2 .
(t 2 to t 6 )
Then, a similar operation takes place from time t 2 to t 6 . At this time, the charging and discharging of the voltage of the smoothing capacitor C 1 is repeatedly performed, and the voltage of the smoothing capacitor C 1 gradually rises as shown in FIG. 8 . The charging and discharging of the stray capacitance between the windings of the transformer T 1 (or a capacitor C 5 of the snubber circuit (the stray capacitance is not shown in the diagram; the snubber circuit is shown briefly with the capacitor C 5 and resistance R 1 )) is also repeatedly performed, and the voltage thereof also gradually rises. However, the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 discharges more easily than the smoothing capacitor C 1 because the stray capacitance and the windings of the transformer T 1 are connected in parallel. Therefore, the voltage of the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 rises more slowly than the voltage of the smoothing capacitor C 1 . As the load becomes lighter, an ON period of the switching element Q 1 and a charging period of the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 become shorter. Thus, when the load is light, it is difficult to charge the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 . However, the stray capacitance discharges easily. As the load becomes lighter, the above slowdown trends to intensify because the pulse width becomes narrower during the charging process. As a result, it takes more time for the secondary voltage of the transformer T 1 to rise to the output voltage Vo after an ON pulse has been supplied to the gate of the switching element Q 1 from the control circuit CTL 5 . Meanwhile, the voltage of the smoothing capacitor C 1 goes higher.
(t 7 to t 9 )
At time t 8 , a middle point between time T 7 and t 9 , current starts to flow through the diode D 2 , meaning that at time t 8 , the voltage of the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 is being charged, and that the voltage that occurs at the secondary winding N 2 has risen to voltage VC 2 where the smoothing capacitor 2 can be charged. With the voltage that occurs at the secondary winding N 2 of the transformer T 1 , the smoothing capacitor C 2 is being charged via the diode D 2 during the period of time t 8 to t 9 . Incidentally, from time t 0 to t 8 , the smoothing capacitor C 2 is not charged by the secondary winding N 2 of the transformer T 1 , and the output voltage Vo (voltage VC 2 of the smoothing capacitor C 2 ) continues to fall.
(t 9 to t 10 )
After the switching element Q 1 is turned on at time t 9 , the voltage waveform of the drain-to-source voltage Vds of the switching element Q 1 becomes substantially 0V as shown in FIG. 8 . The voltage VC 1 of the smoothing capacitor C 1 discharges via the first and second primary windings N 1 a and N 1 b of the transformer T 1 (the discharge current is IC 1 ), and therefore falls over time t 9 to t 10 . From time t 9 to t 10 , the current IL 1 of the reactor L 1 flows through the second primary winding N 1 b of the transformer T 1 and the switching element Q 1 , rising from 0 A. At this time, the drain current IQ 1 of the switching element Q 1 is a flow of current that is the sum of the discharge current IC 1 of the smoothing capacitor C 1 and the current IL 1 from the reactor L 1 .
(t 10 to t 11 )
At time t 10 , after the switching element Q 1 is turned off by OFF signal, the magnetic energy accumulated in the reactor L 1 charges the smoothing capacitor C 1 via the first primary winding N 1 a of the transformer T 1 . At this time, because of the voltage applied to the first primary winding N 1 a , the voltage of the secondary winding N 2 occurs in proportion to the turns ratio. At this time, the voltage of the secondary winding N 2 has already risen to voltage VC 2 . Therefore, the diode D 2 is turned on and, from time t 10 to t 11 , the smoothing capacitor C 2 is charged with the voltage of the secondary winding N 2 .
(t 11 to t 15 )
Then, a similar operation takes place from time t 11 to t 15 . At this time, the voltage of the smoothing capacitor C 1 changes as the charging and discharging of the smoothing capacitor C 1 is repeatedly performed. However, when compared with the situation between time t 0 and t 8 , the amount of charge becomes smaller, and the amount of discharge larger, because energy has been transferred to the secondary side of the transformer T 1 . Therefore, the voltage of the smoothing capacitor C 1 gradually decreases as shown in FIG. 8 . The voltage VC 2 (=output voltage Vo) of the smoothing capacitor C 2 gradually rises as the smoothing capacitor C 2 is charged with the secondary voltage of the transformer T 1 . During the above period of time t 8 to t 15 , the magnetic energy released from the reactor of the PFC circuit is transferred to the secondary side of the transformer T 1 .
(t 15 to t 16 )
After the output voltage Vo rises to a target rated voltage at time t 15 , the control circuit CTL 5 detects the output voltage Vo reaching the target rated voltage and outputs an OFF signal to the switching element Q 1 . In response, the switching element Q 1 remains in a halting state until time t 16 . At this time, the voltage of the smoothing capacitor C 1 has risen above the voltage of time t 0 . Since there is no circuit for discharging electric charge from the smoothing capacitor C 1 , the voltage VC 1 is substantially kept constant. Meanwhile, the electric charge of the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 is discharged through the windings of the transformer T 1 . Therefore, like the above-described situation between time t 0 to t 8 , even if the switching of the switching element Q 1 restarts, the voltage of the secondary winding N 2 of the transformer T 1 does not rise immediately.
(t 16 to t 17 )
Then, at time t 16 , the output voltage Vo drops to a switching operation restart voltage, which is detected by the control circuit CTL 5 . The control circuit CTL 5 outputs a gate signal, as in the case of time t 0 , to the switching element Q 1 to prompt ON/OFF control. As a result, the switching operation starts. However, from time t 15 to t 16 , the electric charge of the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 has been discharged. Therefore, until t 17 , for the same reason as the above situation between time t 0 and t 8 , the smoothing capacitor C 2 is not charged with the voltage that occurs at the secondary winding N 2 of the transformer T 1 . If the period of time t 16 to t 17 is almost equal to the period of time t 0 to t 8 , the voltage of the smoothing capacitor C 1 rises from a starting point at time t 16 by an amount substantially equivalent to the rise in voltage between time t 0 to t 8 . Therefore, the voltage of the smoothing capacitor C 1 goes higher than that at time t 8 .
(t 17 to t 18 )
At time t 17 , current starts to flow through the diode D 2 , meaning that as in the case of time t 8 , the voltage of the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 is being charged, and that the voltage that occurs at the secondary winding N 2 has risen to voltage VC 2 where the smoothing capacitor 2 can be charged. Therefore, during the period of time t 17 to t 18 , a similar operation to that during the above period of t 8 to t 15 takes place. When the switching operation stops at time t 18 , the voltage of the smoothing capacitor C 1 goes higher than that at time t 16 as in the case where the voltage of the smoothing capacitor C 1 goes higher at time t 15 than that at time to.
(t 18 and Thereafter)
After time t 18 , a similar operation is repeatedly performed, and the voltage of the smoothing capacitor C 1 rises. However, after the magnetic energy released from the reactor L 1 and the energy output from the secondary side of the transformer T 1 rise and are equally matched, the magnetic energy from the reactor L 1 and the energy from the secondary side of the transformer T 1 become balanced, and the voltage of the smoothing capacitor C 1 stops rising. In this manner, the output voltage Vo is controlled by the control circuit CTL 5 and kept at the rated voltage. However, the voltage of the smoothing capacitor C 1 is not controlled by the control circuit CTL 5 and goes higher than that at the start of the switching operation.
As described above, the voltage of the smoothing capacitor C 1 is unstable, and there is a fear that the voltage of the smoothing capacitor C 1 could rise above the withstanding voltage of the capacitor at a time when the load is light. Therefore, according to a conventional technique, the following has been required: a capacitor having a sufficient withstanding voltage rating, or an operation of connecting two or more capacitors in series or any other operation to secure a voltage-withstanding capability. Or alternatively, an overvoltage protection circuit has been provided to protect the capacitor against overvoltage. The measures described above, however, lead to an increase in costs and become a snag in terms of implementation when the device is made smaller.
SUMMARY OF THE INVENTION
The object of the present invention is to solve the problems of the conventional techniques in view of the above problems and to provide a direct-current power supply device, in which a switch used by a PFC circuit is shared as a switching element by a DC/DC converter and which prevents terminal voltage of a smoothing capacitor of the PFC circuit from rising at a time when the DC/DC converter is a light load.
As for a direct-current device of the present invention, a direct-current power supply device, which converts energy obtained from an alternating-current power supply into direct-current energy, includes: a rectifier that converts alternating-current voltage of the alternating-current power supply into direct-current voltage; a transformer that includes a primary winding, which includes a tap at a connection point where a first primary winding and a second primary winding are connected, and a secondary winding; a primary-side smoothing capacitor whose positive electrode-side terminal is connected to a terminal at a side opposite to the tap of the first primary winding and whose negative electrode-side terminal is connected to a negative electrode-side output terminal of the rectifier; a first switching element whose drain and source terminals are connected between the negative electrode-side output terminal of the rectifier and a terminal at a side opposite to the tap of the second primary winding; a reactor and backflow preventing diode that are connected in series between a positive electrode-side output terminal of the rectifier and the tap of the transformer; a direct-current smoothing circuit that includes a rectifying diode, which is connected to the secondary winding of the transformer, and a secondary-side smoothing capacitor; and discharging means for detecting a light-load state of an output and discharging electric charge of the primary-side smoothing capacitor in a way that suppresses an increase in voltage of the primary-side smoothing capacitor.
Moreover, in the direct-current power supply device of the present invention, the discharging means is so formed that the electric charge of the primary-side smoothing capacitor is supplied to power supply of a control circuit that performs ON/OFF control of the first switching element.
Moreover, in the direct-current power supply device of the present invention, the discharging means includes: a second switching element whose drain and source terminals are connected between a power supply terminal of the control circuit and a connection point where the first primary winding and the positive electrode-side terminal of the primary-side smoothing capacitor are connected; resistance that is connected between drain and gate terminals of the second switching element; a third switching element whose drain and source terminals are connected between the gate terminal of the second switching element and the negative electrode-side output terminal of the rectifier; and a control circuit that outputs an ON/OFF signal to a gate terminal of the third switching element, wherein the control circuit is so formed as to detect a decrease in power supply voltage of the control circuit and output, when the decrease in power supply voltage is detected, an OFF signal to the third switching element.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, which converts energy obtained from an alternating-current power supply into direct-current energy, includes: a rectifier that converts alternating-current voltage of the alternating-current power supply into direct-current voltage; a transformer that includes a primary winding, which includes a tap at a connection point where a first primary winding and a second primary winding are connected, and a secondary winding; a primary-side smoothing capacitor whose positive electrode-side terminal is connected to a terminal at a side opposite to the tap of the first primary winding and whose negative electrode-side terminal is connected to a negative electrode-side output terminal of the rectifier; a first switching element whose drain and source terminals are connected between the negative electrode-side output terminal of the rectifier and a terminal at a side opposite to the tap of the second primary winding; a reactor and backflow preventing diode that are connected in series between a positive electrode-side output terminal of the rectifier and the tap of the transformer; a direct-current smoothing circuit that includes a rectifying diode, which is connected to the secondary winding of the transformer, and a secondary-side smoothing capacitor; and electromagnetic energy supplying means for detecting a light-load state of an output and supplying part of electromagnetic energy of the reactor to a power supply of a control circuit, which performs ON/OFF control of the first switching element, via the second primary winding.
Moreover, in the direct-current power supply device of the present invention, the electromagnetic energy supplying means includes: a second switching element whose drain and source terminals are connected between a power supply terminal of the control circuit and a connection point where the second primary winding and the drain terminal of the first switching element are connected; resistance that is connected between drain and gate terminals of the second switching element; a third switching element whose drain and source terminals are connected between the gate terminal of the second switching element and the negative electrode-side output terminal of the rectifier; and a control circuit that outputs an ON/OFF signal to a gate terminal of the third switching element, wherein the control circuit is so formed as to detect a decrease in power supply voltage of the control circuit and output, when the decrease in power supply voltage is detected, an OFF signal to the third switching element.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, which converts energy obtained from an alternating-current power supply into direct-current energy, includes: a rectifier that converts alternating-current voltage of the alternating-current power supply into direct-current voltage; a transformer that includes a primary winding, which includes a tap at a connection point where a first primary winding and a second primary winding are connected, and a secondary winding; a primary-side smoothing capacitor whose positive electrode-side terminal is connected to a terminal at a side opposite to the tap of the first primary winding and whose negative electrode-side terminal is connected to a negative electrode-side output terminal of the rectifier; a first switching element whose drain and source terminals are connected between the negative electrode-side output terminal of the rectifier and a terminal at a side opposite to the tap of the second primary winding; a reactor and backflow preventing diode that are connected in series between a positive electrode-side output terminal of the rectifier and the tap of the transformer; a direct-current smoothing circuit that includes a rectifying diode, which is connected to the secondary winding of the transformer, and a secondary-side smoothing capacitor; and electromagnetic energy supplying means for supplying part of electromagnetic energy of the reactor to a power supply of a control circuit, which performs ON/OFF control of the first switching element, via a diode using an auxiliary winding provided in the reactor.
Moreover, in the direct-current power supply device of the present invention, the electromagnetic energy supplying means is so formed that: the auxiliary winding of the reactor and the diode are connected in series between the negative electrode-side output terminal of the rectifier and the power supply of the control circuit; and current flows from the auxiliary winding to the power supply of the control circuit via the diode as the power supply voltage of the control circuit decreases.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, which converts energy obtained from an alternating-current power supply into direct-current energy, includes: a rectifier that converts alternating-current voltage of the alternating-current power supply into direct-current voltage; a transformer that includes a primary winding, which includes a tap at a connection point where a first primary winding and a second primary winding are connected, and a secondary winding; a primary-side smoothing capacitor whose positive electrode-side terminal is connected to a terminal at a side opposite to the tap of the first primary winding and whose negative electrode-side terminal is connected to a negative electrode-side output terminal of the rectifier; a first switching element whose drain and source terminals are connected between the negative electrode-side output terminal of the rectifier and a terminal at a side opposite to the tap of the second primary winding; a reactor and backflow preventing diode that are connected in series between a positive electrode-side output terminal of the rectifier and the tap of the transformer; a direct-current smoothing circuit that includes a rectifying diode, which is connected to the secondary winding of the transformer, and a secondary-side smoothing capacitor; a control circuit that outputs an ON/OFF signal to the first switching element to control output voltage so that the output voltage becomes predetermined voltage; and an output voltage detection circuit that increases detection voltage relative to the same output voltage and outputs a feedback signal to the control circuit at a time when a load is light, wherein an operation takes place in a way that lowers the output voltage when the load is light.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, in which a switch used by a PFC circuit is shared as a switching element by a DC/DC converter, includes voltage suppression means for suppressing a rise in voltage of a primary-side smoothing capacitor of the PFC circuit at a time when a load is light.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, in which a switch used by a PFC circuit is shared as a switching element by a DC/DC converter, includes voltage suppression means for supplying electric charge accumulated in a primary-side smoothing capacitor to a power supply of a control circuit that controls the switching element at a time when a load is light in order to suppress a rise in voltage in the primary-side smoothing capacitor.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, in which a switch used by a PFC circuit is shared as a switching element by a DC/DC converter, includes voltage suppression means for also supplying magnetic energy released from a reactor of the PFC circuit to a power supply of a control circuit that controls the switching element via a second winding of a primary winding of a transformer at a time when a load is light in order to suppress an amount of charge of a primary-side smoothing capacitor.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, in which a switch used by a PFC circuit is shared as a switching element by a DC/DC converter, includes voltage suppression means for supplying, with a main winding and auxiliary winding provided in a reactor of the PFC circuit, magnetic energy of the reactor to a power supply of a control circuit via a diode from the auxiliary winding after power supply voltage of the control circuit that controls the switching element at a time when a load is light falls.
Moreover, as for a direct-current power supply device of the present invention, the direct-current power supply device, in which a switch used by a PFC circuit is shared as a switching element by a DC/DC converter, includes voltage suppression means for controlling the DC/DC converter in a way that lowers output voltage at a time when a load is light in order to suppress an amount of charge of a primary-side smoothing capacitor.
According to the present invention, the direct-current power supply device, in which the switch used by the PFC circuit is shared as a switching element by the DC/DC converter, can prevent the terminal voltage of the smoothing capacitor of the PFC circuit from rising at a time when the DC/DC converter is a light load.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing the circuit configuration of a direct-current power supply device 1 according to a first embodiment of the present invention;
FIG. 2 is a diagram showing a voltage characteristic of a smoothing capacitor of the direct-current power supply device 1 according to first to fourth embodiments of the present invention;
FIG. 3 is a diagram showing the circuit configuration of a direct-current power supply device 2 according to the second embodiment of the present invention;
FIG. 4 is a diagram showing the circuit configuration of a direct-current power supply device 3 according to the third embodiment of the present invention;
FIG. 5 is a diagram showing the circuit configuration of a direct-current power supply device 4 according to the fourth embodiment of the present invention;
FIG. 6 is a diagram showing a voltage characteristic of a smoothing capacitor of a direct-current power supply device 100 of a conventional technique;
FIG. 7 is a diagram showing the circuit configuration of the direct-current power supply device 100 of a conventional technique; and
FIG. 8 is a diagram showing the operational waveform of each section of the direct-current power supply device 100 of a conventional technique.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following describes embodiments of the present invention in a concrete way with reference to the accompanying drawings. A direct-current power supply device illustrated in an embodiment of the present invention is a direct-current power supply device in which a switch used by a PFC circuit is shared as a switching element by a DC/DC converter, including voltage suppression means for suppressing an increase in voltage of a smoothing capacitor of the PFC circuit at a time when a load is light.
A direct-current power supply device 1 of a first embodiment shown in FIG. 1 is one that, as voltage suppression means, suppresses a rise in voltage of the smoothing capacitor C 1 by supplying electric charge accumulated in the smoothing capacitor C 1 to power supply of the control circuit CTL 1 at a time when a load is light.
A direct-current power supply device 2 of a second embodiment shown in FIG. 3 is one that, as voltage suppression means, suppresses an amount of charge of a smoothing capacitor C 1 by also supplying magnetic energy released from a reactor L 1 of a PFC circuit to power supply of a control circuit CTL 2 via the other winding of a primary winding of a transformer T 1 at a time when a load is light.
A direct-current power supply device 3 of a third embodiment shown in FIG. 4 is one in which a main winding P and an auxiliary winding S are provided, as voltage suppression means, in a reactor L 2 of a PFC circuit. The main winding P is used in the same way as a reactor L 1 ; as the power supply voltage of a control circuit CTL 3 falls at a time when a load is light, magnetic energy of the reactor L 2 is supplied to power supply of the control circuit CTL 3 from the auxiliary winding S via a diode D 4 .
A direct-current power supply device 4 of a fourth embodiment shown in FIG. 5 is one that controls a DC/DC converter in such a way that output voltage decreases at a time when a load is light, thereby shortening the period of time t 0 to t 8 (the period of time t 16 to t 17 ) shown in FIG. 8 and curbing an amount of charge of a smoothing capacitor C 1 .
(First Embodiment)
FIG. 1 shows the circuit configuration of a direct-current power supply device 1 of the first embodiment of the present invention. The direct-current power supply device 1 is different from the direct-current power supply device 100 of the conventional technique shown in FIG. 7 in that a circuit (switching elements Q 2 and Q 3 , and resistance R 2 ) for supplying electric charge of a smoothing capacitor C 1 to power supply Vcc of a control circuit CTL 1 is provided, with the switching elements Q 2 and Q 3 controlled by an ON/OFF signal from the control circuit CTL 1 at a time when a load is light. The switching elements Q 2 and Q 3 and the resistance R 2 make up a circuit that also serves as a start-up circuit of a control circuit. Incidentally, an auxiliary winding N 3 of a transformer T 1 , a diode D 3 , a smoothing capacitor C 4 and the like are not shown in FIG. 7 but are shown in FIG. 1 . The bypass capacitor C 3 , which is shown in FIG. 7 but not in FIG. 1 , a high frequency component removing capacitor and a filter provided between a commercial alternating-current power supply Vs and a rectification circuit RC 1 , which are disclosed in Patent Document 1, or the like may be provided when needed.
The circuit configuration of the direct-current power supply device 1 will be described with reference to FIG. 1 . A rectification circuit RC 1 where diodes are so connected as to form a bridge is connected to a commercial alternating-current power supply Vs. To a positive electrode-side output terminal (voltage Vin) of the rectification circuit RC 1 , one terminal of a reactor L 1 is connected. To the other terminal of the reactor L 1 , an anode terminal of a fast recovery diode D 1 is connected. A cathode terminal of the fast recovery diode D 1 is connected to a tap section of a primary winding N 1 of the transformer T 1 . The primary winding N 1 of the transformer T 1 is made up of two windings N 1 a (first primary winding) and Nib (second primary winding). A connection point for the other terminal of the first primary winding N 1 a and one terminal (at the side indicated by ● in the diagram) of the second primary winding N 1 b is the tap section described above. One terminal (at the side indicated by ● in the diagram) of the first primary winding N 1 a is connected to one terminal (at the positive electrode side) of the smoothing capacitor C 1 . The other terminal (at the negative electrode side) of the smoothing capacitor C 1 is connected to a negative electrode-side output terminal (GND) of the rectification circuit RC 1 . The other terminal of the second primary winding N 1 b is connected to a drain terminal of the switching element Q 1 . A source terminal of the switching element Q 1 is connected to a connection point where the negative electrode-side output terminal of the rectification circuit RC 1 and the other end of the smoothing capacitor C 1 are connected. The voltage polarity of the primary winding of the transformer T 1 is set as indicated by ● in the diagram.
The other end of a secondary winding N 2 of the transformer T 1 is connected to an anode terminal of the diode D 2 . A cathode terminal of the diode D 2 is connected to one terminal (at the positive electrode side) of a smoothing capacitor C 2 . One terminal (at the side indicated by ● in the diagram) of the secondary winding N 2 of the transformer T 1 is connected to the other terminal (at the negative electrode side) of the smoothing capacitor C 2 . The voltage polarity of the transformer T 1 is set as indicated by ● in the diagram so as to work as a flyback converter. One terminal and the other terminal of the smoothing capacitor C 2 work as a positive electrode-side output terminal A and negative electrode-side output terminal B of the direct-current power supply device 1 , respectively. The voltage between the positive electrode-side output terminal A and negative electrode-side output terminal B of the direct-current power supply device 1 is detected by an output voltage detection circuit DTC, which is connected between the positive electrode-side output terminal A and the negative electrode-side output terminal B. A resultant detection signal is input, as a feedback signal FB, to the control circuit CTL 1 . The control circuit CTL 1 makes a comparison between a preset chopping-wave voltage and the feedback signal FB; a pulse signal for turning the switching element ON/OFF is output from an OUT terminal of the control circuit CTL 1 to a gate terminal of the switching element Q 1 so that output voltage Vo (=voltage VC 2 of the smoothing capacitor C 2 ) comes to a desired target voltage. Adjustments to the output voltage Vo can be made by changing the size of the feedback signal FB with the use of an output voltage control signal vc, which is input into the output voltage detection circuit DTC.
In the transformer T 1 , an auxiliary winding N 3 is provided for power supply of the control circuit CTL 1 . The voltage of the auxiliary winding N 3 is rectified and smoothed by a diode D 3 and a smoothing capacitor C 4 before being supplied as power supply Vcc of the control circuit CTL 1 . The voltage polarity of the primary winding N 1 of the transformer T 1 and of the auxiliary winding N 3 is set as indicated by ● in the diagram.
What is provided for the smoothing capacitor C 1 is a circuit (switching elements Q 2 and Q 3 , and resistance R 2 ) that also serves as a start-up circuit of the control circuit CTL 1 and supplies electric charge of the smoothing capacitor C 1 to the power supply Vcc of the control circuit CTL 1 at a time when the load is light: the smoothing capacitor C 1 is connected in parallel to the circuit. That is, to one terminal (at the positive electrode side) of the smoothing capacitor C 1 , a drain terminal of the switching element Q 2 (FET, for example) is connected. A source terminal of the switching element Q 2 is connected to a terminal of power supply Vcc of the control circuit CTL 1 . To a gate terminal of the switching element Q 2 , a drain terminal of the switching element Q 3 is connected. A source terminal of the switching element Q 3 is connected to GND. Resistance R 2 is connected between the gate and drain of the switching element Q 2 . A gate terminal of the switching element Q 3 is connected to an ON/OFF signal output terminal of the control circuit CTL 1 .
As the voltage of the power supply Vcc of the control circuit CTL 1 decreases, the decrease is detected by the control circuit CTL 1 , which then outputs a signal for turning the switching element Q 3 off from an ON/OFF signal output terminal of the control circuit CTL 1 . As a result, the switching element Q 3 is turned off. Therefore, the switching element Q 2 is turned on, supplying power from the smoothing capacitor C 1 to the power supply Vcc of the control circuit CTL 1 . That is, when the output of the direct-current power supply device 1 turns into a light-load state or when the output voltage is lowered by the output voltage control signal vc, a period during which the switching element Q 1 is ON is shortened. Accordingly, the average value of the voltage waveform that appears at the auxiliary winding N 3 of the transformer T 1 falls, resulting in a decrease in voltage of the power supply Vcc. After the decrease in voltage of the power supply Vcc is detected by the control circuit CTL 1 , a signal for turning the switching element Q 3 off is output from the ON/OFF signal output terminal of the control circuit CTL 1 . As a result, the switching element Q 3 is turned off. Therefore, the switching element Q 2 is turned on, and the electric charge of the smoothing capacitor C 1 is discharged. Thus, it is possible to lower the voltage of the smoothing capacitor C 1 .
FIG. 2 shows a characteristic, with the horizontal axis representing the output voltage (the state of the load) of the DC/DC converter and the vertical axis representing the terminal voltage of the smoothing capacitor of the PFC circuit. Among characteristic curves, the solid-line characteristic curve represents a characteristic of the direct-current power supply device 1 of the first embodiment of the present invention. The dotted-line characteristic curve represents a characteristic of the direct-current power supply device 100 made up of conventional circuits. It is clear that when compared with the conventional circuits, the terminal voltage of the smoothing capacitor C 1 of the PFC circuit of the present invention is kept lower at a time when the load is light.
According to the present first embodiment, with the circuit that also serves as a start-up circuit, it is possible to curb an increase in voltage of the smoothing capacitor C 1 at a time when the load is light. Therefore, the advantage is that the circuit configuration is simplified. Moreover, according to the present embodiment, part of the magnetic energy released from the reactor L 1 can be used as power of the power supply of the control circuit CTL 1 . Therefore, compared with the one in which the energy generated by a rise in voltage of the smoothing capacitor C 1 is simply consumed by resistance, it is possible to improve the efficiency of the direct-current power supply device. Since the voltage of the smoothing capacitor C 1 falls, a capacitor with low voltage-withstanding capability can be used. Thus, it is possible to achieve a reduction in costs of smoothing capacitors and an improvement in reliability. If the power supply Vcc of the control circuit CTL 1 is obtained by rectifying the voltage of the auxiliary winding N 3 of the transformer T 1 , the power supply Vcc decreases when the output of the direct-current power supply device 1 turns into a light-load state or when the output voltage is lowered by the output voltage control signal vc. However, according to the present first embodiment, power is supplied from the smoothing capacitor C 1 . Therefore, it is possible to keep the power supply Vcc of the control circuit CTL 1 from decreasing.
(Second Embodiment)
FIG. 3 shows the circuit configuration of the direct-current power supply device 2 of the second embodiment of the present invention. The direct-current power supply device 2 is different from the direct-current power supply device 1 of the first embodiment shown in FIG. 1 : while the drain terminal of the switching element Q 2 is connected to one terminal (positive-electrode terminal) of the smoothing capacitor C 1 in the direct-current power supply device 1 , the drain terminal of the switching element Q 2 is connected to a connection point where the other terminal of the second primary winding N 1 b of the transformer T 1 and the drain terminal of the switching element Q 1 are connected together in the direct-current power supply device 2 . The configuration of the other parts is the same as that of the first embodiment and therefore will not be described in detail.
According to the present second embodiment, unlike the first embodiment, the energy accumulated in the smoothing capacitor C 1 is not supplied to the power supply Vcc of the control circuit CTL 1 ; part of the electromagnetic energy released from the reactor L 1 is supplied to the power supply Vcc of a control circuit CTL 2 via the second primary winding N 1 b of the transformer T 1 . As in the case of the first embodiment, even in the present second embodiment, when the voltage of the power supply Vcc of the control circuit CTL 2 decreases, the decrease is detected by the control circuit CTL 2 . A signal for turning the switching element Q 3 off is output from the ON/OFF signal output terminal of the control circuit CTL 2 , and the switching element Q 3 is turned off. As a result, the switching element Q 2 is turned on, supplying power from the smoothing capacitor C 1 to the power supply Vcc of the control circuit CTL 2 .
That is, when the output of the direct-current power supply device 2 turns into a light-load state or when the output voltage is lowered by the output voltage control signal vc, a period during which the switching element Q 1 is ON is shortened. Accordingly, the average value of the voltage waveform that appears at the auxiliary winding N 3 of the transformer T 1 falls, resulting in a decrease in voltage of the power supply Vcc. After the decrease in voltage of the power supply Vcc is detected by the control circuit CTL 2 , a signal for turning the switching element Q 3 off is output from the ON/OFF signal output terminal of the control circuit CTL 2 . As a result, the switching element Q 3 is turned off. Therefore, the switching element Q 2 is turned on, and part of the magnetic energy released from the reactor L 1 is consumed as power supply of the control circuit CTL 2 . Thus, it is possible to lower the voltage of the smoothing capacitor C 1 . Even in the present second embodiment, the circuit also serves as a start-up circuit. Moreover, it is possible to curb an increase in voltage of the smoothing capacitor C 1 at a time when the load is light, and the advantage is that the circuit configuration is simplified. Moreover, even in the present second embodiment, part of the magnetic energy released from the reactor L 1 can be used as power of the power supply of the control circuit CTL 2 . Therefore, compared with the one in which the energy generated by a rise in voltage of the smoothing capacitor C 1 is simply consumed by resistance, it is possible to improve the efficiency of the direct-current power supply device 2 . Moreover, since the voltage of the smoothing capacitor C 1 falls, a capacitor with low voltage-withstanding capability can be used. Thus, it is possible to achieve a reduction in costs of smoothing capacitors and an improvement in reliability. If the power supply Vcc of the control circuit CTL 2 is obtained by rectifying the voltage of the auxiliary winding N 3 of the transformer T 1 , the power supply Vcc decreases when the output of the direct-current power supply device 2 turns into a light-load state or when the output voltage is lowered by the output voltage control signal vc. However, according to the present second embodiment, power is supplied from the reactor L 1 . Therefore, it is possible to keep the power supply Vcc of the control circuit CTL 2 from decreasing.
(Third Embodiment)
FIG. 4 shows the circuit configuration of the direct-current power supply device 3 of the third embodiment of the present invention. In the direct-current power supply device 3 , the switching elements Q 2 and Q 3 and resistance R 2 , which the direct-current power supply devices of the first and second embodiments include, are removed. Instead of the reactor L 1 , a reactor L 2 including a main winding P and an auxiliary winding S is provided. The main winding P is used in the same way as the reactor L 1 of the first or second embodiment. Part of the magnetic energy of the reactor L 2 is supplied to the power supply Vcc of a control circuit CTL 3 from the auxiliary winding S via a diode D 4 at a time when the load is light. The configuration of the other parts is the same as that of the first or second embodiment and therefore will not be described in detail.
When the load is heavy, as in the case of a circuit of a conventional technique, the power supply Vcc of the control circuit CTL 3 is supplied from the auxiliary winding N 3 of the transformer T 1 . However, when the output turns into a light-load state or when the output voltage Vo is lowered by the output voltage control signal vc, a period during which the switching element Q 1 is ON is shortened. Accordingly, the average value of the voltage waveform that appears at the auxiliary winding N 3 of the transformer T 1 falls, and part of the magnetic energy of the reactor L 2 is supplied to the power supply Vcc of the control circuit CTL 3 from the auxiliary winding S via the diode D 4 . Therefore, part of the magnetic energy, which is accumulated in the reactor L 2 when the switching element Q 1 is turned on, is supplied to the power supply of the control circuit CTL 3 ; the electric charge that is supplied to the smoothing capacitor C 1 decreases. Thus, it is possible to lower the voltage of the smoothing capacitor C 1 . According to the present third embodiment, the switching elements Q 2 and Q 3 are unnecessary; a portion of the control circuit for the switching elements Q 2 and Q 3 is also unnecessary. Thus, the advantage is that the circuit configuration is simplified. Moreover, since the voltage of the smoothing capacitor C 1 falls, a capacitor with low voltage-withstanding capability can be used. Thus, it is possible to achieve a reduction in costs of smoothing capacitors and an improvement in reliability. If the power supply Vcc of the control circuit CTL 3 is obtained by rectifying the voltage of the auxiliary winding N 3 of the transformer T 1 , the power supply Vcc decreases when the output of the direct-current power supply device 3 turns into a light-load state or when the output voltage is lowered by the output voltage control signal vc. However, according to the present third embodiment, power is supplied from the auxiliary winding S of the reactor L 2 . Therefore, it is possible to keep the power supply Vcc of the control circuit CTL 3 from decreasing.
(Fourth Embodiment)
FIG. 5 shows the circuit configuration of the direct-current power supply device 4 of the fourth embodiment of the present invention. The direct-current power supply device 4 is substantially the same as the direct-current power supply device 100 of the conventional technique shown in FIG. 7 . However, the direct-current power supply device 4 is different from the direct-current power supply device 100 in that the output voltage Vo is controlled so as to be lowered by the output voltage control signal vc at a time when the load is light. In this case, the output voltage can be decreased when the output voltage detection circuit DTC increases the detection voltage relative to the same output voltage and outputs a feedback signal FB to a control circuit CTL 4 . When the target output voltage of the output voltage Vo is lowered, the voltage of the stray capacitance (or the capacitor C 5 of the snubber circuit) between the windings of the transformer T 1 is being charged after the start of a switching operation of the switching element Q 1 . A period of time (the period of time t 0 to t 8 shown in FIG. 8 , or the period of time t 16 to t 17 ) required for the voltage occurring at the secondary winding N 2 to rise to voltage VC 2 where the smoothing capacitor C 2 can be charged is shortened, thereby curbing an increase in voltage of the smoothing capacitor. According to the present fourth embodiment, the switching elements Q 2 and Q 3 are unnecessary; a portion of the control circuit for the switching elements Q 2 and Q 3 is also unnecessary. Thus, the advantage is that the circuit configuration is simplified. Moreover, since the voltage of the smoothing capacitor C 1 falls, a capacitor with low voltage-withstanding capability can be used. Thus, it is possible to achieve a reduction in costs of smoothing capacitors and an improvement in reliability.
The above has described the present invention through specific examples. However, the above description is given for illustrative purposes only. Needless to say, the present invention may be modified and embodied without departing from the scope of the present invention. For example, according to the present embodiment, to the direct-current power supply device shown in FIG. 1 of the specification of Patent Document 1, the present invention is applied. However, the present invention is not limited to the above. The present invention may be applied in a way that curbs an increase in voltage of a smoothing capacitor Cdc (equivalent to the smoothing capacitor C 1 of the embodiments of the present invention) shown in FIGS. 5 to 11 of the specification of Patent Document 1. Moreover, in the examples described above, a MOSFET is used for the switching element Q 1 . However, a bipolar transistor, FET, IGBT or any other transistor can also be used. Moreover, in the examples described above, FETs are used for the switching elements Q 2 and Q 3 . However, bipolar transistors or MOSFETs can also be used. | In a direct-current power supply device that includes a smoothing capacitor C 1 , which performs a DC/DC converter operation, a transformer T 1 , a switching element Q 1 , a diode D 2 , a smoothing capacitor C 2 , a reactor L 1 , which performs a PFC operation, a fast recovery diode D 1 and a switching element Q 1 , when compared with the case of a rated load, the voltage of the smoothing capacitor C 1 of a PFC circuit rises at a time when a load is light. Therefore, the following has been required: a capacitor having a sufficient withstanding voltage rating, or an operation of connecting a plurality of capacitors in series or any other operation to secure a voltage-withstanding capability.
A direct-current power supply device 1 , in which a switching element Q 1 used by a PFC circuit is shared as a switching element Q 1 by a DC/DC converter, includes voltage suppression means (switching elements Q 2 and Q 3 and resistance R 2 ) for supplying electric charge accumulated in a smoothing capacitor C 1 to a power supply Vcc of a control circuit CTL 1 that controls the switching element Q 1 at a time when a load is light in order to suppress a rise in voltage in the smoothing capacitor C 1. | 8 |
TECHNICAL FIELD
[0001] The present invention relates to new isolated human antibodies raised against peptides being derivatives of apolipoprotein B, in particular antibodies to be used for immunization therapy for treatment of atherosclerosis, method for their preparation, and method for passive immunization using said antibodies.
[0002] In particular the invention includes:
[0003] The use of any isolated antibody raised against an oxidized form of the peptides listed in table 1, in particular MDA-modified peptides, preferably together with a suitable carrier and adjuvant as an immunotherapy or “anti-atherosclerosis “vaccine” for prevention and treatment of ischemic cardiovascular disease.
BACKGROUND OF THE INVENTION
[0004] The protective effects of humoral immunity are known to be mediated by a family of structurally related glycoproteins called antibodies. Antibodies initiate their biological activity by binding to antigens. Antibody binding to antigens is generally specific for one antigen and the binding is usually of high affinity. Antibodies are produced by B-lymphocytes. Blood contains many different antibodies, each derived from a clone of B-cells and each having a distinct structure and specificity for antigen. Antibodies are present on the surface of B-lymphocytes, in the plasma, in interstitial fluid of the tissues and in secretory fluids such as saliva and mucous on mucosal surfaces.
[0005] All antibodies are similar in their overall structure, accounting for certain similarities in physico-chemical features such as charge and solubility. All antibodies have a common core structure of two identical light chains, each about 24 kilo Daltons, and two identical heavy chains of about 55-70 kilo Daltons each. One light chain is attached to each heavy chain, and the two heavy chains are attached to each other. Both the light and heavy chains contain a series of repeating homologous units, each of about 110 amino acid residues in length which fold independently in a common globular motif, called an immunoglobulin (Ig) domain. The region of an antibody formed by the association of the two heavy chains is hydrophobic. Antibodies, and especially monoclonal antibodies, are known to cleave at the site where the light chain attaches to the heavy chain when they are subjected to adverse physical or chemical conditions. Because antibodies contain numerous cysteine residues, they have many cysteine-cysteine disulfide bonds. All Ig domains contain two layers of beta-pleated sheets with three or four strands of anti-parallel polypeptide chains.
[0006] Despite their overall similarity, antibody molecules can be divided into a small number of distinct classes and subclasses based on physicochemical characteristics such as size, charge and solubility, and on their behavior in binding to antigens. In humans, the classes of antibody molecules are: IgA, IgD, IgE, IgG and IgM. Members of each class are said to be of the same isotype. IgA and IgG isotypes are further subdivided into subtypes called IgA1, IgA2 and IgG1, IgG2, IgG3 and IgG4. The heavy chains of all antibodies in an isotype share extensive regions of amino acid sequence identity, but differ from antibodies belonging to other isotypes or subtypes. Heavy chains are designated by the letters of the Greek alphabet corresponding to the overall isotype of the antibody, e.g., IgA contains .alpha., IgD contains .delta., IgE contains .epsilon., IgG contains .gamma., and IgM contains .mu. heavy chains. IgG, IgE and IgD circulate as monomers, whereas secreted forms of IgA and IgM are dimers or pentamers, respectively, stabilized by the J chain. Some IgA molecules exist as monomers or trimers.
[0007] There are between 10 8 and 10 10 structurally different antibody molecules in every individual, each with a unique amino acid sequence in their antigen combining sites. Sequence diversity in antibodies is predominantly found in three short stretches within the amino terminal domains of the heavy and light chains called variable (V) regions, to distinguish them from the more conserved constant (C) regions.
[0008] Atherosclerosis is a chronic disease that causes a thickening of the innermost layer (the intima) of large and medium-sized arteries. It decreases blood flow and may cause ischemia and tissue destruction in organs supplied by the affected vessel. Atherosclerosis is the major cause of cardiovascular disease including myocardial infarction, stroke and peripheral artery disease. It is the major cause of death in the western world and is predicted to become the leading cause of death in the entire world within two decades.
[0009] The disease is initiated by accumulation of lipoproteins, primarily low-density lipoprotein (LDL), in the extracellular matrix of the vessel. These LDL particles aggregate and undergo oxidative modification. Oxidized LDL is toxic and cause vascular injury.
[0010] Atherosclerosis represents in many respects a response to this injury including inflammation and fibrosis.
[0011] In 1989 Palinski and coworkers identified circulating autoantibodies against oxidized LDL in humans. This observation suggested that atherosclerosis may be an autoimmune disease caused by immune reactions against oxidized lipoproteins. At this time several laboratories began searching for associations between antibody titers against oxidized LDL and cardiovascular disease. However, the picture that emerged from these studies was far from clear. Antibodies existed against a large number of different epitopes in oxidized LDL, but the structure of these epitopes was unknown. The term “oxidized LDL antibodies” thus referred to an unknown mixture of different antibodies rather than to one specific antibody. T cell-independent IgM antibodies were more frequent than T-cell dependent IgG antibodies.
[0012] Antibodies against oxidized LDL were present in both patients with cardiovascular disease and in healthy controls. Although some early studies reported associations between oxidized LDL antibody titers and cardiovascular disease, others were unable to find such associations. A major weakness of these studies was that the ELISA tests used to determine antibody titers used oxidized LDL particles as ligand. LDL composition is different in different individuals, the degree of oxidative modification is difficult both to control and assess and levels of antibodies against the different epitopes in the oxidized LDL particles can not be determined. To some extent, due to the technical problems it has been difficult to evaluate the role of antibody responses against oxidized LDL using the techniques available so far, but, however, it is not possible to create well defined and reproducable components of a vaccine if one should use intact oxidized LDL particles.
[0013] Another way to investigate the possibility that autoimmune reactions against oxidized LDL in the vascular wall play a key role in the development of atherosderosis is to immunize animals against its own oxidized LDL. The idea behind this approach is that if autoimmune reactions against oxidized LDL are reinforced using classical immunization techniques this would result in increased vascular inflammation and progressive of atherosclerosis. To test this hypothesis rabbits were immunized with homologous oxidized LDL and then induced atherosderosis by feeding the animals a high-cholesterol diet for 3 months.
[0014] However, in contrast to the original hypothesis immunization with oxidized LDL had a protective effect reducing atherosderosis with about 50%. Similar results were also obtained in a subsequent study in which the high-cholesterol diet was combined with vascular balloon-injury to produce a more aggressive plaque development. In parallel with our studies several other laboratories reported similar observations. Taken together the available data clearly demonstrates that there exist immune reactions that protect against the development of atherosclerosis and that these involves autoimmunity against oxidized LDL.
[0015] These observations also suggest the possibility of developing an immune therapy or “vaccine” for treatment of atherosclerosis-based cardiovascular disease in man. One approach to do this would be to immunize an individual with his own LDL after it has been oxidized by exposure to for example copper. However, this approach is complicated by the fact that it is not known which structure in oxidized LDL that is responsible for inducing the protective immunity and if oxidized LDL also may contain epitopes that may give rise to adverse immune reactions.
[0016] The identification of epitopes in oxidized LDL is important for several aspects:
[0017] First, one or several of these epitopes are likely to be responsible for activating the anti-atherogenic immune response observed in animals immunized with oxidized LDL. Peptides containing these epitopes may therefore represent a possibility for development of an immune therapy or “atherosclerosis vaccine” in man. Further, they can be used for therapeutic treatment of atheroschlerosis developed in man.
[0018] Secondly, peptides containing the identified epitopes can be used to develop ELISAs able to detect antibodies against specific structure in oxidized LDL. Such ELISAs would be more precise and reliable than ones presently available using oxidized LDL particles as antigen. It would also allow the analyses of immune responses against different epitopes in oxidized LDL associated with cardiovascular disease.
[0019] U.S. Pat. No. 5,972,890 relates to a use of peptides for diagnosing atherosclerosis. The technique presented in said US patent is as a principle a form of radiophysical diagnosis. A peptide sequence is radioactively labelled and is injected into the bloodstream. If this peptide sequence should be identical with sequences present in apolipoprotein B it will bind to the tissue where there are receptors present for apolipoprotein B. In vessels this is above all atherosderotic plaque. The concentration of radioactivity in the wall of the vessel can then be determined e.g., by means of a gamma camera. The technique is thus a radiophysical diagnostic method based on that radioactively labelled peptide sequences will bound to their normal tissue receptors present in atherosclerotic plaque and are detected using an external radioactivity analysis. It is a direct analysis method to identify atherosclerotic plaque. It requires that the patient be given radioactive compounds.
[0020] Published studies (Palinski et al., 1995, and George et al., 1998) have shown that immunisation against oxidised LDL reduces the development of atherosclerosis. This would indicate that immuno reactions against oxidised LDL in general have a protecting effect. The results given herein have, however, surprisingly shown that this is not always the case. E.g., immunisation using a mixture of peptides #10, 45, 154, 199, and 240 gave rise to an increase of the development of atherosderosis. Immunisation using other peptide sequences, e.g., peptide sequences #1, and 30 to 34 lacks total effect on the development of atherosderosis. The results are surprising because they provide basis for the fact that immuno reactions against oxidised LDL, can protect against the development, contribute to the development of atherosclerosis, and be without any effect at all depending on which structures in oxidised LDL they are directed to. These findings make it possible to develop immunisation methods, which isolate the activation of protecting immuno reactions. Further, they show that immunisation using intact oxidised LDL could have a detrimental effect if the particles used contain a high level of structures that give rise to atherogenic immuno reactions.
[0021] The technique of the present invention is based on quite different principles and methods. In accordance with claim 1 the invention relates to antibodies raised against oxidized fragments of apolipoprotein B, which antibodies are used for immunisation against cardiovascular disease.
[0022] As an alternative to active immunisation, using the identified peptides described above, passive immunisation with pre-made antibodies directed to the same peptides is an attractive possibility. Such antibodies may be given desired properties concerning e.g. specificity and crossreactivity, isotype, affinity and plasma halflife. The possibility to develop antibodies with predetermined properties became apparent already with the advent of the monoclonal antibody technology (Milstein and Köhler, 1975 Nature, 256:495-7). This technology used murine hybridoma cells producing large amounts of identical, but murine, antibodies. In fact, a large number of preclinical, and also clinical trials were started using murine monoclonal antibodies for treatment of e.g. cancers. However, due to the fact that the antibodies were of non-human origin the immune system of the patients recognised them as foreign and developed antibodies to them. As a consequence the efficacy and plasma half-lives of the murine antibodies were decreased, and often side effects from allergic reactions, caused by the foreign antibody, prevented successful treatment.
[0023] To solve these problems several approaches to reduce the murine component of the specific and potentially therapeutic antibody were taken. The first approach comprised technology to make so called chimearic antibodies where the murine variable domains of the antibody were transferred to human constant regions resulting in an antibody that was mainly human (Neuberger et al. 1985, Nature 314:268-70). A further refinement of this approach was to develop humanised antibodies where the regions of the murine antibody that contacted the antigen, the so called Complementarity Determining Regions (CDRs) were transferred to a human antibody framework. Such antibodies are almost completely human and seldom cause any harmful antibody responses when administered to patients. Several chimearic or humanised antibodies have been registered as therapeutic drugs and are now widely used within various indications (Borrebaeck and Carlsson, 2001, Curr. Opin. Pharmacol. 1:404-408).
[0024] Today also completely human antibodies may be produced using recombinant technologies. Typically large libraries comprising billions of different antibodies are used. In contrast to the previous technologies employing chimearisation or humanisation of e.g. murine antibodies this technology does not rely on immunisation of animals to generate the specific antibody. In stead the recombinant libraries comprise a huge number of pre-made antibody variants why it is likely that the library will have at least one antibody specific for any antigen. Thus, using such libraries the problem becomes the one to find the specific binder already existing in the library, and not to generate it through immunisations. In order to find the good binder in a library in an efficient manner, various systems where phenotype i.e. the antibody or antibody fragment is linked to its genotype i.e. the encoding gene have been devised. The most commonly used such system is the so called phage display system where antibody fragments are expressed, displayed, as fusions with phage coat proteins on the surface of filamentous phage particles, while simultaneously carrying the genetic information encoding the displayed molecule (McCafferty et al., 1990, Nature 348:552-554). Phage displaying antibody fragments specific for a particular antigen may be selected through binding to the antigen in question. Isolated phage may then be amplified and the gene encoding the selected antibody variable domains may optionally be transferred to other antibody formats as e.g. full length immunoglobulin and expressed in high amounts using appropriate vectors and host cells well known in the art.
[0025] The format of displayed antibody specificities on phage particles may differ. The most commonly used formats are Fab (Griffiths et al., 1994. EMBO J. 13:3245-3260) and single chain (scFv) (Hoogenboom et al., 1992, J Mol Biol. 227:381-388) both comprising the variable antigen binding domains of antibodies. The single chain format is composed of a variable heavy domain (VH) linked to a variable light domain (VL) via a flexible linker (U.S. Pat. No. 4,946,778). Before use as analytical reagents, or therapeutic agents, the displayed antibody specificity is transferred to a soluble format e.g. Fab or scFv and analysed as such. In later steps the antibody fragment identified to have desireable characteristics may be transferred into yet other formats such as full length antibodies.
[0026] Recently a novel technology for generation of variability in antibody libraries was presented (WO98/32845, Soderlind et al., 2000, Nature BioTechnol. 18:852-856).
[0027] Antibody fragments derived from this library all have the same framework regions and only differ in their CDRs. Since the framework regions are of germline sequence the immunogenicity of antibodies derived from the library, or similar libraies produced using the same technology, are expected to be particularly low (Soderlind et al., 2000, Nature BioTechnol. 18:852-856). This property is expected to be of great value for therapeutic antibodies reducing the risk for the patient to form antibodies to the administered antibody thereby reducing risks for allergic reactions, the occurrence of blocking antibodies, and allowing a long plasma half-life of the antibody. Several antibodies derived from recombinant libraries have now reached into the clinic and are expected to provide therapeutic drugs in the near future.
[0028] Thus, when met with the challenge to develop therapeutic antibodies to be used in humans the art teaches away from the earlier hybridoma technology and towards use of modern recombinant library technology (Soderlind et al., 2001, Comb. Chem. & High Throughput Screen. 4:409-416). It was realised that the peptides identified (PCT/SE02/00679), and being a integral part of this invention, could be used as antigens for generation of fully human antibodies with predetermined properties. In contrast to earlier art (U.S. Pat. No. 6,225,070) the antigenic structures i.e. the peptides used in the present invention were identified as being particularly relevant as target sequences for therapeutic antibodies (PCT/SE02/00679). Also, in the present invention the antibodies are derived from antibody libraries omitting the need for immunisation of lipoprotein deficient mice to raise murine antibodies (U.S. Pat. No. 6,225,070). Moreover, the resulting antibodies are fully human and are not expected to generate any undesired immunological reaction when administered into patients.
[0029] The peptides used, and previously identified (PCT/SE02/00679) are the following:
TABLE 1 A. High IgG, MDA-difference P 11. FLDTVYGNCSTHFTVKTRKG P 25. PQCSTHILQWLKRVHANPLL P 74. VISIPRLQAEARSEILAHWS B. High IgM, no MDA-difference P 40. KLVKEALKESQLPTVMDFRK P 68. LKFVTQAEGAKQTEATMTFK P 94. DGSLRHKFLDSNIKFSHVEK P 99. KGTYGLSCQRDPNTGRLNGE P 100. RLNGESNLRFNSSYLQGTNQ P 102. SLTSTSDLQSGIIKNTASLK P 103. TASLKYENYELTLKSDTNGK P 105. DMTFSKQNALLRSEYQADYE P 177. MKVKIIRTIDQMQNSELQWP C. High IgG, no MDA difference P 143. IALDDAKINFNEKLSQLQTY P 210. KTTKQSFDLSVKAQYKKNKH D. NHS/AHP, IgG-ak > 2, MDA-difference P1. EEEMLENVSLVCPKDATRFK P 129. GSTSHHLVSRKSISMLEHK P 148. IENIDFNKSGSSTASWIQNV P 162. IREVTQRLNGEIQALELPQK P 252. EVDVLTKYSQPEDSLIPFFE E. NHS/AHP, IgM-ak > 2, MDA-difference P 301. HTFLIYITELLKKLQSTTVM P 30. LLDIANYLMEQIQDDCTGDE P 31. CTGDEDYTYKIKRVIGNMGQ P 32. GNMGQTMEQLTPELKSSILK P 33. SSILKCVQSTKPSLMIQKAA P 34. IQKAAIQALRKMEPKDKDQE P 100. RLNGESNLRFNSSYLQGTNQ P 107. SLNSHGLELNADILGTDKIN P 149. WIQNVDTKYQIRIQIQEKLQ P 169. TYISDWWTLAAKNLTDFAEQ P 236. EATLQRIYSLWEHSTKNHLQ F. NHS/AHP, IgG-ak <0.5, no MDA-difference P 10. ALLVPPETEEAKQVLFLDTV P 45. IEIGLEGKGFEPTLEALFGK P 111. SGASMKLTTNGRFREHNAKF P 154. NLIGDFEVAEKINAFRAKVH P 199. GHSVLTAKGMALFGEGKAEF P 222. FKSSVITLNTNAELFNQSDI P 240. FPDLGQEVALNANTKNQKIR or an active site of one or more of these peptides.
SUMMARY OF THE INVENTION
[0030] The present invention relates to the use of at least one recombinant human antibody or an antibody fragment thereof directed towards at least one oxidized fragment of apolipoprotein B in the manufacture of a pharmaceutical composition for therapeutical or prophylactical treatment of atherosclerosis by means of passive immunization.
[0031] Further the invention relates to the recombinant preparation of such antibodies, as well as the invention relates to method for passive immunization using such antibodies raised using an oxidized apolipoprotein B fragement, as antigen, in particular a fragemnt as identified above.
[0032] The present invention utilises an isolated antibody fragment library to generate specific human antibody fragments against oxidized, in particular MDA modified peptides derived from Apo B100. Identified antibody fragments with desired characteristics may then rebuilt into full length human immunoglobulin to be used for therapeutic purposes.
DETAILED DESCRIPTION OF THE INVENTION
[0033] Below will follow a detailed description of the invention examplified by, but not limited to, human antibodies derived from an isolated antibody fragment library and directed towards two MDA modified peptides from ApoB 100.
EXAMPLE 1
[0034] Selection of scFv Against MDA Modified Peptides IEIGL EGKGF EPTLE ALFGK (P45. Table 1) and KTTKQ SFDLS VKAQY KKNKH (P210, Table 1)
[0035] The target antigens were chemically modified to carry Malone-di-aldehyde (MDA) groups on lysines and histidines. The modified peptides were denoted IEI (P45) and KTT (P210).
[0036] Selections were performed using BioInvent's n-CoDeR™scFv library for which the principle of construction and production have been described in Soderlind et al. 2000, Nature BioTechnology. 18, 852-856. Briefly, CDRs are isolated from human immunoglobulin genes and are shuffled into a fixed framework. Thus variability in the resulting immunoglobulin variable regions is a consequence of recombination of all six CDRs into the fixed framework. The framework regions are all germline and are identical in all antibodies. Thus variability is restricted to the CDRs which are all natural and of human origin. The library contains approximately 2×10 10 independent clones and a 2000 fold excess of clones were used as input for each selection. Selections were performed in three rounds. In selection round 1, Immunotubes (NUNC maxisorb 444202) were coated with 1.2 ml of 20 μg/ml MDA-modified target peptides in PBS (137 mM NaCl, 2.7 mM KCl, 4.3 mM Na 2 HPO 4 , 1.4 mM KH 2 PO 4 ) with end over end agitation at +4° C. over night. The tubes were then blocked with TPBSB5% (5 % BSA, 0.05% Tween 20, 0.02% sodium Azide in PBS) for 30 minutes and washed twice with TPBSB3% (3% BSA, 0.05% Tween 20, 0.02% sodium Azide in PBS) before use. Each target tube was then incubated with approximately 2×10 13 CFU phages from the n-CodeR™ library in 1.8 ml TPBSB3% for 2 h at room temperature, using end over end agitation. The tubes were then washed with 15×3 ml TPBSB3% and 2×1 ml PBS before the bound phages were eluted with 1 ml/tube of 2 mg/ml trypsin (Roche, 109819) for 30 minutes at room temperature. This procedure takes advantage of a specific trypsin site in the scFv-fusion protein to release the phage from the target. The reaction was stopped by the addition of 100 μl of Aprotein (0.2 mg/ml, Roche, cat.236624), and the immunotubes were washed with 300 ul PBS, giving a final volume of 1.4 ml.
[0037] For amplification of the selected phage E. Coli HB101F′ cells were grown exponentially in 10 ml of LB medium (Merck, cat. 1.10285) to OD 600 =0.5 and infected with the selected and eluted phage principally as described (Soderlind et al., 2000, Nature BioTechnol. 18, 852-856. The resulting phage supernatant was then precipitated by addition of ¼ volume of 20% PEG 6000 in 2.5 M NaCl and incubated for 5 h at +4° C. The phages were then pelleted by centrifugation for 30 minutes, 13000×g, re-suspended in 500 μl PBS and used in selection round 2.
[0038] The amplified phagestock was used in selection round 2 in a final volume of 1.5 ml of 5% BSA, 0.05% Tween 20, 0.02% sodium Azide in PBS. Peptide without MDA modification (4×10 −7 M) was also included for competition against binders to MDA-unmodified target peptide. The mixture was incubated in immunotubes prepared with antigen as described above, except that the tubes were blocked with 1% Casein instead of TPBSB3%. The incubations and washing of the immunotubes were as described for selection 1. Bound phages were then eluted for 30 minutes using 600 μl of 100 mM Tris-Glycine buffer, pH 2.2. The tubes were washed with additional 200 μl glycin buffer and the eluates were pooled and then neutralised with 96 μl of 1 M Tris-HCl, pH 8.0. The samples were re-natured for 1 h at room temperature and used for selection round 3.
[0039] For selection round 3, BSA, Tween 20 and Sodium Azide were added to the renaturated phage pool to a final concentration of 3%, 0.05% and 0.02%, respectively. Competitor peptides, MDA modified unrelated peptides as well as native target peptides without modification were added to a concentration of 1×10 −7 M. The phage mixtures (1100 μl) were added to immunotubes coated with target antigen as described in selection 1 and incubated over night at 4° C. with agitation. The tubes were then washed with 3×3 ml TPBSB 3%, 5×3 ml PBS and eventually bound phages were eluted using trypsin as described in selection round 1 above. Each eluate was infected to 10 ml of logarithmically growing HB101F′ in LB containing 100 μg/ml ampicillin, 15 μg/ml tetracycline, 0.1% glucose, and grown over night at 30° C., 200 rpm in a shaker incubator.
[0040] The over night cultures were used for mini scale preparation of plasmid DNA, using Biorad mini prepp Kit (Cat. 732 6100). To remove the phage gene III part from the expression vector, 0.25 μg of the plasmid DNA was cut for 2 h at 37° C. using 2.5 U Eag-1 (New England Biolabs, cat. R050) in the buffer recommended by the supplier. The samples were then heat inactivated for 20 minutes at 65° C. and ligated over night at 16° C. using 1 U T4 DNA ligase in 30 μl of 1× ligase buffer (Gibco/BRL). This procedure will join two Eag-1 sites situated on opposite sides of the phage gene III fragment, thus creating a free scFv displaying a terminal 6×his tag. After ligation the material was digested for 2 h at 37° C. in a solution containing 30 ul ligation mix, 3.6 μl 10×REACT3 stock, 0.4 μl, 1 M NaCl, 5 pi H 2 O 2 , in order to destroy clones in which the phage gene III segment had been religated. Twenty (20) ng of the final product were transformed into chemical competent Top10F′ and spread on 500 cm 2 Q-tray LA-plates (100 μg/ml Amp, 1% glucose), to enable the picking of single colonies for further screening.
[0041] Screening of the n-CoDeR™scFv Library for Specific Antibody Fragments Binding to MDA Modified Peptides from Apolipoprotein B-100
[0042] In order to identify scFv that could discriminate between MDA modified IEI (P45) peptide and native IEI and between MDA modified KTT (P210) and native KTT respectively screenings were performed on bacterial supernatants from selected scFv expressing clones.
[0043] Colony picking of single clones, expression of scFv and screening number 1 was performed on BioInvent's automatic system according to standard methods. 1088 and 831 single clones selected against the MDA modified 1EI and KTT peptides respectively were picked and cultured and expressed in micro titre plates in 100 μl LB containing 100 μg ampicillin/ml.
[0044] For screening number 1 white Assay plates (Greiner 655074) were coated with 54 pmol peptide/well in coating buffer (0.1 M Sodium carbonate, pH 9.5), either with MDA modified peptide which served as positive target or with corresponding unmodified peptide which served as non target. In the ELISA the expressed scFv were detected through a myc-tag situated C-terminal to the scFv using 1 μg/ml of anti-c-myc monoclonal (9E10 Roche 1667 149) in wash buffer. As a secondary antibody Goat-anti-mouse alkaline phosphatase conjugate (Applied Biosystems Cat #AC32ML) was used at 25000 fold dilution. For luminescence detection CDP-Star Ready to use with Emerald II Tropix (Applied Biosystems Cat #MS100RY) were used according to suppliers recommendation.
[0045] ScFv clones that bound MDA modified peptide but not native peptide were re expressed as described above and to screening another time in a luminescent ELISA (Table 2 and FIG. 1). Tests were run both against directly coated peptides (108 pmol/well coated with PBS) and the more physiological target, LDL particles (1 μg/well coated in PBS+1 mM EDTA) containing the ApoB-100 protein with and without MDA modification were used as targets. Positive clones were those that bound oxidised LDL and MDA modified peptide but not native LDL or peptide. The ELISA was performed as above except that the anti-His antibody (MaBO50 RaD) was used as the detection antibody. Twelve IEI clones and 2 KTT clones were found to give more than three fold higher luminescence signal at 700 nm for the MDA modified form than for the native form both for the peptide and LDL.
[0046] The identified clones were further tested through titration against a fixed amount (1 μg/well) of MDA LDL and native LDL in order to evaluate the dose response of the scFv (FIG. 2).
TABLE 2 Screening results. The number of clones tested in each screening step for each target. The scored hits in percent are shown within brackets. Target IEI KTT Screening Tested Clones 1088 831 number 1 Scored Hits 64 33 (%) (5.9%) (4.0%) Screening Tested Clones 64 33 number 2 Scored Hits 12 2 (%) (1.1%) (0.2%) Dose Tested Clones 12 2 response Scored Hits 8 2 (%) (0.7%) (0.2%)
[0047] The sequences of the chosen scFv clones were determined in order to find unique clones. Bacterial PCR was performed with the Boeringer Mannheim Expand kit using primers (5′-CCC AGT CAC GAC GTT GTA MA CG-3′) and (5′-GAA ACA GCT ATG AAA TAC CTA TTG C-3′) and a GeneAmp PCR system 9700 (PE Applied system) using the temperature cycling program 94° C. 5 min, 30 cycles of 94° C. 30 s, 52° C. for 30 s and 68° C. for 2 min and finally 5 min at 68 min. The sequencing reaction was performed with the bacterial PCR product (five fold diluted) as template, using Big Dye Terminator mix from PE Applied Biosystems and the GeneAmp PCR system 9700 (PE Applied system) and the temperature cycling program 25 cycles of 96° C. 10 s, 50° C. for 5 s and 60° C. for 4 min. The extension products were purified according to the supplier's instructions and the separation and detection of extension products was done by using a 3100 Genetic analyser (PE Applied Biosystems). The sequences were analysed by the in house computer program. From the sequence information homologous clones and clones with inappropriate restriction sites were excluded, leaving six clones for IgG conversion. The DNA sequence of the variable heavy (VH) and variable light (VL) domains of the finally selected clones are shown in FIG. 3.
EXAMPLE 2
[0048] Transfer of Genes Encoding the Variable Parts of Selected scFv to Full Length Human IgG1 Vestors.
[0049] Bacteria containing scFv clones to be converted to Ig-format were grown over night in LB supplemented with 100 μg/ml ampicillin. Plasmid DNA was prepared from over night cultures using the Quantum Prep, plasmid miniprep kit from Biorad (#732-6100). The DNA concentration was estimated by measuring absorbance at 260 nm, and the DNA was diluted to a concentration of 2 ng/μl. VH and VL from the different scFv-plasmids were PCR amplified in order to supply these segments with restriction sites compatible with the expression vectors (see below). 5′ primers contain a BsmI and 3′ primers contain a BsiWI restriction enzyme cleavage site (shown in italics). 3′ primers also contained a splice donor site (shown in bold).
[0050] Primers for amplification of VH-segments:
(SEQ. ID. NO: 13) 5′VH: 5′-GGTGTGCATTCCGAGGTGCAGCTGTTGGAG (SEQ. ID. NO: 14) 3′VH: 5′-GACGTACG ACTCACCT GAGCTCACGGTGACCAG
[0051] Primers for amplification of VL-segments:
(SEQ. ID. NO: 15) 5′VL: 5′-GGTGTGCATTCCCAGTCTGTGCTGACTCAG (SEQ. ID. NO: 16) 3′VL: 5′-GACGTACGTTCT ACTCACCT AGGACCGTCAGCTT
[0052] PCR was conducted in a total volume of 50 μl, containing 10 ng template DNA, 0.4 μM 5′ primer, 0.4 μM 3′ primer and 0.6 mM dNTP (Roche, #1 969 064). The polymerase used was Expand long template PCR system (Roche #1 759 060), 3.5 u per reaction, together with each of the supplied buffers in 3 separate reactions. Each PCR amplification cycle consisted of a denaturing step at 94° C. for 30 seconds, an annealing step at 55° C. for 30 seconds, and an elongating step at 68° C. for 1.5 minutes. This amplification cycle was repeated 25 times. Each reaction began with a single denaturing step at 94° C. for 2 minutes and ended with a single elongating step at 68° C. for 10 minutes. The existence of PCR product was checked by agarose gel electrophoresis, and reactions containing the same amplified material (from reactions with different buffers) were pooled. The PCR amplification products were subsequently purified by spin column chromatography using S400-HR columns (Amersham-Pharmacia Biotech #27-5240-01).
[0053] Four (4) μl of from each pool of PCR products were used for TOPO TA cloning (pCR 2.1 TOPO, InVitrogen #K4550-01) according to the manufacturers recommendations. Bacterial colonies containing plasmids with inserts were grown over night in LB supplemented with 100 μg/ml ampicillin and 20 μg/ml kanamycin. Plasmid DNA was prepared from over night cultures using the Quantum Prep, plasmid miniprep kit from Biorad (#732-6100). Plasmid preparations were purified by spin column chromatography using S400-HR columns (Amersham-Pharmacia Biotech #27-5240-01). Three plasmids from each individual VH and VL cloning were subjected to sequence analysis using BigDye Cycle Sequencing (Perkin Elmer Applied Biosystem, #4303150). The cycle sequencing program consisted of a denaturing step at 96° C. for 10 seconds, an annealing step at 50° C. for 15 seconds, and an elongating step at 60° C. for 4 minutes. This cycle was repeated 25 times. Each reaction began with a single denaturing step at 94° C. for 1 minute. The reactions were performed in a volume of 10 μl consisting of 1 μM primer (5′-CAGGMACAGCTATGAC), 3 μl plasmid DNA and 4 μl Big Dye reaction mix. The reactions were precipitated according to the manufacturers recommendations, and samples were run on a ABI PRISM 3100 Genetic Analyzer. Sequences were compared to the original scFv sequence using the alignment function of the OMIGA sequence analysis software (Oxford Molecular Ltd).
[0054] Plasmids containing VH and VL segments without mutations were restriction enzyme digested. To disrupt the pCR 2.1 TOPO vector, plasmids were initially digested with DraI (Roche #1 417 983) at 37° C. for 2 hours. Digestions were heat inactivated at 70° C. for 20 minutes and purified by spin column chromatography using S400-HR columns (Amersham-Pharmacia Biotech #27-5240-01). The purified DraI digestions were subsequently digested with BsmI (Roche #1 292 307) and BsiWI (Roche #1 388 959) at 55° C. over night. Digestions were purified using phenol extraction and precipitation. The precipitated DNA was dissolved in 10 μl H 2 O and used for ligation.
[0055] The expression vectors were obtained from Lars Norderhaug (J. Immunol. Meth. 204 (1997) 77-87). After some modifications, the vectors (FIG. 4) contain a CMV promoter, an Ig-leader peptide, a cloning linker containing BsmI and BsiWI restriction sites for cloning of VH/VL, genomic constant regions of IgG1(heavy chain (HC) vector) or lambda (light chain (LC) vector), neomycin (HC vector) or methotrexate (LC vector) resistance genes for selection in eukaryotic cells, SV40 and ColEI origins of replication and ampicillin (HC vector) or kanamycin (LC vector) resistance genes for selection in bacteria.
[0056] The HC and LC vectors were digested with BsmI and BsiWI, phosphatase treated and purified using phenol extraction and precipitation. Ligation were set up at 16° C. over night in a volume of 10 μl, containing 100 ng digested vector, 2 μl digested VH/VL-pCR 2.1 TOPO vector (see above), 1 U T4 DNA ligase (Life Technologies, #15224-025) and the supplied buffer. 2 μl of the ligation mixture were subsequently transformed into 50 μl chemocompetent top10F′ bacteria, and plated on selective (100 μg/ml ampicillin or 20 μg/ml kanamycin) agar plates.
[0057] Colonies containing HC/LC plasmids with VH/VL inserts were identified by colony PCR:
Forward primer: 5′-ATGGGTGACAATGACATC Reverse primer: 5′-AAGCTTGCTAGCGTACG
[0058] PCR was conducted in a total volume of 20 μl, containing bacterias, 0.5 μM forward primer, 0.5 μM reverse primer and 0.5 mM dNTP (Roche, #1 969 064). The polymerase used was Expand long template PCR system (Roche #1 759 060), 0.7 U per reaction, together with the supplied buffer #3. Each PCR amplification cycle consisted of a denaturing step at 94° C. for 30 seconds, an annealing step at 52° C. for 30 seconds, and an elongating step at 68° C. for 1.5 minutes. This amplification cycle was repeated 30 times. Each reaction began with a single denaturing step at 94° C. for 2 minutes and ended with a single elongating step at 68° C. for 5 minutes. The existence of PCR product was checked by agarose gel electrophoresis. Colonies containing HC/LC plasmids with VH/VL inserts were grown over night in LB supplemented with 100 μg/ml ampicillin or 20 μg/ml kanamycin. Plasmid DNA was prepared from over night cultures using the Quantum Prep, plasmid miniprep kit from Biorad (#732-6100). Plasmid preparations were purified by spin column chromatography using S400-HR columns (Amersham-Pharmacia Biotech #27-5240-01). To confirm the integrity of the DNA sequence, three plasmids from each individual VH and VL were subjected to sequence analysis using BigDye Cycle Sequencing (Perkin Elmer Applied Biosystem, #4303150). The cycle sequencing program consisted of a denaturing step at 96° C. for 10 seconds, an annealing step at 50° C. for 15 seconds, and an elongating step at 60° C. for 4 minutes. This cycle was repeated 25 times. Each reaction began with a single denaturing step at 94° C. for 1 minute. The reactions were performed in a volume of 10 μl, consisting of 1 μM primer (5′-AGACCCAAGCTAGCTTGGTAC), 3 μl plasmid DNA and 4 μl Big Dye reaction mix. The reactions were precipitated according to the manufacturers recommendations, and samples were run on a ABI PRISM 3100 Genetic Analyzer. Sequences were analysed using the OMIGA sequence analysis software (Oxford Molecular Ltd). The plasmid DNA was used for transient transfection of COS-7 cells (see below) and were digested for production of a joined vector, containing heavy- and light chain genes on the same plasmid.
[0059] Heavy and light chain vectors containing VH and VL segments originating from the same scFv were cleaved by restriction enzymes and ligated: HC- and LC-vectors were initially digested with MunI (Roche #1 441 337) after which digestions were heat inactivated at 70° C. for 20 minutes and purified by spin column chromatography using S200-HR columns (Amersham-Pharmacia Biotech #27-5120-01). HC-vector digestions were subsequently digested with NruI (Roche #776 769) and LC-vector digestions with Bst1107I (Roche #1 378 953). Digestions were then heat inactivated at 70° C. for 20 minutes and purified by spin column chromatography using S400-HR columns (Amersham-Pharmacia Biotech #27-5240-01). 5 μl of each digested plasmid were ligated at 16° C. over night in a total volume of 20 μl, contaning 2 U T4 DNA ligase (Life Technologies, #15224-025) and the supplied buffer. 2 μl of the ligation mixture were subsequently transformed into 50 μl chemocompetent top10F′ bacteria, and plated on selective (100 μg/ml ampicillin and 20 μg/ml kanamycin) agar plates.
[0060] Bacterial colonies were grown over night in LB supplemented with 100 μg/ml ampicillin and 20 μg/ml kanamycin. Plasmid DNA was prepared from over night cultures using the Quantum Prep, plasmid miniprep kit from Biorad (#732-6100). Correctly joined vectors were identified by restriction enzyme digestion followed by analyses of fragment sizes by agarose gel-electrophoreses.
[0061] Plasmid preparations were purified by spin column chromatography using S400-HR columns (Amersham-Pharmacia Biotech #27-5240-01) and used for transient transfection of COS-7 cells.
[0062] COS-7 cells (ATCC #CRL-1651) were cultured at 37° C. with 5% CO 2 in Dulbeccos MEM, high glucose+GlutamaxI (Invitrogen #31966021), supplementd with 0.1 mM non-essential amino acids (Invitrogen #11140035) and 10% fetal bovine sera (Invitrogen #12476-024, batch #1128016). The day before transfection, the cells were plated in 12-well plates (Nunc, #150628) at a density of 1.5×10 5 cells per well.
[0063] Prior to transfection, the plasmid DNA was heated at 70° C. for 15 minutes. Cells were transfected with 1 μg HC-plasmid+1 μg LC-plasmid, or 2 μg joined plasmid per well, using Lipofectamine 2000 Reagent (Invitrogen, #11668019) according to the manufacturers recommendations. 24 hours post transfection, cell culture media was changed and the cells were allowed to grow for 5 days. After that, medium was collected and protein production was assayed for using ELISA.
[0064] Ninetysix (96)-well plates (Costar #9018, flat bottom, high binding) were coated at 4° C. over night by adding 100 μl/well rabbit anti-human lamda light chain antibody (DAKO, #A0193) diluted 4000 times in coatingbuffer (0.1M sodium carbonate, pH 9.5). Plates were washed 4 times in PBS containing 0.05% Tween 20 and thereafter blocked with 100 μl/well PBS+3% BSA (Albumin, fraction V, Roche #735108) for 1 h. at room temperature. After washing as above, 100 μl/well of sample were added and incubated in room temperature for 1 hour. As a standard for estimation of concentration, human purified IgG1 (Sigma, #I5029) was used. Samples and standard were diluted in sample buffer (1×PBS containing 2% BSA and 0.5% rabbit serum (Sigma #R4505). Subsequently, plates were washed as described above and 100 μl/well of rabbit anti-human IgG (y-chain) HRP-conjugated antibody (DAKO, #P214) diluted 8000 times in sample buffer was added and incubated at room temperature for 1 hour. After washing 8 times with PBS containing 0.05% Tween 20, 100 μl/well of a substrate solution containing one OPD tablet (10 mg, Sigma #P8287,) dissolved in 15 ml citric acid buffer and 4.5 μl H 2 O 2 (30%) was added. After 10 minutes, the reaction was terminated by adding 150 μl/well of 1M HCl. Absorbance was measured at 490-650 nm and data was analyzed using the Softmax software.
[0065] Bacteria containing correctly joined HC- and LC-vectors were grown over night in 500 ml LB supplemented with ampicillin and kanamycin. Plasmid DNA was prepared from over night cultures using the Quantum Prep, plasmid maxiprep kit from Biorad (#732-6130). Vectors were linearized using PvuI restriction enzyme (Roche #650 129). Prior to transfection, the linearized DNA was purified by spin column chromatography using S400-HR columns (Amersham-Pharmacia Biotech #27-5240-01) and heated at 70° C. for 15 minutes.
EXAMPLE 3
[0066] Stable Transfection of NSO Cells Expressing Antibodies Against MDA Modified Peptides frm Apolipoprotein B-100.
[0067] NSO cells (ECACC no. 85110503) were cultured in DMEM (cat nr 31966-021, Invitrogen) supplemented with 10% Fetal Bovine Serum (cat no. 12476-024, lot: 1128016, Invitrogen) and 1×NEAA (non-essential amino acids, cat no. 11140-053, Invitrogen). Cell cultures are maintained at 37° C. with 5% CO 2 in humidified environment.
[0068] DNA constructs to be transfected were four constructs of IEI specific antibodies (IEI-A8, IEI-D8, IEI-E3, IEI-G8), two of KTT specific antibodies (KTT-B8, KTT-D6) and one control antibody (JFPA12).The day before transfection, the cells were trypsinized and counted, before plating them in a T-75 flask at 12×10 6 cells/flask. On the day of transfection, when the cells were 85-90% confluent, the cells were plated in 15 ml DMEM+1×NEAA+10% FBS (as above). For each flask of cells to be transfected, 35-40 μg of DNA were diluted into 1.9 ml of OPTI-MEM I Reduced Serum Medium (Cat no. 51985-026, lot: 3062314, Invitrogen) without serum. For each flask of cells, 114 μl of Lipofectamine 2000 Reagent (Cat nr. 11668-019, lot: 1116546, Invitrogen) were diluted into 1.9 ml OPTI-MEM I Reduced Serum Medium in another tube and incubated for 5 min at room temperature. The diluted DNA was combined with the diluted Lipofectamine 2000 Reagent (within 30 min) and incubated at room temperature for 20 min to allow DNA-LF2000 Reagent complexes to form.
[0069] The cells were washed with medium once and 11 ml DMEM +1×NEM +10% FBS were added. The DNA-LF2000 Reagent complexes (3.8 ml) were then added directly to each flask and gently mixed by rocking the flask back and forth. The cells were incubated at 37° C. in a 5% CO 2 incubator for 24 h.
[0070] The cells were then trypsinized and counted, and subsequently plated in 96-well plates at 2×10 4 cells/well using five 96-well plates/construct. Cells were plated in 100 μl/well of DMEM+1×NEAA+10% FBS (as above) containing G418-sulphate (cat nr.10131-027, lot: 3066651, Invitrogen) at 600 μg/ml. The selection pressure was kept unchanged until harvest of the cells.
[0071] The cells were grown for 12 days and assayed for antibody production using ELISA. From each construct cells from the 24 wells containing the highest amounts of IgG were transferred to 24-well plates and were allowed to reach confluency. The antibody production from cells in these wells was then assayed with ELISA and 5-21 pools/construct were selected for re-screening (Table 3). Finally cells from the best 1-4 wells for each construct were chosen. These cells were expanded successively in cell culture flasks and finally transferred into triple layer flasks (500 cm2) in 200 ml of (DMEM+1×NEAA+10% Ultra low IgG FBS (cat.no. 16250-078, lot.no. 113466, Invitrogen)+G418 (600 μg/ml)) for antibody production. The cells were incubated for 7-10 days and the supernatants were assayed by ELISA, harvested and sterile filtered for purification.
EXAMPLE 4
[0072] Production and Purification of Human IgG1
[0073] Supernatants from NSO cells transfected with the different IgG1 antibodies were sterile filtered using a 0.22 μm filter and purified using an affinity medium MabSelect™ with recombinant protein A, (Cat. No. 17519901 Amersham Biosciences).
[0074] Bound human IgG1 was eluted with HCL-glycine buffer pH 2.8. The eluate was collected in 0.5 ml fractions and OD 280 was used to determine presence of protein. The peak fractions were pooled and absorbance was measured at 280 nm and 320 nm. Buffer was changed through dialysis against a large volume of PBS. The presence of endotoxins in the purified IgG-1 preparations was tested using a LAL test (QCL-1000R, cat. No. 50-647U Bio Whittaker). The samples contained between 1 and 12 EU/ml endotoxin. The purity of the preparations were estimated to exceed 98% by PAGE analysis.
TABLE 3 Summary of Production and Purification of human IgG1 Volume culture Total IgG1 in Total IgG1 Clone supernatant supernatant Purified name (ml) (mg) (mg) Yield (%) IEI-A8 600 68 42 61.8 IEI-D8 700 45 21 46.7 IEI-E3 700 44.9 25.6 60 IEI-G8 600 74 42.4 57.3 KTT-B8 1790 77.3 37.6 48.6 KTT-D6 1845 47.8 31.8 66.5 JFPA12 2000 32.2 19.2 59.6
[0075] The purified IgG1 preparations were tested in ELISA for reactivity to MDA modified and un-modified peptides (FIG. 5) and were then used in functional in vitro and in vivo studies.
EXAMPLE 5
[0076] Analysis of Possible Anti-Atherogenic Effect of Antibodies are Performed both in Experimental Animals and in Cell Culture Studies.
[0077] 1. Effect of antibodies on atherosclerosis in apolipoprotein E knockout (apo E−) mice. Five weeks old apo E− mice are fed a cholesterol-rich diet for 15 weeks. This treatment is known to produce a significant amount of atherosclerotic plaques in the aorta and carotid arteries. The mice are then given an intraperitoneal injection containing 500 pg of the respective antibody identified above. Control mice are given 500 μg of an irrelevant control antibody or PBS alone. Treatments are repeated after 1 and 2 weeks. The mice are sacrificed 4 weeks after the initial antibody injection. The severity of atherosclerosis in the aorta is determined by Oil Red O staining of flat preparations and by determining the size of subvalvular atherosclerotic plaques. Collagen, macrophage and T cell content of subvalvular atherosclerotic plaques is determined by Masson trichrome staining and cell-specific immunohistochemistry. Quantification of Oil Red O staining, the size of the subvalvular plaques, trichrome staining and immunohistochemical staining is done using computer-based image analysis.
[0078] In a first experiment the effect of the antibodies on development of atherosclerosis was analysed in apo E−/− mice fed a high-cholesterol diet. The mice were given three intraperitoneal injections of 0.5 mg antibody with week intervals starting at 21 weeks of age, using PBS as control. They were sacrificed two weeks after the last antibody injection, and the extent of atherosclerosis was assessed by Oil Red O staining of descending aorta flat preparations. A pronounced effect was observed in mice treated with the IEI-E3 antibody, with more than 50% reduction of atherosclerosis as compared to the PBS group (P=0.02) and to a control group receiving a human IgG1 antibody (FITC8) directed against a non-relevant fluorescein isothiocynate (FITC) antigen (P=0.03) (FIG. 6). The mice tolerated the human antibodies well and no effects on the general health status of the mice were evident.
[0079] To verify the inhibitory effect of the IEI-E3 antibody on development of atherosclerosis we then performed a dose-response study. The schedule was identical to that of the initial study. In mice treated with IEI-E3 antibodies atherosclerosis was reduced by 2% in the 0.25 mg group (n.s.), by 25% in the 0.5 mg group (n.s.) and by 41% (P=0.02) in the 2.0 mg group as compared to the corresponding FITC antibody-treated groups (FIG. 7).
[0080] 2. Effect of antibodies on neo-intima formation following mechanical injury of carotid arteries in apo E− mice. Mechanical injury of arteries results in development of fibro-muscular neo-intimal plaque within 3 weeks. This plaque resembles morphologically a fibro-muscular atherosclerotic plaque and has been used as one model for studies of the development of raised lesion. Placing a plastic collar around the carotid artery causes the mechanical injury. Five weeks old apo E− mice are fed a cholesterol-rich diet for 14 weeks. The mice are then given an intraperitoneal injection containing 500 μg of the respective antibody. Control mice are given 500 μg of an irrelevant control antibody or PBS alone. The treatment is repeated after 7 days and the surgical placement of the plastic collar is performed 1 day later. A last injection of antibodies or PBS is given 6 days after surgery and the animals are sacrificed 15 days later. The injured carotid artery is fixed, embedded in paraffin and sectioned. The size of the neo-intimal plaque is measured using computer-based image analysis.
[0081] 3. Effect of antibodies on uptake of oxidized LDL in cultured human macrophages. Uptake of oxidized LDL in arterial macrophages leading to formation of cholesterol-loaded macrophage foam cells is one of the most characteristic features of the atherosclerotic plaque. Several lines of evidence suggest that inhibiting uptake of oxidized LDL in arterial macrophages represent a possible target for treatment of atherosclerosis. To study the effect of antibodies on macrophage uptake of oxidized c are pre-incubated with 125 I-labeled human oxidized LDL for 2 hours. Human macrophages are isolated from blood donor buffy coats by centrifugation in Ficoll hypaque followed by culture in presence of 10% serum for 6 days. The cells are then incubated with medium containing antibody/oxidized LDL complexes for 6 hours, washed and cell-associated radioactivity determined in a gamma-counter. Addition of IEI-E3 antibodies resulted in a five-fold increase in the binding (P=0.001) and uptake (P=0.004) of oxidized LDL compared to FITC-8 into macrophages, but had no effect on binding or uptake of native LDL (FIG. 8a and 8b).
[0082] 4. Effect of antibodies on oxidized LDL-dependent cytotoxicity. Oxidized LDL is highly cytotoxic. It is believed that much of the inflammatory activity in atherosclerotic plaques is explained by cell injury caused by oxidized LDL. Inhibition of oxidized LDL cytotoxicity thus represents another possible target for treatment of atherosclerosis. To study the effect of antibodies on oxidized LDL cytotoxicity cultured human arterial smooth muscle cells are exposed to 100 ng/ml of human oxidized LDL in the presence of increasing concentrations of antibodies (0-200 ng/ml) for 48 hours. The rate of cell injury is determined by measuring the release of the enzyme LDH.
[0083] The experiment shown discloses an effect for a particular antibody raised against a particular peptide, but it is evident to the one skilled in the art that all other antibodies raised against the peptides disclosed will behave in the same manner.
[0084] The antibodies of the present invention are used in pharmaceutical compositions for passive immunization, whereby the pharmaceutical compositions primarily are intended for injection, comprising a solution, suspension, or emulsion of a single antibody or a mixture of antibodies of the invention in a dosage to provide a therapeutically or prophylactically active level in the body treated. The compositions may be provided with commonly used adjuvants to enhance absorption of the antibody or mixture of antibodies. Other routes of administration may be the nasal route by inhaling the antibody/antibody mixture in combination with inhalable excipients.
[0085] Such pharmaceutical compositions may contain the active antibody in an amount of 0.5 to 99.5% by weight, or 5 to 90% by weight, or 10 to 90% by weight, or 25 to 80% by weight, or 40 to 90% by weight.
[0086] The daily dosage of the antibody, or a booster dosage shall provide for a therapeutically or prophylactically active level in the body treated to reduce or prevent signs and sympthoms of atherosclerosis by way of passive immunization. A dosage of antibody according to the invention may be 1 μg to 1 mg per kg bodyweight, or more.
[0087] The antibody composition can be supplemented with other drugs for treating or preventing atherosclerosis or heart-vascular diseases, such as blood pressure lowering drugs, such as beta-receptor blockers, calcium antagonists, diurethics, and other antihypertensive agents.
[0088] [0088]FIG. 9 shows binding of isolated scFv to MDA modified ApoB100 derived peptides and to a MDA modified control peptide of irrelevant sequence. Also depicted are the ratios between binding of the scFv to MDA modified and native ApoB100 protein and human LDL respectively. Columns appear in the order they are defined from top to bottom in right hand column of the respective subfigure.
[0089] References
[0090] Dimayuga, P., B. Cercek, et al. (2002). “Inhibitory effect on arterial injury-induced neointimal formation by adoptive B-cell transfer in Rag-1 knockout mice.” Arteriosclerosis, Thrombosis and Vascular Biology 22: 644-649.
[0091] Jovinge, S., M. Crisby, et al. (1997). “DNA fragmentation and ultrastructural changes of degenerating cells in atherosclerotic lesions and smooth muscle cells exposed to oxidized LDL in vitro.” Arteriosclerosis, Thrombosis and Vascular Biology 17: 2225-2231.
[0092] Regnström, J., G. Walldius, et al. (1990). “Effect of probucol treatment on suspectibility of low density lipoprotein isolated from hypercholesterolemic patients to become oxidativery modified in vitro.” Atherosclerosis 82: 43-51.
[0093] Steinberg, D., S. Parthasarathy, et al. (1989). “Beyond cholesterol modifications of low-density lipoprotein that increase its atherogenicity.” New England Journal of Medicine 320(14): 915-924.
[0094] Zhou, X., G. Paulsson, et al. (1998). “Hypercholesterolemia is associated with a T helper (Th) 1/Th2 switch of the autoimmune response in atherosclerotic apo E-knockout Mice.” Journal of Clinical Investigation 101: 1717-1725.
1
79
1
369
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
1
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcaat aacgcctgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtagta gtagtagtta catatactac 180
gcagactcag tgaagggccg attcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagagtcagt 300
aggtactact acggaccatc tttctacttt gactcctggg gccagggtac actggtcacc 360
gtgagcagc 369
2
336
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
2
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcaggtc caacattggg aataattatg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat ggtaacaaca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagcctgaa tggtcattgg 300
gtgttcggcg gaggaaccaa gctgacggtc ctaggt 336
3
366
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
3
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcgg cctctggatt caccttcagt gactactaca tgagctgggt ccgccaggct 120
cccgggaagg ggctggagtg ggtatcgggt gttagttgga atggcagtag gacgcactat 180
gcagactctg tgaagggccg attcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagagcggct 300
aggtactcct actactacta cggtatggac gtctggggcc aaggtacact ggtcaccgtg 360
agcagc 366
4
327
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
4
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgttctg gaagcagctc caacatcgga aataatgctg taaactggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat gggaatgatc ggcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtcag acctggggca ctggccgggg ggtattcggc 300
ggaggaacca agctgacggt cctaggt 327
5
366
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
5
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt cacctttagt agctattgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcaagt atcagtggta gtggtcgtag gacatactac 180
gcagactccg tgcagggccg gttcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagattggtc 300
tcctatggtt cggggagttt cggttttgac tactggggcc aaggtacact ggtcaccgtg 360
agcagc 366
6
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
6
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcttgttctg gaagcagctc caatatcgga agtaattatg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat ggtaactaca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagcctgag tggttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
7
378
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
7
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt aacgcctgga tgagctgggt ccgccaggtt 120
ccagggaagg ggctggagtg ggtctcaact cttggtggta gtggtggtgg tagcacatac 180
tacgcagact ccgtgaaggg ccggttcacc atctccagag acaattccaa gaacacgctg 240
tatctgcaaa tgaacagcct gagagccgag gacactgccg tgtattactg tgcgaagtta 300
ggggggcgat cccgatatgg gcggtggccc cgccaatttg actactgggg ccaaggtaca 360
ctggtcaccg tgagcagc 378
8
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
8
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcagctc caacattgga aataactatg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat agtaataatc agcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagcctgag tcattggctg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
9
372
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
9
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt gactactaca tgagctggat ccgccaggct 120
ccagggaagg ggctggagtg ggtctcaagt atcagtggcc gtgggggtag ttcctactac 180
gcagactccg tgaggggccg gttcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagactttcc 300
tacagctatg gttacgaggg ggcctactac tttgactact ggggccaggg tacactggtc 360
accgtgagca gc 372
10
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
10
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcagctc caacattggg aataattatg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat aggaataatc agcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc ttagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca acctgggatg acagcctgaa tggttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
11
363
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
11
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt cacctttagc agctatgcca tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtagta gtggtcgttt catttactac 180
gcagactcaa tgaagggccg cttcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtac gaggctccgg 300
agagggagct acttctgggc ttttgatatc tggggccaag gtacactggt caccgtgagc 360
agc 363
12
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
12
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgttctg gaagcagctc caacattggc ggtgagtctg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat agtaataatc agcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagcctgaa tggttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
13
30
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
13
ggtgtgcatt ccgaggtgca gctgttggag 30
14
33
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
14
gacgtacgac tcacctgagc tcacggtgac cag 33
15
30
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
15
ggtgtgcatt cccagtctgt gctgactcag 30
16
34
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
16
gacgtacgtt ctactcacct aggaccgtca gctt 34
17
18
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
17
atgggtgaca atgacatc 18
18
17
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
18
aagcttgcta gcgtacg 17
19
369
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
19
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt cacctttaga acgtattgga tgacctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatct attagcagta gcagtaatta catattctac 180
gcagactcag tgaagggccg attcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagactcaga 300
cggagcagct ggtacggggg gtactggttc gacccctggg gccaaggtac actggtcacc 360
gtgagctca 369
20
336
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
20
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcagctc caacattggg aataattatg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat aggaataatc agcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagcctgaa tggtcattgg 300
gtgttcggcg gaggaaccaa gctgacggtc ctaggt 336
21
369
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
21
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt agcaactaca tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtagta gtagtagtta catatactac 180
gcagactcag tgaagggccg attcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagagtaggc 300
cggtataact ggaagacggg gcatgctttt gatatctggg gccagggtac actggtcacc 360
gtgagctca 369
22
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
22
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaaggaccta caacattgga aataattatg tatcgtggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat ggtaacatca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg tcaggctgaa tggttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
23
381
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
23
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttccgt gactactacg tgagctggat ccgccaggct 120
ccagggaagg ggctggagtg ggtctcaagt attagtggta gtgggggtag gacatactac 180
gcagactccg tggagggccg gttcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccatgt attactgtgc cagagtatcc 300
gcccttcgga gacccatgac tacagtaact acttactggt tcgacccctg gggccaaggt 360
acactggtca ccgtgagctc a 381
24
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
24
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaaggagctc caacattggg aatagttatg tctcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat aggaataatc agcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca ggatgggatg acaccctgcg tgcttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
25
360
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
25
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt aacgcctgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctccgct attagtggta gtggtaacac atactatgca 180
gactccgtga agggccggtt caccatctcc agagacaatt ccaagaacac gctgtatctg 240
caaatgaaca gcctgagagc cgaggacact gccgtgtatt actgtgcgag agcctcccac 300
cgtatattag gttatgcttt tgatatctgg ggccagggta cactggtcac cgtgagctca 360
26
328
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
26
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcttgttctg gaagccgctc caacatcggg agaaatgctg ttagttggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat gctaacagca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg gcagcctgaa tggttgggtg 300
ttcggcggag gaaccaagct gacggtcc 328
27
363
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
27
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt aacgcctgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcaagt attagtgttg gtggacatag gacatattat 180
gcagattccg tgaagggccg gtccaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc acggatacgg 300
gtgggtccgt ccggcggggc ctttgactac tggggccagg gtacactggt caccgtgagc 360
tca 363
28
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
28
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcaacac caacattggg aagaactatg tatcttggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat gctaatagca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgcg tcatgggatg ccagcctgaa tggttgggta 300
ttcggcggag gaaccaagct gacggtccta ggt 333
29
378
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
29
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt aacgcctgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtagta gtagtagtta catatactac 180
gcagactcag tgaagggccg atccaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gaggctcaca 300
aatattttga ctggttatta tacctcagga tatgcttttg atatctgggg ccaaggtaca 360
ctggtcaccg tgagctca 378
30
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
30
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcacctc caacattggg aagaattatg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat ggtaacagca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg ccagcctcag tggttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
31
363
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
31
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt agttcttgga tgagttgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtagta gtagtagtta catatactac 180
gcagactcag tgaagggccg attcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagagtaggg 300
aactacggtt tctaccacta catggacgtc tggggccaag gtacactggt caccgtgagc 360
tca 363
32
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
32
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcttgttctg gaggcagctc aaacatcgga aaaagaggtg taaattggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat ggtaacagaa atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgct acatgggatt acagcctcaa tgcttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
33
366
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
33
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt cacctttagt agctattgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtagta gtagtagtta catatactac 180
gcagactcag tgaagggccg attcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagaattaaa 300
cggttacgat tcggctggac cccttttgac tactggggcc agggtacact ggtcaccgtg 360
agctca 366
34
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
34
cagtctgttc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgttctg gaagcagctc caacatcgga aataatggtg taaactggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat ggtaacaaca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagcctgcg tggttggctg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
35
369
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
35
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt aacgcctgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtagta gtagtagtta catatactac 180
gcagactcag tgaagggccg attcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagagtcaat 300
agcaaaaagt ggtatgaggg ctacttcttt gactactggg gccagggtac actggtcacc 360
gtgagctca 369
36
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
36
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcagctc caacattggg aataattatg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat ggtaacagca atcggccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagtctgag tggttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
37
375
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
37
gaggtgcagc tgttggagtc tgggggaggc ttggtacagc ctggggggtc cctgagactc 60
tcctgtgcag cctctggatt caccttcagt aacgcctgga tgagctgggt ccgccaggct 120
ccagggaagg ggctggagtg ggtctcatcc attagtacta gtagtaatta catatactac 180
gcagactcag tgaagggccg gttcaccatc tccagagaca attccaagaa cacgctgtat 240
ctgcaaatga acagcctgag agccgaggac actgccgtgt attactgtgc gagagtcaag 300
aagtatagca gtggctggta ctcgaattat gcttttgata tctggggcca aggtacactg 360
gtcaccgtga gctca 375
38
333
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
nucleotide sequence
38
cagtctgtgc tgactcagcc accctcagcg tctgggaccc ccgggcagag ggtcaccatc 60
tcctgctctg gaagcagctc cagcattggg aataattttg tatcctggta tcagcagctc 120
ccaggaacgg cccccaaact cctcatctat gacaataata agcgaccctc aggggtccct 180
gaccgattct ctggctccaa gtctggcacc tcagcctccc tggccatcag tgggctccgg 240
tccgaggatg aggctgatta ttactgtgca gcatgggatg acagcctgaa tggttgggtg 300
ttcggcggag gaaccaagct gacggtccta ggt 333
39
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
39
Phe Leu Asp Thr Val Tyr Gly Asn Cys Ser Thr His Phe Thr Val Lys
1 5 10 15
Thr Arg Lys Gly
20
40
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
40
Pro Gln Cys Ser Thr His Ile Leu Gln Trp Leu Lys Arg Val His Ala
1 5 10 15
Asn Pro Leu Leu
20
41
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
41
Val Ile Ser Ile Pro Arg Leu Gln Ala Glu Ala Arg Ser Glu Ile Leu
1 5 10 15
Ala His Trp Ser
20
42
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
42
Lys Leu Val Lys Glu Ala Leu Lys Glu Ser Gln Leu Pro Thr Val Met
1 5 10 15
Asp Phe Arg Lys
20
43
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
43
Leu Lys Phe Val Thr Gln Ala Glu Gly Ala Lys Gln Thr Glu Ala Thr
1 5 10 15
Met Thr Phe Lys
20
44
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
44
Asp Gly Ser Leu Arg His Lys Phe Leu Asp Ser Asn Ile Lys Phe Ser
1 5 10 15
His Val Glu Lys
20
45
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
45
Lys Gly Thr Tyr Gly Leu Ser Cys Gln Arg Asp Pro Asn Thr Gly Arg
1 5 10 15
Leu Asn Gly Glu
20
46
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
46
Arg Leu Asn Gly Glu Ser Asn Leu Arg Phe Asn Ser Ser Tyr Leu Gln
1 5 10 15
Gly Thr Asn Gln
20
47
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
47
Ser Leu Thr Ser Thr Ser Asp Leu Gln Ser Gly Ile Ile Lys Asn Thr
1 5 10 15
Ala Ser Leu Lys
20
48
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
48
Thr Ala Ser Leu Lys Tyr Glu Asn Tyr Glu Leu Thr Leu Lys Ser Asp
1 5 10 15
Thr Asn Gly Lys
20
49
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
49
Asp Met Thr Phe Ser Lys Gln Asn Ala Leu Leu Arg Ser Glu Tyr Gln
1 5 10 15
Ala Asp Tyr Glu
20
50
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
50
Met Lys Val Lys Ile Ile Arg Thr Ile Asp Gln Met Gln Asn Ser Glu
1 5 10 15
Leu Gln Trp Pro
20
51
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
51
Ile Ala Leu Asp Asp Ala Lys Ile Asn Phe Asn Glu Lys Leu Ser Gln
1 5 10 15
Leu Gln Thr Tyr
20
52
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
52
Lys Thr Thr Lys Gln Ser Phe Asp Leu Ser Val Lys Ala Gln Tyr Lys
1 5 10 15
Lys Asn Lys His
20
53
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
53
Glu Glu Glu Met Leu Glu Asn Val Ser Leu Val Cys Pro Lys Asp Ala
1 5 10 15
Thr Arg Phe Lys
20
54
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
54
Gly Ser Thr Ser His His Leu Val Ser Arg Lys Ser Ile Ser Ala Ala
1 5 10 15
Leu Glu His Lys
20
55
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
55
Ile Glu Asn Ile Asp Phe Asn Lys Ser Gly Ser Ser Thr Ala Ser Trp
1 5 10 15
Ile Gln Asn Val
20
56
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
56
Ile Arg Glu Val Thr Gln Arg Leu Asn Gly Glu Ile Gln Ala Leu Glu
1 5 10 15
Leu Pro Gln Lys
20
57
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
57
Glu Val Asp Val Leu Thr Lys Tyr Ser Gln Pro Glu Asp Ser Leu Ile
1 5 10 15
Pro Phe Phe Glu
20
58
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
58
His Thr Phe Leu Ile Tyr Ile Thr Glu Leu Leu Lys Lys Leu Gln Ser
1 5 10 15
Thr Thr Val Met
20
59
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
59
Leu Leu Asp Ile Ala Asn Tyr Leu Met Glu Gln Ile Gln Asp Asp Cys
1 5 10 15
Thr Gly Asp Glu
20
60
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
60
Cys Thr Gly Asp Glu Asp Tyr Thr Tyr Lys Ile Lys Arg Val Ile Gly
1 5 10 15
Asn Met Gly Gln
20
61
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
61
Gly Asn Met Gly Gln Thr Met Glu Gln Leu Thr Pro Glu Leu Lys Ser
1 5 10 15
Ser Ile Leu Lys
20
62
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
62
Ser Ser Ile Leu Lys Cys Val Gln Ser Thr Lys Pro Ser Leu Met Ile
1 5 10 15
Gln Lys Ala Ala
20
63
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
63
Ile Gln Lys Ala Ala Ile Gln Ala Leu Arg Lys Met Glu Pro Lys Asp
1 5 10 15
Lys Asp Gln Glu
20
64
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
64
Arg Leu Asn Gly Glu Ser Asn Leu Arg Phe Asn Ser Ser Tyr Leu Gln
1 5 10 15
Gly Thr Asn Gln
20
65
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
65
Ser Leu Asn Ser His Gly Leu Glu Leu Asn Ala Asp Ile Leu Gly Thr
1 5 10 15
Asp Lys Ile Asn
20
66
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
66
Trp Ile Gln Asn Val Asp Thr Lys Tyr Gln Ile Arg Ile Gln Ile Gln
1 5 10 15
Glu Lys Leu Gln
20
67
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
67
Thr Tyr Ile Ser Asp Trp Trp Thr Leu Ala Ala Lys Asn Leu Thr Asp
1 5 10 15
Phe Ala Glu Gln
20
68
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
68
Glu Ala Thr Leu Gln Arg Ile Tyr Ser Leu Trp Glu His Ser Thr Lys
1 5 10 15
Asn His Leu Gln
20
69
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
69
Ala Leu Leu Val Pro Pro Glu Thr Glu Glu Ala Lys Gln Val Leu Phe
1 5 10 15
Leu Asp Thr Val
20
70
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
70
Ile Glu Ile Gly Leu Glu Gly Lys Gly Phe Glu Pro Thr Leu Glu Ala
1 5 10 15
Leu Phe Gly Lys
20
71
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
71
Ser Gly Ala Ser Met Lys Leu Thr Thr Asn Gly Arg Phe Arg Glu His
1 5 10 15
Asn Ala Lys Phe
20
72
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
72
Asn Leu Ile Gly Asp Phe Glu Val Ala Glu Lys Ile Asn Ala Phe Arg
1 5 10 15
Ala Lys Val His
20
73
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
73
Gly His Ser Val Leu Thr Ala Lys Gly Met Ala Leu Phe Gly Glu Gly
1 5 10 15
Lys Ala Glu Phe
20
74
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
74
Phe Lys Ser Ser Val Ile Thr Leu Asn Thr Asn Ala Glu Leu Phe Asn
1 5 10 15
Gln Ser Asp Ile
20
75
20
PRT
Artificial Sequence
Description of Artificial Sequence Synthetic
peptide
75
Phe Pro Asp Leu Gly Gln Glu Val Ala Leu Asn Ala Asn Thr Lys Asn
1 5 10 15
Gln Lys Ile Arg
20
76
23
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
76
cccagtcacg acgttgtaaa acg 23
77
25
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
77
gaaacagcta tgaaatacct attgc 25
78
17
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
78
caggaaacag ctatgac 17
79
21
DNA
Artificial Sequence
Description of Artificial Sequence Synthetic
primer
79
agacccaagc tagcttggta c 21 | The present invention relates to passive immunization for treating or preventing atherosclerosis using an isolated human antibody directed towards at least one oxidized fragment of apolipoprotein B in the manufacture of a pharmaceutical composition for therapeutical or prophylactical treatment of atherosclerosis by means of passive immunization, as well as method for preparing such antibodies, and a method for treating a mammal, preferably a human using such an antibody to provide for passive immunization. | 2 |
This is a division of application Ser. No. 527,105 filed on Nov. 25, 1974, now abandoned, which is a continuation of application Ser. No. 307,327 filed Nov. 16, 1972, now abandoned.
FIELD OF INVENTION
This invention relates to improvements in the flame proofing of normally flammable fabrics. More particularly it relates to the flame proofing of normally flammable fabrics composed of certain synthetic polymers and especially it relates to fabrics composed of poly(m-phenyleneisophthalamides) having an Oxygen Index of at least 40.
BACKGROUND OF THE INVENTION
Apparel for use in applications where under emergency conditions a hazardous thermal environment might exist should satisfy the following minimum requirements.
A. The fabric from which the apparel is made should be resistant to burning, melting or disintegration on exposure to open flames or elevated temperatures.
B. The fabric should possess good dimensional stability on exposure to elevated thermal conditions since large thermal shrinkages tend to restrict mobility of the wearer.
C. The apparel should function as an effective thermal barrier in order to prevent severe skin burns, and
D. The garments should be durable and comfortable to encourage their use.
It is known to treat normally flammable textile materials, of both natural and synthetic nature, with chemicals such as ammonium phosphate, tetrakis(hydroxymethyl) phosphonium oxides and polymers thereof, and the like to render them fire retardant. Such treatments while effective for rendering fabrics fire retardant under normal conditions of use, such as fabrics designed for use as curtains, rugs, sweaters and the like, are not satisfactory for use under emergency or highly hazardous conditions as in aviators flying suits or apparel designed for use in oxygen enriched atmospheres.
Synthetic materials, such as polybenzimidazoles and polyamides such as poly(m-phenyleneisophthalamides),polyhexamethyleneadipamides and polycaproamides which exhibit improved heat resistance compared to other synthetics such as polypropylene are known and these improved fibers have replaced the more conventional fire retartant materials in many special applications. In applicant's copending U.S. application Ser. No. 230,999 filed Mar. 1, 1972, now abandoned it was disclosed that normally flammable fabrics such as fabrics composed of polypropylene and polyamides such as poly (m-phenylene isophthalamides) and the like could be rendered flame proof by the intimate association therewith of a flame proofing amount of a phosphoric acid. It was disclosed also, that although such a flame proofing treatment initially results in fabrics having an Oxygen Index of at least 40, this value was found to decrease on repeated washing of the treated fabric. It was disclosed in the aforementioned application, that the flame proofing treatment disclosed therein could be rendered fast to washing by applying to the treated material a coating of a synthetic resin material, e.g., polyvinylidene chloride, perfluorinated organic polymers and the like, having an Oxygen Index of at least 40. Such coatings while generally effective on unfinished fabrics, e.g., vard coods and unwoven filaments, are difficult to apply efficiently to finished articles. The coating resin leaves unprotected the seams and other protected areas, such as the overlapping areas of the woven articles. Accordingly, a need still exists for a fiber with thermal characteristics superior to those of the aforementioned fibers and which is fast to washing in water.
OBJECTS OF THE INVENTION
It is, therefore, a principal object of this invention to devise improved wash fast flame proofed textile fabrics comprising normally flammable synthetic materials.
Another object is to provide a process for treating normally flammable synthetic materials to render them wash fast as well as flame proof.
A particular object is to devise compositions of normally flammable synthetic materials comprising an effective flame proofing amount of a phosphoric acid intimately associated therewith.
These and other objects of the present invention will be obvious from the following description.
BRIEF SUMMARY OF THE INVENTION
In accordance with the present invention there is provided flame proofed synthetic fibrous material which is fast to washing in water comprising a normally flammable synthetic material selected from the group consisting of polypropylene, poly(hexamethylene adipamide), polycaproamide, and poly(m-phenylene isophthalamide) which material contains a flame retardant amount of a phosphoric acid and which has been reacted, in-situ, with an epoxy resin.
These improved products are obtained by a process which comprises the steps of applying an epoxy resin to a normally flammable synthetic fibrous material of the above defined group which material has been rendered highly flame proof by intimately mixing the material with a flame proofing amount of a phosphoric acid and reaction said epoxy resin and said phosphoric acid, in situ.
The resultant flame proof character of the fabric is thereby rendered fast to washing in water.
By "effective flame proofing amount" is meant that amount of a phosphoric acid which suffices to increase the Oxygen Index of the treated material to 40 or above.
By the term "Oxygen Index" it is intended to define the percentage concentration of oxygen in a mixture of oxygen and nitrogen which will maintain equilibrium burning conditions, i.e., the heat produced during combustion just balances the heat lost to the surroundings. Physically, the Oxygen Index is the lowest concentration of oxygen, in an atmosphere of oxygen and nitrogen, which will support sustained combustion of the material and is calculated from the following equation ##EQU1## where O 2 is the oxygen concentration at equilibrium and N 2 is the associated nitrogen concentration. (See "The Oxygen Flame Flammability Test," J. L. Isaacs, J. Fire and Flammability, Vol. 1 (January 1970) page 36 et seq.)
In the practice of the present invention, the materials treated may be formed in whole or in part of the normally flammable synthetic polymer material and may be in various forms including yard or sheet goods, as well as various finished articles, such as articles of clothing including coats, shirts, trousers, skirts, jump suits, gloves, and the like, and such non textile articles as containers, bags, and the like. The materials may be woven, non woven, knitted, and the like. Accordingly although, hereinafter primary reference will be made to the treatment of fibrous woven synthetic polymer yard goods, this is not to be taken as a limitation as other forms of synthetic polymer materials, such as non-woven, films, foils, sheets, fibers and yarns, may, in many instances, be utilized as the materials treated in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with a preferred mode of carrying out the present invention normally flammable synthetic polymers, such as polypropylene, polycaproamides, polyhexamethylene adipamides and poly(m-phenylene isophthalamides) having intimately associated therewith an effective flame proofing amount of a phosphoric acid, and thus having been rendered flame proof in character are reacted in situ with an epoxy resin to fix the phosphoric acid in and on the synthetic polymer material.
It has been found as disclosed in the aforementioned Ser. No. 230,999, that normally flammable synthetic polymers which contain, intimately mixed therewith, at least about 0.4 percent by weight, and preferably from about 2 to about 25 percent by weight, of a phosphoric acid, preferably ortho phosphoric acid or pyrophosphoric acid, are rendered flame proof, that is the Oxygen Index of the treated synthetic polymer has been increased to about 40 or higher.
The flame proofing treatment can be accomplished by several means. For example the synthetic material, in the fibrous or woven condition, can be immersed, padded, sprayed, or dipped in or with an aqueous solution of a phosphoric acid and the thoroughly wetted material dried to remove excess moisture. The treated fabric may be heated to below the decomposition point of the synthetic polymer without significant effect on the treatment.
Alternatively the treatment can be effected by application of a solvent solution of elemental white phosphorus and thereafter the solvent evaporated under relatively mild conditions. Also, the polymer material may be exposed to vapors of phosphorus and thereby phosphorus is condensed on the surface of the material. The elemental phosphorus residue can then be oxidized on the fibrous material and hydrolyzed to pyrophosphoric acid in a known manner. "White phosphorus" as used herein includes various impure and commercial grades sometimes referred to as "yellow phosphorus".
The solvents used to assist in the application of the elemental white phosphorus to the polymer material should be one or a mixture of organic solvents which do not react with the material or the phosphorus, and should be readily removable from the treated material. Typical of such solvents are carbon disulfide, chloroform, perchloroethylene, trichloroethylene, benzene and the like. Trichloroethylene because of its non-reactive nature and ease of removal is the preferred solvent for the elemental white phosphorus.
The treatment can be carried out using cold or hot solutions of the phosphoric acid and with either dilute or concentrated solutions of the treatment acid. Conveniently 85 percent ortho phosphoric acid is used although higher or lower concentrations are useful also.
Any of the inorganic phosphoric acids can be used. Thus ortho, meta-, or pyrophosphoric acids and mixtures thereof are contemplated for use in the process of the present invention. Ortho phosphoric acid because of its general availability and effectiveness is preferred. As indicated above the phosphoric acid can be applied to the synthetic polymer by first impregnating the material with elemental phosphorus and thereafter oxidizing the elemental phosphorus on the fiber and hydrolyzing the oxidized phosphorus. This procedure probably results in the formation of a mixture of phosphoric acids, but for convenience, it is presumed that hydrolyzed product is essentially pyrophosphoric acid and such will be so-called hereinafter.
Although the flame proofing treatment of this invention initially results in fabrics having an Oxygen Index of at least 40, this value has been found to decrease as a result of repeated washing of the treated fabric. It has now been found, that the flame proof character of the phosphoric acid treated materials can be stabilized, that is flame proofing treatment can be rendered fast to washing, by applying to the treated material an epoxy resin and causing the latter to react with the phosphoric acid, in situ. It is known that epoxy resins react with acids forming acido-hydrins according to the general reaction ##STR1## wherein X is the acid anion.
It is believed that in the present instance, that the epoxy resin reacts with the phosphoric acid on the fabric to produce in situ a substantially insoluble phospho-hydrin according to the general reactions ##STR2##
As indicated, one mol proportion of phosphoric acid may react with up to three mol equivalent proportions of the epoxy resin. It has been found that by controlling the temperature, time and concentration of reactants in and during this reaction, from nil reaction to substantially complete reaction can be effected.
It has thus been found that by dipping, immersing, spraying, roller coating, or otherwise applying to the phosphoric acid treated fabric an organic solvent solution of an epoxy resin, and thereafter heating the thus impregnated fabric to cause the epoxy resin to react, in situ, with the phosphoric acid, the treated fabric is thereby rendered fast to washing in cold water.
In accordance with a preferred mode of carrying out the process of the present invention a normally flammable synthetic material is treated in accordance with the process disclosed in Ser. No. 230,999, to effect an add on of about 0.5 to 15 percent by weight of phosphoric acid, preferably from about 2 to about 10 percent by weight phosphoric acid. The treated material is dried and then treated by immersion, spraying, or the like, with a solvent solution of an epoxy resin sufficient in amount to provide from about one to about three moles of epoxy resin per mole of phosphoric acid in the fabric. The epoxy solution contains from about one to about 50 percent by weight of the epoxy resin preferably from about 5 to about 20 percent by weight. Thereafter the fabric is dried to remove the solvent and heated to cause the epoxy resin to react, in situ, with the phosphoric acid. Generally a temperature of from about 75 to about 150 degrees centigrade and preferably from about 100 to about 120 degrees centigrade is required for this in situ reaction, although higher or lower temperatures may be required depending upon the reactivity of the specific epoxy resin used.
Any epoxy resin which will react with phosphoric acid to form a phospho-hydrin type compound, as disclosed above can be used in the process of the present invention. Suitable epoxy resins, many of which are commercially available articles of commerce, preferably are of the epoxidized fatty oils and esters such as soy bean oil, tall oil fatty acids, oleic acid and the like epoxidized polyols such as bisphenol A (4,4'-isopropylidenediphenol) aliphatic glycols and the like, and epoxidized novolac resins. The following typical epoxy resins are representative of the epoxy resins suitable for use in the present invention.
Epoxidized soybean oil, available commercially under the trade designation of Drapex 6.8, of Paraplex G-60, G-61 and G-62, and of Plastoflex ESO.
Epoxidized linseed oil, available commercially under the trade designation of Epoxol 9-5 (see U.S. Pat. No. 3,377,304).
Dicyclopentadiene Dioxide
Diglycidyl ether of bisphenol A available commercially under the trade designation of Epon 828,
Diglycidyl ether of bisphenol-hexafluoroacetone,
triglycidyl-p-aminophenol [4-(2,3-epoxy)propoxy-N,N-bis(2,3-epoxypropyl)aniline].
As is known, the commercially available epoxy resins are not pure chemicals but rather complex mixtures and are utilized with reference to their oxirane or epoxy value which is a measure of the number of epoxy moieties per 100 grams of epoxy product.
The epoxy resin is applied to the phosphoric acid treated fabric preferably as a solvent solution. Among the solvents which may be used following are mentioned as typical examples
acetone
methyl isobutyl ketone
1,1,1, trichloroethane
dimethylformamide
dimethylacetamide
ethylene dichloride
Following application of the epoxy resin solution, the treated material may be freed of solvent by evaporation of the latter in a circulating air oven, by hanging the solvent wet cloth in air or by any other suitable means. The substantially solvent freed material is then "cured" by heating in a suitable oven at about 75° to about 150° centigrade, preferably at 100° to 120° centigrade for about 2 to about 20 minutes, to permit the reaction of the phosphoric acid epoxy compound to proceed substantially to completion. Therefter the "cured" material may be rinsed in cold water for about 2 to about 5 minutes to remove excess reagents and the treated cloth dried in any suitable fashion.
The following examples will illustrate the present invention. Parts and percentages are by weight and temperatures are given in ° C.
In these Examples 1-16, several strips, measuring 16 in. × 24 in. of a woven poly (m-phenyleneisophthalamide) fabric weighing 170 grams per square yard in 300 parts of an aqueous solution containing 15 percent of 85 percent ortho-phosphoric acid and to which 12 drops of Triton X-100, (a commercially available non-ionic surfactant being essentially a mixture of acetyl phenoxy polyethoxy ethanols), were added. The wetted material was pressed on padder rolls under 30 pounds pressure and then dried in a heated current of air.
Strips measuring 4 in. × 12 in. of the treated material were immersed in solutions of four different epoxy resins, and of two different concentrations. The epoxy resins used were as follows:
A. epoxidized soybean oil - available commercially as Paraplex G-61.
B. epoxidized soybean oil available commercially as Drapex 6.8.
C. diglycidyl ether of bisphenol A -- available commercially as Enon 288.
D. epoxidized linseed oil available commercially as Epoxol 9.5.
Thus a 5 percent and a 20 percent solution of each of the four epoxy resins in 1,1,1-trichloroethane was prepared and used to treat the phosphoric acid impregnated cloth strips. In addition 5 percent and 20 percent solutions of the four epoxy resins were prepared using acetone as the solvent and strips of the treated cloth immersed in these solutions also. The epoxy resin treated strips were heated to evaporate the solvents substantially completely and the dried strips were heated in an oven at 90° for 5 minutes.
Thereafter each of the "cured" strips were cut into six, 2 in. × 4 in. sections. One section of each group was then treated as follows after which the Oxygen Index was determined to ascertain the effect of the treatment on the flammable character of the treated material.
a. No. water wash - control
b. 5 minute cold water wash
c. 15 minute cold water wash
TABLE I__________________________________________________________________________ Epoxy Oxygen Index Epoxy Conc. No 5 min. 15 min.Example Compound Solvent % Wash Cold/H.sub.2 O.sup.1 Cold/H.sub.2 O.sup.2__________________________________________________________________________1 "A" Acetone 20 60 58 402 "B" " 20 54 54 483 "C" " 20 58 40 454 "D" " 20 56 52 425 "A" " 5 48 36 326 "B" " 5 48 38 327 "C" " 5 60 28 358 "D" " 5 60 38 349 "A" Trichloroethane 20 60 54 5510 "B" " 20 62 58 5411 "C" " 20 60 58 5512 "D" " 20 62 50 5513 "A" " 5 62 30 3014 "B" " 5 62 34 4815 "C" " 5 62 30 3516 "D" " 5 62 32 32__________________________________________________________________________ Notes: Oxygen Index of untreated fabric = 29 ± Oxygen Index of H.sub.3 PO.sub.4 treated fabric = 60 ± 2 .sup.1 Treated samples heated at 90° for 5 minutes .sup.2 Treated samples reheated at 150° for 5 minutes
These results indicate that in general treatment of the H 3 PO 4 treated material with 5% solutions of the epoxy resin results in considerable leaching of the phosphoric acid and/or insufficient curing of the epoxy resin on the fiber ("in situ"). This latter explanation is particularly indicated by the results obtained with Epon 828, especially 5% acetone solution of Epon 828, (Example 7) where the 5 minute washing test resulted in complete removal of the phosphoric (O.I. of 28).
To confirm this, sections treated with 20% and 5% acetone solutions of Epon 828 and Epoxol 905 (See Examples 3, 4, 7 and 8) were reheated at 150° for 5 minutes and these sections were washed for 5 minutes in cold (23°) water. The Oxygen Index of these sections were as follows:
20% Epon 828 in Acetone -- 52
5% Epon 828 in Acetone -- 40
20% Epoxol 9.5 in Acetone -- 50
5% Epoxol 9.5 in Acetone -- 44
These results indicated that Epon 828 requires a higher curing temperature than other epoxy resins to form in situ the desired wash resistant reaction product with phosphoric acid. With respect to the Epoxol 9.5 treated materials, only in the instance of the 5% acetone solution was nay improvement noted by the higher curing temperature. In this instance the more concentrated (20%) solution evidently produces sufficient cured product at 90° to give a desirable degree of wash fastness.
Inasmuch as the results in the above table appear to indicate that the epoxy resin treatment with 5% solutions of the epoxy resins followed by in situ reaction at 90° does not give satisfactory wash fastness, two sections, one treated with Paraflex G-61 and one treated with Epon 828 (5% in trichloroethane solvent) were reheated to 150° for 5 minutes, and then washed for 5 minutes in cold water. The Oxygen Index of the reheated sections were 54 (Paraplex G-61) and 46 (Epon 828) indicating that insufficient in-situ reaction had occurred at 90°.
As a result of the improvement in "in situ" reaction shown by the higher curing temperature with the above two sections, all of the remaining sections of epoxy treated material were reheated at 150° for 5 minutes and one of the reheated sections in each category of treatment was washed in cold water for 15 minutes. After drying, the Oxygen Index of each section was determined. The results obtained are set out in the last column of Table I above.
Again, these results indicate the importance of applying sufficient epoxy resin to the material prior to effecting the in situ reaction. The Oxygen Indexes of the sections treated with the 20 percent solutions show acceptable flame retardance after 15 minute washing in cold water, (Examples 1-4 and 9-12) whereas the sections treated with the more dilute, 5 percent solutions, except in one instance, that of Drapex 6.8 in 5 percent trichloroethane, Example 14, show little or no retention of the flame retardance characteristic after the 15 minute cold washing. (See Examples 5-8, 13, 15 and 16).
EXAMPLE 17
Woven poly(m-phenylene isophthamide) fabric was immersed in a 7.5 percent aqueous solution of 85 percent ortho phosphoric acid. The impregnated material was freed of excess liquor and then dried in a 110° oven for 5 minutes. The resulting material was immersed in a 10 percent solution of epoxidized soybean oil(Paraplex G-61) in 1,1,1-trichloroethane to thoroughly wet the phosphoric acid treated material. The thus treated material was then dried at 110° for 5 minutes.
The Oxygen Index of the dried treated material was 58.
Three equal sized sections of the treated material, taken from the top, center and bottom portions of the treated material were washed in cold water for 15 minutes and then dried. The Oxygen Indexes of the washed sections varied from 46 to 54 to 50.
The invention has been described in the above specification and illustrated by reference to specific embodiments in the illustrative examples. However, it is to be understood that it is not to be so limited since changes and alterations in the specific details disclosed hereinabove may be made without departing from the scope or spirit of the invention disclosed herein. | Normally flammable fabrics, such as fabrics composed of polypropylene and polyamides such as polycaproamides, poly(m-phenyleneisophthalamides) and the like which have been rendered flame proof by the intimate association therewith of a flame proofing amount of a phosphoric acid and reacted in situ with an epoxy compound. The resultant compositions can be washed in water without substantial loss in flame proof character. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to a concealed fastening building finishing element system that enables concealed fastening of finishing elements such as trim components, fascia boards, frieze boards, belly band boards, and the like to an underlying structure and to the fixings used in these systems.
The invention is particularly useful with trim elements around window and door frame openings and at building corners and will be described hereinafter with reference to these applications. It will be appreciated, however, that the invention is not limited to these particular fields of use and can be used in connection with other building finishing elements where concealed fastening is desired, including but not limited to, band board features, fascia boards, soffits and the like.
Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.
In one popular form of building structure, trim installations are applied around window or door frame openings and at internal or external corners of a building. The trim serves both an aesthetic purpose in adding a decorative feature to building envelopes and also adds an additional weatherproofing purpose in allowing for more complete weatherproofing of building envelope corners and openings.
Without trim at the external corners of the building, for example, cladding such as planks or panels are each necessarily cut, nailed in place, and sealed against weather effects individually. Traditionally, a favored method was to mitre cut the plank edges to form a joint line which requires a high skill level. However, any building movements tended to cause the mitre joints to open up which as well as being unsightly, exposed the edges and the underlying structure to the weather. Additionally, because primary framing members are traditionally located at the external corners of buildings, it is important for the long term durability of a building that corner treatments are both easy to install and provide improved weather resistance for protection of the structural elements of the building.
Again, without finishing trim at window and door openings, the surrounding cladding panels or planks are necessarily individually cut, fixed in place and weatherproofed to a sophisticated level.
Trim may also allow for simplified installation of cladding such as planks and panels. At corners, for example, the trim is fixed in place first and then the cladding planks are simply square cut and fixed so that the cut edges of the planks butt up against the sides edges of the trim. A sealing compound is also used between the side edges of the trim and the cut edges of the planks to provide additional weatherproofing, without the need to individually treat each plank.
Trim is typically installed by driving fasteners, such as nails or screws through each the surface of trim member and into the underlying structure. The head of the nail or screw is thus visible on the face of the trim. On a pre-finished trim piece, if a smooth surface appearance on the face of the trim is required, the nails must be installed flush with the surface of the trim and the nail heads touched up with paint. If the nails are overdriven below the surface of the trim, the resulting holes must be filled with a water-proof filling compound and/or touched up with paint. It will be appreciated that these additional steps are time consuming and add additional cost to the installation.
U.S. Pat. No. 7,028,436 describes a corner trim piece which includes a cementitious layer moulded on a rigid right-angle backing. The rigid backing reinforces the cementitious layer and overhangs along one longitudinal side of the trim to provide a nailing flange for fixing the sheathing product to an exterior surface of a building. Holes may also be provided through the cementitious layer to allow nailing through the integrated sheathing product. While the reinforcing provided by the backing member provides resistance to cracking of the cementitious layer, it is also likely to increase the overall weight and cost of the trim piece. Additionally, manufacture of the integrated product is likely to be more complex than the manufacture of a simple discrete trim piece suitable for nail or screw fixing, as described above. Furthermore, this sheathing product is likely to have limited installation flexibility, in particular relating to ease of positioning the product in situ due to the nailing flange extending along the entire length of the trim piece. Furthermore, the described trim piece is necessarily provided as a pre-fabricated product and can only be used on corners limiting the flexibility on window and door trim installation.
Similar issues arise with the installation of other standard building finishing elements such as fascia boards, band boards, soffits and the like, in that face fixing through the element complicates the finishing process by requiring touch up painting or the use of prefinished or capped fasteners or the like. This is particularly relevant when prefinished finishing elements are to be used.
BRIEF SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention, there is provided a load-bearing concealed building finishing element fixing tab, the tab including a first portion and a second portion, the first portion being adapted for connection to a structure-facing surface of a building finishing element such that said second portion of said tab extends outwardly from said building finishing element, and said second portion being adapted for connection to a support structure thereby to secure a portion of said building finishing element to said support structure whereby the connection between said first portion of said tab and said structure-facing surface of said building finishing element is substantially concealed from an outwardly directed exterior-facing surface of said building finishing element, the tab being configured, and defined as being load-bearing, in its ability to support said portion of the building finishing element and retain it in a fixed position.
According to another aspect of the invention, there is provided a concealed building finishing element system including a building finishing element having a structure-facing surface and an exterior-facing surface; and at least one load-bearing concealed building finishing element fixing tab, the tab including a first portion and a second portion, the first portion being adapted for connection to a structure-facing surface of a building finishing element such that said second portion of said tab extends outwardly from said building finishing element, and said second portion being adapted for connection to a support structure thereby to secure a portion of said building finishing element to said support structure whereby the connection between said first portion of said tab and said structure-facing surface of said building finishing element is substantially concealed from an outwardly directed exterior-facing surface of said building finishing element, the tab being configured so as to support said portion of the building finishing element and retain it in a fixed position.
According to another aspect of the invention, there is provided a method of securing a building finishing element to a support structure, said method including the steps of selecting one or more load bearing concealed building finishing element fixing tabs, each tab including a first portion and a second portion, connecting said first portion of the tab to a structure-facing surface of the building finishing element such that the second portion extends outwardly from the building finishing element, and connecting the second portion of the tab to a support structure to thereby secure the building finishing element to the support structure whereby the connection between the first portion of the tab and said structure facing surface of the building finishing element is concealed from an outwardly directed exterior facing surface of said building finishing element, the tab or tabs being configured to support the building finishing element and retain it in a fixed position.
According to another aspect of the invention, there is provided a load-bearing concealed corner trim fixing tab, said tab being substantially L-shaped and including a pair of perpendicularly extending arms, each arm including a first portion and a second portion, wherein each said first portion is adapted for connection to one of a pair of perpendicular structure-facing surfaces provided on a corner trim and such that each said second portion extends outwardly from its respective structure facing surface, said second portions each being adapted for connection to a corner structure, thereby to secure a portion of said corner trim to said corner structure such that the connection between each said first portion and said structure-facing surface of the trim is substantially concealed from an outwardly directed exterior-facing surface of said trim, the tab being configured so as to support said trim and retain it in a fixed position. This substantially L-shaped tab can be used for inside or outside corners of a structure.
In a preferred form the trim comprises a pair of trim members which are affixed together in a substantially L shaped configuration by connection of the perpendicular first portions of the tab to each of the structure facing surfaces of the trim elements.
According to another aspect of the invention, there is provided a concealed corner trim system including a pair of trim members, each trim member having a structure-facing surface and an exterior-facing surface; and at least one load-bearing concealed corner trim fixing tab, said tab being substantially L-shaped and including a pair of perpendicularly extending arms, each arm including a first portion and a second portion, wherein each said first portion is adapted for connection to a structure-facing surface of a respective one of a pair of trim members such that said trim members are affixed together in a substantially L-shaped configuration and such that each said second portion extends outwardly from its respective trim member, said second portions each being adapted for connection to a corner structure, thereby to secure a portion of each of said trim members to said corner structure such that the connection between each said first portion and said structure-facing surface of said respective trim member is substantially concealed from an outwardly directed exterior-facing surface of said respective trim member, the tab being configured so as to support said portions of the trim members and retain them in a fixed position.
According to another aspect of the invention, there is provided a method of securing a pair of trim members to a corner structure, said method including the steps of selecting one or more substantially L-shaped load bearing concealed corner trim fixing tabs, each tab including a pair of extending arms, each arm including a first portion and a second portion, connecting said first portions of the tab on each arm to a structure facing surface of a corresponding one of a pair of trim members such that the trim members are affixed together in a substantially L-shaped configuration and such that each second portion extends outwardly from its respective trim member, and connecting said second portions of the tab to a corner structure whereby connection between the first portion of the tab and said structure facing surface of the trim members is substantially concealed from an outwardly facing surface of the trim members, the tab or tabs being configured to support the trim members and retain them in a fixed position.
Preferably, the substantially L-shaped load bearing tabs may be utilized to connect a pair of trim members to either an external corner or an optional internal corner.
The above referenced system and method set out in the above aspects of the invention can be modified for use with a unitary corner trim element as described with reference to the substantially L-shaped fixing tab aspect of the invention. The tab in all aspects may be configured to support and positionally retain the building finishing elements via selection of various features including, for example, material properties, size and shape. Generally, the tabs will require a combination of load bearing strength, bending resistance under cantilevered loads and a resistance to buckling or extension under compressive or tensile loads.
In one embodiment the tab material is selected so as to have sufficient holding strength and rigidity while also being penetrable in situ with a suitable impact fastener such as a nail, staple or screw fastener. In such cases, the tab may be made of any suitable material including metals, plastics, timber or composites such as glass reinforced plastic, etc. Requisite strength and rigidity properties would depend on the properties of the trim component and the number of tabs proposed per trim component.
In accordance with one preferred embodiment of the invention, the first and/or second portions of the tab include one or more pre-formed fastener receiving perforations or areas directed to receive the fasteners, thereby enabling use of a harder, and, possibly structurally more rigid material, which in turn may facilitate use of thinner sectioned tabs which will allow the trim to sit closer for a more flush mounting to the supporting structure.
Alternately, each portion of the load-bearing tabs may include more than one perforation. Additionally, the load-bearing tabs may be multi-perforate. In such embodiments, the first and second portions may each be respectively connected to the corresponding trim member and the underlying structure via one or more of the available perforations. In other embodiments both portions may be solid and without perforations. Yet further embodiments may include a combination of any two or more of solid, single perforation, multiple positioned perforations or general and/or continuous perforations. The first and second portions each include at least one optional perforation for fastening and may be multi-perforate. The number of fasteners used to attach the tab to the trim member and the tab to the underlying building structure will typically depend on the size and weight of the trim member and in some circumstances regard may also be had to the resulting load requirements on the tab.
Advantageously, the perforations in the load-bearing tabs may allow the use of both impact fasteners and screw fasteners with thicker and/or harder high strength material tabs than would otherwise be possible. Again, the required overall strength of the tabs is typically determined by the strength required across one or more tabs to support a trim member having a given length and specific orientation, usually horizontal or vertical. The required strength of the tab may also be determined to some degree by the effect of winds loading on the trim member where this is a relevant consideration.
Additionally, the use of perforations advantageously assists with positioning the tabs relative to the trim members and the underlying structure and/or may provide a guide to appropriate fastener spacing and positioning relative to the tab boundaries. The perforations can be sized and located as necessary depending on the size and weight of the trim member, the number of fasteners required for the forces acting on the load-bearing tab, ease of installation, and for aesthetic reasons.
The perforations are preferably configured to correspond to the received fastener. The perforations may be of any suitable shape and size, including a clearance hole, aperture, cross, circle, square, etc. The perforations may include a screw thread.
Preferably, the fasteners are impact fasteners. The number of fasteners used to attach the tab to the trim member and the tab to the underlying building structure will typically depend on the size and weight of the trim member and the resulting load requirements on the load-bearing tab. In one embodiment staples are used to attach the tab to the trim member, however, alternate fastening means may be used. It is also preferred that nails are used to attach the tab to the structure. However, it will be appreciated that any suitable means of fastening may be used that are in compliance with local building codes. This may include, for example, screws, rivets, bolts, staples, adhesives etc.
In preferred embodiments of the invention the tabs include some form of indicia to provide fastener positioning guides and/or other information that may be useful to the installer. The indicia can be formed in any suitable manner including, for example, by embossing, engraving, etching or printing, and may be in multiple locations on the tabs. In one embodiment of the present invention, a positioning guide is located along a length of the tab. In another embodiment of the present invention, a positioning guide is located along a width of the tab. In another embodiment of the present invention, multiple positioning guides are located on the tab, such multiple positioning guides may be in the same or different directions from one another, depending on the desired positioning for the specific installation. For example, in one embodiment of the present invention, the tab contains a positioning guide running the length of the tab, and a shorter positioning guide perpendicular to the lengthwise positioning guide and running from the lengthwise positioning guide to the edge of the tab.
The invention advantageously allows the use of standard fastening guns and standard commercially available fasteners. This advantageously results in minimum cost of implementation and minimum additional skills required for installers. These advantages are further enhanced when the tabs include indicia in the form of fastening guides.
Preferably, the load-bearing tabs are discrete tabs. Advantageously, tabs are able to be connected to any position on the structure facing surface of the trim member. This provides flexibility of positioning the tabs to suit various installation requirements and work around various obstructions, etc. The width of each tab is preferably smaller than the edge dimensions of the building finishing element to which it is connected. In this regard, the width is preferably selected such that when a tab is secured to the end of a first building finishing element which is to abut with an adjacent second building finishing element, such as happens with trim at the corners of openings and the like, there is room for the second trim member to sit over the second portion of the tab securing the adjacent end of the first trim member, without the first portion of the tab on the second trim member overlapping with the second portion of the first trim member.
Preferably, the first portion and second portion of the tab are substantially collinear with respect to each other. The second portion preferably extends outwardly from the building finishing element in a direction parallel to the structure-facing surface.
When installed, the load-bearing tabs are required to resist compression loads, tension loads and cantilevered bending loads. In a preferred form, the load-bearing tabs are formed from steel or aluminum strips, however, it will be appreciated that a wide variety of materials and configurations could be used to achieve the desired result of supporting the building finishing element and fixing them to the underlying building structure.
In preferred forms, the building finishing elements are trim members which are preferably formed of fibre reinforced cement but can be made of other materials including but not limited to wood, vinyl, plastics, and the like and composites thereof.
Preferably the support structure and corner structure are formed using a weatherproof material. This material may be in the form of sheets or weather barriers. In one preferred form, the support structure and corner structure are formed from an OSB substrate. Alternatively, the support structure and corner structure may be formed from plywood sheets.
Preferably, each building finishing element is secured to the support structure by a plurality of the load-bearing tabs. It will be appreciated that the number, size and configuration of the tabs will depend upon the size and weight of the trim member. Other factors may, in some situations, include external forces acting on the building finishing element when installed, for example, wind loading.
Preferably, the structure facing surface of each building finishing element is substantially planar. In some embodiments, the rear-surface of each building finishing element includes a recess for locating the load-bearing tab such that, when connected to the trim member, the first portion of the tab lies generally flush with the structure-facing surface of the trim member. The structure facing surface of the trim member may also have one or more grooves along its length and/or width.
In some preferred applications, cladding is installed adjacent the edge of each installed trim member. Further preferably, the installed cladding covers the exposed second portion of each load bearing tab. A sealing compound is preferably applied between the edges of the trim and the adjacent ends of the cladding pieces.
While the preferred forms of the tabs, system and construction method relate to the installation of building finishing elements in the form of trim, other embodiments can be configured for use with other building finishing elements such as fascia boards, band boards, soffits and any other finishing elements where concealed fixing is desired using the basic principles described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention will now be described, by way of example only, with reference to the accompanying drawings in which:
FIG. 1 is a front view of a window trim installation of trim members incorporating fixing tabs in accordance with one embodiment of the present invention;
FIG. 2 is a rear view of one of the trim members from FIG. 1 , showing a use of load bearing tabs connected thereto;
FIG. 3 is a front view of the window from FIG. 1 , showing one side trim member installed;
FIG. 4 is a view similar to FIG. 3 , showing the side trim member as transparent to show the connection between the tabs and the structure facing side of the side trim member;
FIG. 5 is another front view of the window of FIG. 1 , showing the other side trim member installed;
FIG. 6 is a front view of the window of FIG. 1 , showing the bottom trim member installed;
FIG. 7 is a view similar to FIG. 6 , showing the bottom trim member as transparent to show the connection between the tabs and the structure facing side of the bottom trim member;
FIG. 8 is a perspective view of a corner trim member;
FIG. 9 is a perspective view showing one trim member connected to an L-shaped tab;
FIG. 10 is a top view showing the L-shaped configuration of the connected trim members;
FIG. 11 is an underside plan view of an alternative system incorporating a trim member with a clip retaining groove in its structure facing surface and a second embodiment concealed fixing tab; and
FIG. 12 is a an end view of the trim member and tab assembly shown in FIG. 11 .
DETAILED DESCRIPTION OF THE INVENTION
In the description which follows like parts are marked throughout the specification and drawings with the same reference numerals, respectively. The drawings figures may not necessary be to scale and certain elements may be shown in generalized or somewhat schematic form in the interest of clarity and conciseness.
Referring to FIGS. 1 and 2 of the drawings, a system according to one embodiment of the invention is illustrated in the form of window trim installation which includes a plurality of building finishing elements in the form of trim members 1 , each affixed around a window 2 to the underlying exterior structure of the building 3 by three rigid load bearing tabs 4 .
Each load bearing tab 4 includes a first portion 5 and a second portion 6 , each portion, optionally, having a number of perforations 7 . The tab 4 may be, for example, nailed, stapled, or screwed to a structure-facing surface 8 of each trim member 1 through one or more of the optional perforations 7 in the first portion 5 of the tab 4 , such that the second portion 6 extends outwardly from the trim member, as best shown in FIG. 2 . The second portion 6 of each tab 4 preferably extends directly outwardly in a direction parallel to the structure-facing surface 8 to advantageously provide parallel installation of the trim members relative to the underlying structure 3 . The tab 4 may be attached to the trim members 1 either on the building site during installation or pre-fitted elsewhere and delivered to the site. Tab 4 may be secured to the trim member 1 by laying the trim members 1 in the configuration in which they are to be applied to the structure 3 and utilizing tabs 4 of suitable width. In one embodiment, the width of tab 4 is selected such that when a tab 4 is secured to the end of a first trim member 1 which is to abut with an adjacent second trim member 1 , such as happens with the trim members at the corners of the illustrated window opening, there is room for the second trim member to sit over the second portion of the tab securing the adjacent end of the first trim member, without the first portion of the tab 5 on the second trim member overlapping with the second portion of the first trim member. This is best illustrated with reference to FIG. 7 which shows the first portions 5 of the tabs on the bottom trim member 11 as providing clearance with the second portions of the lowermost tabs on each of the side trim members. For trim member 1 having a width of 4″, the length and width dimensions of tab 4 is preferably about 3.5″×2″, respectively, and the overall thickness of tab 4 is generally 18 gauge. It is understood that tabs 4 may vary in length and width, depending, for example, on the size of the trim member. It is also understood that the thickness of tabs 4 may vary. In one embodiment of the invention tab 4 has a thickness in the range of from about 16 to 20 gauge. It will be further understood that the tabs 4 may be of varying shapes and sizes (and thicknesses) depending on various factors, for example, the type, size, and weight of the trim member utilized.
In some embodiments, the structure-facing surface 8 of each trim member 1 includes a recess (not shown) in which the load-bearing tab may be placed such that, when connected to the trim member, the first portion of the tab lies generally flush with the structure-facing surface of the trim member.
Turning to FIGS. 3 and 4 , there is illustrated an installation of building finishing elements around a window in accordance with one embodiment of the invention. As shown in FIGS. 3 and 4 , a building finishing element 1 is placed in the desired position at one side of the window and the protruding second portion 6 of each tab 4 is secured (e.g., by nailing) to the underlying exterior structure 3 of the building. This secures the building finishing element to the underlying support structure 3 . Referring to FIGS. 5 to 7 and FIG. 1 , additional trim members are installed by the same method to completely surround the window opening 2 . In the embodiment shown, the side trim members 9 which are to be fixed within the ends of the top and bottom trim members are installed first, followed by the top 10 and bottom 11 trim members. It will be appreciated that the order required will vary according to the particular configuration of the trim members in the installation.
As best shown in FIGS. 1 , 3 , 5 and 6 , the connection between the first portion 5 of each tab 4 and the structure facing surface 8 of the trim member 1 is not visible from an outwardly-directed exterior facing surface 12 of the trim member.
The tabs 4 and trim members 1 may also be used to provide a door trim installation (not shown), in which case there is typically no bottom trim member 11 present. The location of the tabs with respect to each trim member may necessarily be altered to suit such an installation. For example, in a door trim installation, the side trim members 9 may each have one tab connected to the upper end of the trim member and one or more tabs connected along the length of the trim member so that the trim member can be installed with the lower end substantially flush to the ground, if desired.
Referring now to FIGS. 8-10 , a corner trim arrangement 13 is shown having a pair of trim members 14 , 15 connected to a substantially L-shaped tab 16 . The structure facing surface 17 of one of the trim members 14 is connected to a first portion 18 of a respective arm 19 of the tab via one or more of the optional perforations 20 in the respective first portion 18 , as shown in FIGS. 8 and 9 . The other trim member 15 is positioned at right angles to the first trim member 14 and its structure facing surface 17 is connected to the first portion 18 of the other arm 21 of the load bearing tab 16 , such that the trim members 14 , 15 form an L-shape when viewed in cross-section. In the embodiment shown, two L-shaped tabs 16 are used to connect the trim members 14 , 15 together. However, it will be appreciated that any number of tabs 16 may be used, depending upon the size and weight of the trim members and, in some circumstances, the forces acting upon them when installed may also need to be taken into consideration. The trim members are back fixed together with the external faces (not shown) of the trim members being free from any fixing marks.
Optionally, the first portion 18 of each arm 19 , 21 includes at least one perforation 20 to facilitate fastening of the tab 16 to each trim member 14 , 15 . In the embodiment shown, each first portion 18 includes four perforations 20 however it will be appreciated that the first portions may each include any number of perforations. The two first portions of the L-shaped tab 16 may each include a different number of perforations, if desired. In some embodiments, each first portion 18 will be multi-perforate to allow for multiple connections points as well as providing a number of options in respect of the location of each of the connection points relative to the L-shaped tab. In other preferred embodiments no perforations will be required and the fasteners can automatically pierce through the tab portions during the fastening process.
It will be appreciated that the trim members 14 , 15 may each be installed on the other side of the L-shaped tab 16 to form an internal corner (not shown).
Each arm 19 , 21 of the load bearing tab 16 is longer than the width 22 of the connected trim member 14 , 15 , forming a second portion 23 which extends outwardly from the respective trim member.
The corner trim arrangement 13 is positioned with the L-shaped tabs 16 placed adjacent a corner structure (not shown), such as a wall or a frame, and the overhanging second portions 23 of the tabs 16 are connected to the underlying structure via the optional perforation or perforations 20 in each second portion 23 . It will be understood that the corner structure may be either an external corner as for the corner trim arrangement 13 shown in FIG. 8 , or an internal corner for a corner trim arrangement (not shown) where the structure facing surfaces of the trim members 14 , 15 are each connected to the other side (not shown) of the L-shaped load-bearing tab 16 .
While the corner trim illustrated is comprised of two planar trim members, it will be appreciated that the L shaped tab can readily be used with preformed three dimensional corner members such as those that may be pre-connected to each other prior to installation, or unitary corner pieces such as those that may be formed by a casting, folding or extrusion process.
Following installation of the trim members 1 , 14 , 15 around a window 2 or door opening or to a corner structure, cladding (not shown) is installed adjacent the edge of each trim member 1 , 14 , 15 . The installed cladding ideally abuts the edge of the adjacent trim member and covers the exposed second portion 6 , 23 of each load bearing tab. A weatherproof sealing compound (not shown) can also be applied to any gaps between the cladding and the trim members to provide additional protection against weather effects.
As shown in FIG. 10 , for trim members 14 , 15 having a width of 4″, the length and width dimensions of tab 16 is preferably about 5.5″ long for the first arm 19 , 5.5″ long for the second arm 19 and 1.5″ in width for both first and second arms, and the overall thickness of tab 16 is generally 18 gauge. It is understood that tab 16 may vary in length and width, depending, for example, on the size of the trim members 14 , 15 . In another embodiment, the length of the first arm 19 of the substantially L-shaped tab 16 is approximately 5.9″ and the length of the second arm 21 of the substantially L-shaped tab 16 is approximately 6.7″. It is also understood that the thickness of tab 16 may vary. It will be further understood that the tab 16 may be of varying shapes and sizes (and thicknesses) depending on various factors, for example, the type, size, and weight of the trim member utilized.
In one embodiment, the length of the planar tab 4 is approximately 3.0 inches. In another embodiment the width of the tab 4 , 16 is about 2″ and the preferred thickness of the tabs is about 0.63″. In a further embodiment of the invention tab 4 has a thickness in the range of from about 16 to 20 gauge.
The optional perforations 7 , 20 are preferably circular in shape and in one embodiment have a diameter of 0.094″. Where the tabs are multi-perforate, the perforations preferably have a centre to centre distance of 0.144″ with a perforate area of approximately 40% of the total tab area. Further preferably, the perforations are arranged in rows with every second row offset to provide a close packing perforation density. It will be appreciated, however, that a circular geometry is not essential and that the perforations may be slot, diamond, square, or any other suitable shape.
While the preferred form of the invention utilizes varying tabs which are not perforated being penetrable in situ with a range of suitable fasteners including nails, staples, and/or screws as required, other embodiments utilize various other perforated sheet materials which have sufficient holding strength and rigidity. Tabs of the present invention may be made of any suitable material including metals, plastics, timber or composites such as glass reinforced plastic, etc. Requisite strength and rigidity properties of the tab would depend on the properties of the trim component and the number of tabs proposed per trim component. As indicated previously, the tab may be configured to support and positionally retain the trim member via selection of various features including, for example, any one or more of: material properties, size and shape. Generally, the tabs will require a combination of load bearing strength, bending resistance under cantilevered loads and a resistance to buckling or extension under compressive or tensile loads respectively.
In preferred forms the tabs may include some form of indicia to provide fastener positioning guides and/or other information that may be useful to the installer. The indicia can be formed in any suitable manner including, for example, by embossing, engraving, etching or printing.
Preferably the support structure and corner structure are formed with a weatherproof material such as, for example, weather resistant and/or water resistant house wrap over an OSB substrate.
While three tabs are connected to each window trim member and two tabs to each corner trim member in the accompanying drawings, it will be appreciated that any number of tabs may be used. For example, in the case of short and/or lightweight window trim pieces, a tab affixed at each end of the trim member is likely to be suitable, while for longer and/or heavier trim pieces, it may be necessary to connect one or more tabs along the length of the trim member.
It will be appreciated that concealed tabs in accordance with the present invention are able to be connected to any position on the trim members. This advantageously provides flexibility of positioning the tabs in situ to suit various installation requirements.
In preferred embodiments, the width 24 of each tab is smaller than the edge dimensions of the trim member or trim member to which it is connected. For example, the width of each tab 4 , 16 is significantly smaller than the length of the trim member 1 , 14 , 15 . For installations where a substantially planar tab 4 is used, it is also preferred that the width of the tab 4 is smaller than the width of the trim member 1 to allow for flexibility of connection of tabs to the ends 25 of the trim member. As best shown in FIG. 7 , the smaller width of tab 4 allows the second portions of the tab 4 connected to side members 9 to be concealed by the adjacent bottom trim member 10 and top trim member 11 without the tabs overlapping.
In one embodiment, staples are used to connect the load bearing tab 4 , 16 to the trim members. These staples are necessarily short enough so that they do not protrude all the way through the trim but have sufficient holding power to maintain the connection between the trim member and the tab under normal load conditions. This is preferably advantageous when the trim member is made of fiber cement. The fasteners used to fix the second portions of the tab 4 , 16 to the support structure and corner structure are typically normal nail gun framing constructions nails
In another embodiment, hardened “T” nails (Brad nails) are used to connect the load bearing tab 4 , 16 to the trim members. These nails are necessarily short enough so that they do not protrude all the way through the trim but have sufficient holding power to maintain the connection between the trim member and the tab under normal load conditions. This is preferably advantageous when the trim member is made of fiber cement. The nails used to fix the second portions of the tab 4 , 16 to the support structure and corner structure are typically normal nail gun framing constructions nails.
While nails have been referred to throughout the specification as one method of connecting the tabs to both the trim members and the underlying building structure, it will be appreciated that any suitable means of fastening may be used. This may include, for example, screws, rivets, bolts, staples, adhesives, etc.
Referring next to FIGS. 11 and 12 , another embodiment of a system for concealed fastening of building finishing elements is illustrated. As shown in FIGS. 11 and 12 , the system incorporates a trim member 26 with a clip retaining groove 27 in its structure facing surface 28 and a concealed fixing tab 29 . The tab 29 includes on its first portion 30 a retaining formation such as the generally v or tick sectioned clip element shown generally at 31 . The clip element is configured in this particular embodiment to have a sprung flange 32 which in use in entering the groove 27 , compresses toward the adjacent planar part 33 of the first portion 30 , and then springs away to engage against the inner surface 34 of the groove to thereby retain the tab. It will be appreciated that the groove may be a simple channel shape of generally u or v shaped cross section or include some element of undercut such as in an “l” or “t”-slot to help retain the clip portion of the tab. Where the building finishing element is longitudinal such as with the illustrated trim component, the groove is preferably provided along the full length of the building element. In some forms more than one groove may be provided.
While the form of the retaining formation can vary, so can the rest of the tab. For example the second portion may be perforate or solid or any combination thereof. The earlier comments apply in terms of preferred methods of securing the second portion of the tab using one or more siding nails although once again other alternative fasteners may be suitable.
Preferably, the load bearing tabs in all embodiments are formed of aluminum or steel. However, it will be appreciated that the tabs may be formed of any material suitable for supporting the trim members and fixing them to the underlying structure.
The optional perforations in the tabs advantageously allow fastener fixing with thicker tabs than would otherwise be possible. The thickness of the tabs is typically determined by the strength required to support a trim member having a given length and specific orientation, usually horizontal or vertical. The thickness of the tab may also be influenced to some degree by the effect of wind loading on the trim member.
The system advantageously allows the use of standard fastening guns and standard commercially available fasteners. This advantageously results in minimum cost of implementation and minimum additional skills required for installers.
Although preferred embodiments of the invention have been described in detail, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms. | In one form of building structure, trim installations are applied around window or door frame openings and at internal or external corners of a building. The trim serves both an aesthetic purpose in adding a decorative feature to building envelopes and also adds an additional weatherproofing purpose in allowing for more complete weatherproofing of building envelope corners and openings. The present invention relates to a concealed fastening building finishing element system that enables concealed fastening of finishing elements such as trim components, fascia boards, frieze boards, belly band boards, and the like to an underlying structure and to the fixings used in these systems. The invention is particularly useful with trim elements around window and door frame openings and at building corners. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a division of application Ser. No. 09/884,786, filed Jun. 19, 2001 to which this application claims benefit under 35 U.S.C. §120.
BACKGROUND OF THE INVENTION
[0002] The perception that nitric oxide (NO), a chemically active gas, plays an essential role in human and animal physiology was first demonstrated in 1987 with the publication of Nitric Oxide Accounts for the Biological Activity of Endothelium Derived Relaxing Factor ; Palmer, R. M., Ferridge, A. G., Moncada, S; Nature 1987; 327:524-526. The authors demonstrated that the endothelial-derived relaxation factor (EDRF) was indeed nitric oxide. Many research publications have since defined more clearly the multiple and complex roles of NO in human, animal and plant physiology. Synthesized endogenously in humans, animals and plants, NO plays many very important physiological roles. For example, research reports have shown that NO may be effective in the treatment of sickle cell anemia.
[0003] Nitric oxide, in conjunction with ventilatory support and other appropriate agents, is used for the treatment of term and near-term (greater than 34 weeks) neonates with hypoxic respiratory failure associated with clinical or echocardiographic evidence of pulmonary hypertension, where it improves oxygenation and reduces the need for extracorporeal membrane oxygenation. It has also been reported to be useful as a selective pulmonary vasodilator in patients with adult respiratory distress syndrome. Lack of systemic vasodilatory effects with nitric oxide is an advantage over other vasodilators (e.g., epoprostenol (prostacyclin), nitroprusside).
[0004] Among the increasing range of pathologies which can be successfully treated with gaseous NO is anal disease. Anal fissure (or fissure-in-ano), anal ulcer, acute hemorrhoidal disease, and levator spasm (proctalgia fugax) are common, benign conditions of the anal canal which affect men and women. An anal fissure or ulcer is a tear or ulcer of the mucosa or lining tissue of the distal anal canal. An anal fissure/ulcer can be associated with other systemic or local diseases, but it is more frequently present as an isolated finding. The typical, idiopathic fissure or ulcer is confined to the anal mucosa, and usually lies in the posterior midline, distal to the dentate line. The person with an anal fissure or ulcer suffers from anal pain and bleeding, more pronounced during and after bowel movements.
[0005] Hemorrhoids are specialized vascular areas lying subjacent to the anal mucosa. Symptomatic hemorrhoidal disease is manifest by bleeding, thrombosis or prolapse of the hemorrhoidal tissues. Men and women are affected. Most commonly, internal hemorrhoidal tissue bulges into the anal canal during defecation causing bleeding. As the tissue enlarges, prolapse pain, thrombosis, and bleeding can ensue. Thrombosis of internal or external hemorrhoids is another cause of pain and bleeding.
[0006] Levator spasm (or proctalgia fugax) is a condition of unknown etiology affecting women more frequently than men. This syndrome is characterized by spasticity of the levator ani muscle, a portion of the anal sphincter complex. The patient suffering from levator spasm complains of severe, episodic rectal pain. Physical exam may reveal spasm of the puborectalis muscle. Pain may be reproduced by direct pressure on this muscle. Bleeding is not associated with this condition.
[0007] The underlying causes of these problems are poorly understood. However, all of these disorders are associated with a relative or absolute degree of anal sphincter hypertonicity. In the case of anal fissure/ulcer the abnormality appears to be an as yet unidentified problem of the internal and sphincter muscle. The internal sphincter is a specialized, involuntary muscle arising from the inner circular muscular layer of the rectum. Intra-anal pressure measurements obtained from people suffering from typical anal fissure/ulcer disease show an exaggerated pressure response to a variety of stimuli. The abnormally high intra-anal pressure is generated by the internal sphincter muscle. The abnormally elevated intra-anal pressure is responsible for non-healing of the fissure/ulcer and the associated pain. U.S. Pat. No. 5,504,117 teaches methods to treat anal pathologies by the topical application of preparations that stimulate the production of endogenous nitric oxide synthase (NOS) which, in turn, causes NO to be generated in endothelial tissue and in the nervous system, by the catalytic action of NOS upon L-Argenine.
[0008] Although safe NO dosage values are at present still evolving, the Occupational Safety and Health Administration (OSHA) has set the time-weighted average inhalation limit for NO at 25 ppm for 10 hours and NOsub2 not to exceed 5 ppm. NIOSH Recommendations for Occupational Safety and Health Standards: Morbidity and Mortality Weekly Report, Vol. 37, No. S-7, p. 21 (1988). The Environmental Protection Agency (EPA) has stated that a health-based national (maximum ambient) air quality standard for NOsub2 is 0.053 ppm (measured as an annual average).
[0009] When exposed to oxygen, NO gas will, depending on environmental conditions, undergo oxidation to NOsub2, also to higher oxides of nitrogen. Gaseous nitrogen dioxide, if inhaled in sufficient concentration (for example, as little as 10 ppm for ten minutes), is toxic to lung tissue and can produce pulmonary edema and this concentration and exposure time, or more, could result in death. Standards with regard to nitrogen dioxide toxicity have not been firmly established. Nitrogen dioxide is a deep lung irritant that can produce pulmonary edema and death if inhaled at high concentrations. The effects of NOsub2 depend on the level and duration of exposure. Exposure to moderate NOsub2 levels, 50 ppm for example, may produce cough, hemoptysis, dyspnea, and chest pain. Exposure to higher concentrations of NOsub2 (greater than 100 ppm) can produce pulmonary edema, that may be fatal or may lead to bronchiolitis obliterans. Some studies suggest that chronic exposure to nitrogen dioxide may predispose to the development of chronic lung diseases, including infection and chronic obstructive pulmonary diseases.
[0010] It is common practice in therapeutic NO inhalation procedures both to monitor and also to remove NOsub2 before it can be inhaled by a subject to whom NO is being applied. For example, the NO respiratory gas mixture may be transported through a soda lime mixture to scavenge nitrogen dioxide. However, NO gas in the therapeutic concentration range (i.e. 1 ppm to as much as 100 ppm) can be administered safely, for short time periods, in dry normal air (21% oxygen) without the formation of toxic concentrations of NOsub2. Moreover, the present invention may include intra-capsular means to adsorb NOsub2.
[0011] Historically, NO gas is commercially manufactured using the Ostwald process (U.S. Pat. No. 4,774,069, U.S. Pat. No. 5,478,549) in which ammonia is catalytically converted to NO and Nitrous Oxide at a temperature above 800 degrees centigrade. This process thus involves the mass production of NO at high temperatures in an industrial setting. The therapeutic advantages of NO over other pulmonary and cardiovascular drugs have led researchers to attempt the design of an instrument that can deliver variable concentrations of NO accurately. For example, U.S. Pat. No. 5,396,882 describes a process for generating NO in an electric arc discharge in air where the electrodes are separated by an air gap in an arc chamber. The application of a high voltage across the air gap produces a localized plasma that breaks down oxygen and nitrogen molecules and generates a mixture of NO, ozone, and other NOx species. The concentration of NO in this system can be varied by adjusting the operating current. The gas mixture is then purified and mixed with air in order to obtain therapeutically significant concentrations of NO prior to administration to a patient. However, the quantification of generated NO by this system is purely empirical making the instrument extremely susceptible to the slightest fluctuations in the internal and external parameters such as ambient humidity and the surface area of the electrodes in the arc chamber.
[0012] Although inhalation of nitric oxide gas has been shown to be effective for treatment of pulmonary hypertension, there are several drawbacks and limitations of this particular mode of therapy. For example, current art therapy requires large and heavy gas tanks, expensive monitoring equipment, and a trained anesthesiologist to operate the tanks and equipment so as to deliver NO gas to a patient with safety. Therefore, NO inhalation therapy is at present limited to hospitals or similar clinical facilities. Thus there is a great needed for a more flexible, portable and less expensive means with which NO may be delivered safely in an organ specific manner without causing systemic vasodilation.
[0013] For over a century, nitroglycerin has been used as a vasodilating agent in the treatment of cardiovascular disease. Nitroglycerin, or glyceryl trinitrate, is an organic nitrate ester which when administered to a subject is converted biologically to nitric oxide by stimulating an enzyme, nitric oxide synthase (NOS), which in turn, catalyzes the production of endogenous NO from L-argenine. However, the effectiveness of nitroglycerin is greatly diminished because the recipient of therapeutic administration of nitroglycerin rapidly develops a tolerance to the beneficial effects of nitroglycerin. Therefore, onset of nitroglycerin tolerance significantly limits the therapeutic value of nitroglycerin because increased nitroglycerin dosages have little or no effect on vasorelaxation or vasodilatation. A further limitation may result from the fact that nitroglycerin is physiologically non specific. That is, vascular response to the drug will be generally distributed over the entire circulatory system.
SUMMARY OF THE INVENTION
[0014] The present invention teaches new and novel methods and means with which NO can be rapidly delivered to alveolar vascular tissue so as to bring about a rapid increase in the concentration of NO in lung and heart vascular epithelia. The effect is to cause rapid dilation of blood vessels in the lung and heart and to a considerably lesser degree, in more distal blood vessels through which blood circulates owing to the rapid absorption of NO by red blood cells.
[0015] The present invention features methods for prevention and treatment of asthma attacks and other forms of bronchial constriction, acute respiratory failure, or reversible pulmonary vasoconstriction (i.e., acute or chronic pulmonary vasoconstriction which has a reversible component). An affected subject may be identified, for example, by acute physical distress symptoms or by traditional diagnostic procedures. The subject will then inhale a therapeutically-effective concentration of gaseous nitric oxide so as to achieve therapeutic relief.
[0016] The present invention teaches methods and devices that produce NO from the inside of portable and disposable capsules containing NO under pressure and from chemical reagents which, when appropriately combined or activated, generate a controlled outflow of pure NO gas to the capsule exterior in free air. It is essential that the concentration of gas inhaled from the above mentioned capsular NO source be large enough to effect therapeutically beneficial results and at the same time not exceed a safe NO concentration maximum for gas inhalation. Both exposure time and gas concentration values together dictate what safe dosage may be.
[0017] The present invention teaches the principles of new devices and new procedures that will provide effective therapeutic application of inhaled NO during coronary and respiratory emergencies such as angina, thrombosis in heart and lung blood vessels; also hypertension in lung vasculature, as well as reversible asthma attacks.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The present invention may be better understood and its numerous objects and advantages will become apparent to those skilled in the art by reference to the accompanying drawings in which:
[0019] [0019]FIG. 1 is a schematic, cross-sectional view of a first embodiment of a NO storage and delivery system in accordance with the invention;
[0020] [0020]FIG. 2 is a schematic, cross-sectional view of a second embodiment of a NO storage and delivery system in accordance with the invention;
[0021] [0021]FIG. 3 is a schematic, cross-sectional view of a third embodiment of a NO storage and delivery system in accordance with the invention; and
[0022] [0022]FIG. 4 is a schematic, cross-sectional view of a fourth embodiment of a NO storage and delivery system in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] A number of compounds have been developed that are capable of delivering nitric oxide in a pharmacologically useful way. Such compounds include compounds that release nitric oxide after being metabolized and compounds that release nitric oxide spontaneously in aqueous solutions. Compounds capable of releasing NO upon being metabolized include the widely used nitrovasodilators glyceryl trinitrate (nitroglycerin) and sodium nitroprusside (SNP). These compounds are relatively stable but they release or cause the release of NO upon activation.
[0024] Many nitric oxide-nucleophile complexes also have been described. Some of these compounds, known as NONOates, evolve nitric oxide upon heating or hydrolysis. These compounds, unlike nitroglycerin or SNP, release NO without requiring activation. NONOates have reproducible half-lives ranging from 2 seconds to 20 hours. Nitricoxide/nucleophile complexes (NONOates) that release nitric oxide in aqueous solution are disclosed in U.S. Pat. No. 5,389,675, U.S. Pat. No. 5,366,977, and U.S. Pat. No. 5,250,550. The nitric oxide-releasing functional group is R—[NONO], where R is an organic or inorganic moiety bonded to the [NONO].
[0025] NO may be generated from S-nitrosothiols (RSNO) in presence of catalyst Cu(I), as outlined in the reaction below:
2RSNO→2 NO+RS−SR (1)
[0026] The concentration of generated NO is equal to the original RSNO concentration after, the addition of the catalyst Cu(I).
[0027] NO may be generated chemically. In a first example, based on the reaction of nitrite with iodide in an acidic medium as in the reaction:
2 KNO 2 +2 KI+2 H 2 SO 4 →2 NO+I 2 +2 H 2 O+2 K 2 SO 4 (2)
[0028] The concentration of NO is determined by the nitrite and iodide concentrations. Ascorbic acid may be used above to replace KI as a reductant.
[0029] In a second example, at room temperature, vanadium (III) rapidly reduces nitrite to nitric oxide in an acidic solution. Vanadium (III), as a reductant is oxidized to vanadium (IV):
NO 2− +2H + +e→NO+H 2 O (3)
[0030] The NO storage and delivery system 10 shown in FIG. 1 employs a gas impermeable capsule 12 as the storage vessel for a gas source 14 composed of compressed NO gas. NO gas is injected into the capsule 12 under pressure in an anaerobic environment. The internal gas-filled cavity 16 has preferably a 1 to 5 ml inner volume. Internal NO gas pressure is typically 15 to 30 psi. The capsule casing is impermeable to gas leakage.
[0031] Gas is released from the capsule 12 via an opening 18 extending through the capsule wall and an applicator sleeve 20 enclosing the opening 18 and extending outwardly from the capsule 12 . Gas release can be effected, for example, by removal of a gas-tight cap 22 from the neck 24 of the applicator sleeve 20 . Alternative capsule sealing methods can be easily implemented by conventional art means.
[0032] A miniature pressure controller 26 within the sleeve 20 limits the exit pressure of the stored gas so as to release NO gas at a constant pressure which is less than that of the initial internal capsule gas pressure. An outlet filter 28 downstream of the pressure controller 26 restricts the rate of gas outflow. For example, gas release pressure regulated at 5 psi would be adequate to assure constant gas outflow for periods of time which can be made to range from a few seconds to hours. The flow rate of exiting gas can be limited to a few micro liters per minute. Prior to use, the capsule 12 is stored in a sterile bag that is gas and moisture impermeable to prevent environmental and bacterial infiltration.
[0033] As an alternative to charging the capsule 12 from an external pressurized NO gas source, the NO gas source 14 can be a NO bearing polymer. The polymer material is sealed within the capsule cavity 16 and slowly decomposes to release the NO gas stored therein, and thus constitutes the intra capsular NO gas supply 14 . The polymer material, is initially loaded into the capsule 12 in an oxygen-free environment. If NONOate is to be the NO source 14 , de-aerated water must be applied to initiate NO release.
[0034] [0034]FIG. 2 illustrates a second embodiment of the system 10 ′ having a NO gas source 30 in which NO gas is created by activation of stored chemical reagents 32 , 34 . Capsule 36 is flexible and gas impermeable. The gas source 30 comprises stored reagents 32 and 34 , which are physically isolated by a breakable divider 38 , for example a glass tube, containing reagent 32 . Bending capsule 38 breaks reagent vessel 38 causing chemical reagents 32 and 34 to mix, resulting in the rapid formation of NO gas within the capsule 36 . The known stoichiometry of the chemical reaction and the volume of the capsule interior allows accurate prediction of the resulting intra capsular NO gas pressure. A single example of several feasible chemical reactions is illustrated in equation (1) above. In this example, reagent 32 is a solution of potassium nitrite and reagent 34 is a mixture of potassium iodide and sufric acid.
[0035] Compressed NO gas flows out of the capsule 36 via a check valve 40 comprised, for example, by a ball 42 and spring 44 . The outflow filter 46 controls the gas outflow rate and also filters water vapor from the fluid reagents in the capsule 36 . The filter 46 may be treated with a nitrogen dioxide adsorbent so as to insure that, if present, virtually no nitrogen dioxide will be present in the generated gas. Prior to use, the capsule 36 is stored in a sterile bag that is gas and moisture impermeable to prevent environmental and bacterial infiltration.
[0036] The embodiment 10 ″ shown in FIG. 3 is similar in form and function to the embodiment 10 ′ of FIG. 2 except that outlet filter 46 of FIG. 2 is replaced by a NO gas permeable capped tube 48 which delivers a diffuse gentle flow of NO into the nostrils or, alternatively, other body cavities of subject humans or animals for therapeutic effect. Internal tubular gas pressure and the gas permeability of the capped tube 48 both determine the rate of the resulting NO gas outflow. Prior to use, the capsule 36 is stored in a sterile bag that is gas and moisture impermeable to prevent environmental and bacterial infiltration.
[0037] The embodiment 10 ′″ illustrated in FIG. 4 has an ovoid or lozenge shaped capsule 50 . The capsule 50 is impermeable to acid or water or other interior reagents 32 , 34 employed therein. The capsule 50 is also NO gas permeable and flexible. Active chemical reagents 32 ′ and 34 ′ are similar in function to reagents 32 and 34 of FIG. 2. Reagent 32 ′ is contained in a breakable compartment 38 ′ or tube as in FIG. 2. In use, the capsule 50 is activated by applying sufficient force to break the reagents tube 38 ′ which initiates a NO gas producing reaction as discussed above. After activation, the capsule 50 may be lubricated with a gas permeable fluid 52 such as silicone and gently inserted into the appropriate body cavity of a subject requiring NO gas therapy as discussed above. Upon completion of the NO treatment, the capsule 50 may be withdrawn by using the attached cord 54 . For respiratory therapy, the capsule 50 may be held under the nostrils for the duration of the treatment. Prior to use, the capsule 50 is stored in sterile bags that are gas and moisture impermeable to prevent environmental or bacterial infiltration and possible contamination.
[0038] It should be appreciated that by using a system 10 , 10 ′, 10 ″, 10 ′″ in accordance with the invention, pure NO gas is generated for inhalation proximal to or within the nostrils of the subject and transported to the lungs by the tidal action of the subject's respiration.
[0039] The concentration of nitric oxide gas is diluted by the respiratory tidal volume of the user. Consequently, the user's own respiration performs the dual function of transporting and diluting the NO gas. Moreover, negligible nitrogen dioxide formation occurs within the time interval in which NO gas is transported by the respiratory tidal volume to the lung alveoli. Theoretical analysis and experimental results indicate the NO 2 concentration is much less than 1 ppm for the time periods used by the inventive methods of the present invention. It should also be appreciated that the subject system 10 , 10 ′, 10 ″, 10 ′″ does not require an expensive and complex gas mixing and delivery system because the subject's own respiration safely delivers NO gas at low ppm concentration levels to the subject's lungs. It should further be appreciated that the subject system 10 , 10 ′, 10 ″, 10 ′″ does not utilize industrial NO gas tanks, which are expensive, heavy and potentially dangerous.
[0040] The above disclosed embodiments are generally single use systems with the amount of pressurized NO gas or reagents sized accordingly. It should be appreciated that once the reagents of embodiments 10 ′, 10 ″, and 10 ′″ are mixed together, the resulting reaction will continue to completion. Further, the absence of a gas-tight cap 22 on the applicator sleeve of the second embodiment 10 ′ and the permeable nature of the capped tube 48 of the third embodiment 10 ″, and the capsule 50 of the fourth embodiment 10 ′″, preclude retention of the NO gas within the capsule 36 , 36 ′, 50 after the reagents 32 , 32 ′, 34 , 34 ′ have been mixed. While it is possible that the gas-tight cap 22 of the first embodiment 10 may be replaced before all of the pressurized NO gas is dispensed through the applicator sleeve 20 , the escaping NO gas will interfere with such replacement and there is no way of assuring that the remaining amount of NO gas will be therapeutically useful.
[0041] While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation. | A storage and delivery system for directly applying nitric oxide to a user includes a portable and disposable capsule and a source of nitric oxide gas disposed within the cavity. Gas flow control apparatus controls the flow of nitric oxide gas from the cavity. Gas flow initiation apparatus allows the user to initiate the flow of nitric oxide gas. The encapsulated nitric oxide gas is applied by positioning the capsule proximate to the objective site of the user and initiating flow of the nitric oxide gas. | 8 |
BACKGROUND OF THE INVENTION
Solid polymer electrolyte (SPE) cells refer to cells in which one or both electrodes are bonded to or embedded in a polymeric ion exchange membrane. Such cells are rather well known in the art and are discussed in detail in the following patents: U.S. Pat. No. 4,315,805 "Solid Polymer Electrolyte Chlor-Alkali Process", Darlington, et al. (Feb. 16, 1982); U.S. Pat. No. 4,364,815 "Solid Polymer Electrolyte Chlor-Alkali Process and Electrolytic Cell", Darlington, et al.(Dec. 12, 1982); U.S. Pat. No. 4,272,353 "Method of Making Solid Polymer Electrolyte Catalytic Electrodes and Electrodes Made Thereby", Lawrence, et al.(June 9, 1981; and U.S. Pat. No. 4,394,229 "Cathode Element For Solid Polymer Electrolyte", Korach (July 19, 1983).
In SPE cells, a current collector is pressed against and contacts the electrode and provides a pathway for electrical current to flow from a power supply to the electrode. Current collectors are electrically conductive, hydraulically permeable matrices which may take a variety of shapes, sizes, and types, including metallic window screen, punched metallic plates, expanded metals, and the like. The following patents describe some commonly-used types of current collectors: U.S. Pat. No. 4,299,674 "Process For Electrolyzing An Alkali Metal Halide Using A Solid Polymer Electrolyte Cell", Korach (Nov. 10, 1981); U.S. Pat. No. 4,468,311 "Electrolysis Cell", de Nora, et al. (Aug. 28, 1984); and U.S. Pat. No. 4,215,183 "Wet Proofed Conductive Current Collectors for the Electrochemical Cells", MacLeod (July 29, 1980).
SPE cells often have major problems due to the high electrical resistance between the embedded or bonded electrodes and the current collectors which are pressed against the electrode. Many workers in the art have attempted to solve the high resistance problem in a variety of ways. Some solutions include the use of a mattress as shown in U.S. Pat. No. 4,468,311 "Electrolysis Cell", de Nora, et al. (Aug. 28, 1984); applying the electrocatalyst directly to a conductive carbon cloth which acts as the current collector as shown in U.S. Pat. No. 4,239,396 "This Carbon-Cloth-Based Electrocatalytic Gas Diffusion Electrodes, And Electrochemical Cells Comprising the Same", Allen, et al. (Oct. 6, 1981).
The present invention provides a SPE structure that minimizes the electrical resistance between the current collector and the embedded or bonded electrode.
SUMMARY OF THE INVENTION
The invention is a method for forming a solid polymer electrolyte structure comprising:
(a) heating a fluorocarbon membrane, while it is in its thermoplastic form, to a temperature at which it softens;
(b) contacting a plurality of electrically conductive, catalytically active particles with at least a portion of one face of the membrane, while said membrane is in a softened state;
(c) subjecting the membrane/particle combination to a pressure sufficient to embed at least a portion of the particles into the membrane;
(d) contacting the particulated membrane with an electrically conductive, hydraulically permeable matrix,
(e) subjecting the particulated membrane/matrix combination to a pressure sufficient to embed at least a portion of the matrix into the particulated membrane.
BRIEF DESCRIPTION OF THE FIGURE
The FIGURE illustrates the SPE structure of the present invention and shows the membrane sheet 120, the plurality of electrically conductive particles 110, and the electrically conductive, hydraulically permeable matrix 130.
DETAILED DESCRIPTION OF THE INVENTION
As a result of the intimate contact between the membrane sheet, the electrically conductive particles, and the electrically conductive, hydraulically permeable matrix (which serves as a current collector and is connected to a power supply), the resistance to the flow of electrical energy is minimized and, thus, the cell operates more efficiently than cells employing the SPE structures of the prior art.
The SPE structure of the present invention includes embodiments where electrically conductive particles are bonded to or embedded in one, or both, sides of the membrane sheet.
The FIGURE shows the SPE structure 100. It is composed of a membrane sheet 120 which has a plurality of electrically conductive particles embedded into it. The particles are in physical and electrical contact with an electrically conductive, hydraulically permeable matrix 130, which is also embedded into the membrane sheet 120.
The membrane sheet divides the anode compartment from the cathode compartment and limits the type and amount of fluids and/or ions that pass between the anode compartment and the cathode compartments. The membrane may be a single layer membrane or a composite layer membrane.
The membrane may be constructed of a fluorocarbon-type material or of a hydrocarbon-type material. Such membrane materials are well known in the art. Preferably, however, fluorocarbon materials are generally preferred because of their chemical stability.
Non-ionic (thermoplastic) forms of perfluorinated polymers described in the following patents are suitable for use in the present invention: U.S. Pat. Nos. 3,282,875; 3,909,378; 4,025,405; 4,065,366; 4,116,888; 4,123,336; 4,126,588; 4,151,052; 4,176,215; 4,178,218; 4,192,725; 4,209,635; 4,212,713; 4,251,333; 4,270,996; 4,329,435; 4,330,654; 4,337,137; 4,337,211; 4,340,680; 4,357,218; 4,358,412; 4,358,545; 4,417,969; 4,462,877; 4,470,889; and 4,478,695; European Patent Application 0,027,009. Such polymers usually have equivalent weight in the range of from about 500 to about 2000.
To allow the cloth and the electrically conductive particles to be embedded into the fluorocarbon membrane, it is desirable for the fluorocarbon membrane to be in its thermoplastic form. It is in a thermoplastic form when it is made and before it is converted into an ion exchange form. By thermoplastic form, it is meant, for instance, that the membrane has SO 2 X pendant groups rather than ionically bonded SO 3 Na or SO 3 H pendant groups, where X is --F, --CO 2 , --CH 3 ,or a quaternary amine.
Particularly preferred fluorocarbon materials for use in forming membranes are copolymers of monomer I with monomer II (as defined below). Optionally, a third type of monomer may be copolymerized with I and II.
The first type of monomer is represented by the general formula:
CF.sub.2 =CZZ' (I)
where: Z and Z' are independently selected from the group consisting of --H, --Cl, --F, or --CF 3 .
The second monomer consists of one or more monomers selected from compounds represented by the general formula:
Y--(CF.sub.2).sub.a --(CFR.sub.f).sub.b --(CFR.sub.f').sub.c --O--[CF(CF.sub.2 X)--CF.sub.2 --O].sub.n --CF═CF.sub.2(II)
where:
Y is selected from the group consisting of --SO 2 Z, --CN, --COZ, and C(R 3 f) (R 4 f)OH;
Z is I, Br, Cl, F, OR, or NR 1 R 2 ;
R is a branched or linear alkyl radical having from 1 to about 10 carbon atoms or an aryl radical;
R 3 f and R 4 f are independently selected from the group consisting of perfluoroalkyl radicals having from 1 to about 10 carbon atoms;
R 1 and R 2 are independently selected from the group consisting of H, a branched or linear alkyl radical having from 1 to about 10 carbon atoms or an aryl radical;
a is 0-6;
b is 0-6;
c is 0 or 1;
provided a+b+c is not equal to 0;
X is Cl, Br, F, or mixtures thereof when n>1;
n is 0 to 6; and
R f and R f' , are independently selected from the group consisting of F, Cl, perfluoroalkyl radicals having from 1 to about 10 carbon atoms and fluorochloroalkyl radicals having from 1 to about 10 carbon atoms.
Particularly preferred is when Y is --SO 2 F or --COOCH 3 ; n is 0 or 1; R f and R f' , are F; X is Cl or F; and a+b+c is 2 or 3.
The third and optional monomer suitable is one or more monomers selected from the components represented by the general formula:
Y''(CF.sub.2).sub.a' --(CFR.sub.f).sub.b' --(CFR.sub.f').sub.c' --O--[CF(CF.sub.2 X')--CF.sub.2--O].sub.n' --CF═CF.sub.2(III)
where:
Y' is F, Cl or Br;
a' and b' are independently 0-3;
c is 0 or 1;
provided a'+b'+c' is not equal to 0;
n' is 0-6;
R f and R f , are independently selected from the group consisting of Br, Cl, F, perfluoroalkyl radicals having from about 1 to about 10 carbon atoms, and chloroperfluoroalkyl radicals having from 1 to about 10 carbon atoms; and
X' is F, Cl, Br, or mixtures thereof when n'>1.
Conversion of Y to ion exchange groups is well known in the art and consists of reaction with an alkaline solution.
While the fluorocarbon membrane is in its thermoplastic form, it is capable of softening when heated and hardening again when cooled. Thus, the cloth can be easily pressed into the fluorocarbon membrane when the fluorocarbon membrane has been heated. The temperature to which the fluorocarbon membrane is preferably heated to make it sufficiently soft to allow the cloth to be embedded therein depends, to a great extent, on the chemical formulation of the fluorocarbon membrane. In general, however, temperatures in the range of from about 150° Celsius to about 350° Celsius for fluorocarbon membranes having Y=--SO 2 F (as defined in Equation II above), or 150° Celsius to 300° Celsius for fluorocarbon membranes having Y=--CO 2 CH 3 (as defined in Equation II above). Hydrocarbon-based membranes may (depending upon the exact composition of the hydrocarbon material) be heated from about 100° Celsius to about 190° Celsius.
For example, a membrane sheet may be prepared by hot pressing a sulfonyl fluoride powder having an equivalent weight of about 1000, as described in U.S. Pat. No. 4,330,654 between two sheets of glass reinforced polytetrafluoroethylene at a temperature of about 310° Celsius under a pressure of about 0.75 tons per square inch for about 1.25 minutes. The resulting 6-7 inch diameter sheet is preferably in the range of from about 0.0001 to about 0.010 inches thick. More preferably, the thickness of the sheet is from about 0.0005 to about 0.015 inches thick. Most preferably, the thickness of the sheet is from about 0.002 to about 0.06 inches thick.
In the present invention, it is important to make an effective bond between the electrically conductive, hydraulically permeable matrix and the membrane. Such a bond may be made with or without the use of externally-applied pressure during bonding. It has been discovered, however, that better bonding is generally obtained when the membrane and the electrically conductive, hydraulically permeable matrix are first contacted and heated at zero pressure for about 1 minute, followed by pressing at about 1 to about 8 tons per square inch for from about 0.2 to about 2 minutes.
The present invention requires that at least one of the electrodes be in the form of a plurality of electrically conductive particles embedded into the membrane sheet. This is what makes an SPE electrode. The electrode composed of a plurality of electrically conductive particles can be either the cathode or the anode. Optionally, both electrodes can be electrically conductive particles embedded into opposite sides of the membrane sheet. For the purposes of the present discussion, the forms of both electrodes will be described as though they are electrically conductive particles and will also be described as if they are separate, conventional electrodes.
Conventional anodes are usually hydraulically permeable, electrically conductive structures made in a variety of shapes and styles including, for example, a sheet of expanded metal, perforated plate, punched plate, unflattened diamond shaped expanded metal, or woven metallic wire. Metals suitable for use as anodes include tantalum, tungsten, columbium, zirconium, molybdenum, and preferably, titanium and alloys containing major amounts of these metals.
Optionally the anodes may be an SPE electrode consisting of a plurality of electrically conductive particles embedded into the membrane sheet. Materials suitable for use as electrocatalytically active anode materials include, for example, activating substances such as oxides of platinum group metals like ruthenium, iridium, rhodium, platinum, palladium, either alone or in combination with an oxide of a film-forming metal. Other suitable activating oxides include cobalt oxide either alone or in combination with other metal oxides. Examples of such activating oxides are found in U.S. Pat. Nos. 3,632,498; 4,142,005; 4,061,549; and 4,214,971.
Conventional cathodes are usually hydraulically permeable, electrically conductive structures made in a variety of shapes and styles including, for example, a sheet of expanded metal, perforated plate, punched plate, unflattened diamond shaped expanded metal, or woven metallic wire. Metals suitable for use as cathode include, for example, copper, iron, nickel, lead, molybdenum, cobalt, alloys including major amounts of these metals, such as low carbon stainless steel, and metals or alloys coated with substances such as silver, gold, platinum, ruthenium, palladium, and rhodium.
Optionally, as has been stated, the cathode may be an SPE electrode consisting of a plurality of electrically conductive particles embedded into the membrane sheet. Materials suitable for use as electrocatalytically active cathode materials include, for example, platinum group metal or metal oxide, such as ruthenium or ruthenium oxide. U.S. Pat. No. 4,465,580 describes such cathodes.
The electrically conductive particles, whether used as an anode or as a cathode are preferably finely divided and have a high surface area. For example, in the case of an oxygen or hydrogen electrode fuel cell, platinum black (surface area greater than 25 m 2 /gram) or high surface area (800-1800 m 2 /g) platinum on activated carbon powder (average particle size 10-30 microns) are quite suitable for use as the anode and the cathode. In the case of a chlorine cell, an may be prepared in which ruthenium dioxide particles are prepared by thermal decomposition of ruthenium nitrate for 2 hours at 450° Celsius. The resulting oxide may then be ground using a mortar and pestle and the portion which passed through a 325 mesh sieve (less than 44 microns) used to prepare an electrode.
The electrically conductive, hydraulically permeable matrix which acts as a current collector to transmit electrical energy to or from the SPE electrode, may be composed of a variety of substances including carbon cloth, carbon paper, carbon felt, metallic screens, metallic felt, and porous metallic sheets. Preferably, however, the electrically conductive, hydraulically permeable matrix is a carbon cloth because carbon cloth is readily available, performs well, is easily handled, and is relatively inexpensive.
The cloth most preferably used in this invention is one having low electrical resistivity, relatively inexpensive, possess sufficient strength for fabrication, and have adequate surface properties, such as roughness, to provide good bonding between the ion exchange membrane and itself. It is also preferable to provide good electrical contact between the carbon cloth and the electrocatalytically active particles of the electrode.
The type of carbon cloth suitable for use in the present invention is commercially available from a variety of sources including: Stackpole Fibers Co. sold under the names Panex PWB-3, PWB-6, KFB and SWB-8; from Union Carbide Corp. sold under the names WCA Graphite Cloth and VCK and VCA carbon cloth. Carbon cloth may also be woven from carbon fibers available from Fiberite Corp. sold under the names Celion 1000, Celion 3000, Celion 6000, Celion 12000, or from Celanese Corporation sold as C-6, or G-50. These materials may vary in physical properties but are acceptable for use in the present invention if they are sufficiently strong to maintain their physical integrity during fabrication. Fiber size and weave patterns may also vary and are not critical to the successful operation of the present invention. Cloth useful in the present invention preferably has a thickness of from about 0.002 inches to about 0.025 inches and have electrical resistivities of from about 600,000 to about 1375 microohm-centimeters. More preferably the cloth used in the present invention has a resistivity of approximately 1500 microohm-centimeters.
The SPE structure may then be fabricated by preparing the membrane in the thermoplastic form, embedding the electrocatalytically active particles into the membrane, bonding the current collector over the particles, and then converting the membrane to its ionic form by reacting it with, in the case of --SO 2 F pendant groups, 25 weight % NaOH under the following conditions: (1) immerse the film in about 25 weight percent sodium hydroxide for about 16 hours at a temperature of about 90° Celsius; (2) rinse the film twice in deionized water heated to about 90° Celsius, using about 30 to about 60 minutes per rinse. The pendant group is then in the --SO 3 - Na + form. Cations other than Na + can be made to replace the Na + if practical (such as H + ).
The electrocatalytically active particles may be incorporated into the surface of the membrane using a variety of techniques including, for example, pressing, slurrying with a solvent and blending with membrane or other polymer powders. Such techniques are rather well known in the art. One technique involves the use of platinum particles applied to carbon powder by being brushed evenly over a fluorocarbon membrane film in its thermoplastic form. The so-coated film is then placed between sheets of glass reinforced polytetrafluoroethylene and hot pressed at temperatures of from about 240° Celsius to about 310° Celsius at about 0.5 to about 1 ton per square inch of pressure for from about 1 to about 10 minutes. Then the current collector may be bonded to the so-coated membrane by placing it onto the membrane so it is in contact with the particles and hot pressing the combination at a temperature of between about 240° and about 310° Celsius at a pressure of from about 0.5 to about 1 ton per square inch for from about 1 to about 10 minutes.
The quantity of particles used on the membrane film to form the SPE electrode may vary depending upon the activity of the electrocatalyst, its cost, etc. For chlor-alkali SPE membranes, the amount of catalyst used is usually from about 0.4 to about 1.0 milligrams catalyst/square centimeter of membrane. There is an upper limit on the amount of particles which may be placed onto the membrane because the particles penetrate the membrane. The upper limit has been determined to be about 25 milligrams catalyst / square centimeter of membrane.
Optionally, the electrically conductive particles may be applied to the carbon cloth prior to the carbon cloth being embedded into the membrane sheet. Such a procedure involves preparing the cloth as described in U.S. Pat. No. 4,293,396, Prototech Company (Oct. 6, 1981). The so-prepared cloth can then be bonded to the membrane by contacting and preheating the membrane/cloth pair at a temperature of about 240° Celsius at atmospheric pressure for about 60 seconds, then applying a pressure of about 4-6 tons per square inch at a temperature of about 240° Celsius for about 40-120 seconds, followed by cooling at about 20°-25° Celsius in air.
The solid polymer electrolyte structure of the present invention is useful in a wide variety of electrochemical cells including, for example, fuel cells for the continuous production of electrical energy; electrolysis cells for the production of chemical products; and batteries for the intermittent production of electrical energy. | The invention is a method for forming a solid polymer electrolyte structure comprising:
(a) heating a fluorocarbon membrane, while it is in its thermoplastic form, to a temperature at which it softens;
(b) contacting a plurality of electrically conductive, catalytically active particles with at least a portion of one face of the membrane, while said membrane is in a softened state;
(c) subjecting the membrane/particle combination to a pressure sufficient to embed at least a portion of the particles into the membrane;
(d) contacting the particulated membrane with an electrically conductive, hydraulically permeable matrix,
(e) subjecting the particulated membrane/matrix combination to a pressure sufficient to embed at least a portion of the matrix into the particulated membrane. | 8 |
[0001] This application is a continuation of U.S. application Ser. No. 11/454,405, filed Jun. 16, 2006 (U.S. Pat. No. 7,361,335), which is a continuation of U.S. application Ser. No. 09/669,051, filed Sep. 24, 2000 (U.S. Pat. No. 7,063,838), which claims the benefit of U.S. Provisional Application Ser. No. 60/155,938, filed Sep. 24, 1999, each of which is incorporated by reference herein in its entirety.
STATEMENT REGARDING GOVERNMENT RIGHTS
[0002] This invention was made with government support under grant no. HL07712-07 awarded by the National Institutes of Health. The government has certain rights in the invention.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates to methods of opening obstructed biological conduits. Preferred methods of the invention include methods and systems for opening obstructed biological conduits using local delivery of a therapeutic agent, particularly a protease, to lyse the extracellular matrix of the obstructing tissue.
[0005] 2. Background
[0006] Obstructions to biological conduits frequently result from trauma to the conduit which can result from transplant, graft or other surgical procedures wherein the extracellular matrix of the obstructing tissue largely comprises collagen. Balloon angioplasty is a common initial treatment for stenosis or stricture obstruction that yields excellent initial results (Pauletto, Clinical Science , (1994) 87:467-79). However, this dilation method does not remove the obstructing tissue.
[0007] It only stretches open the lumen, the trauma of which has been associated with the release of several potent cytokines and growth factors that can cause an injury which induces another round of cell proliferation, cell migration toward the lumen and synthesis of more extracellular matrix. Consequently, balloon angioplasty is associated with restenosis in nearly all patients (Pauletto, Clinical Science , (1994) 87:467-79). There is currently no treatment that can sustain patency over the long term.
[0008] The extracellular matrix, which holds a tissue together, is composed primarily of collagen, the major fibrous component of animal extracellular connective tissue (Krane, J. Investigative Dermatology (1982) 79:83s-86s; Shingleton, Biochem. Cell Biol ., (1996) 74:759-75). The collagen molecule has a base unit of three stands of repeating amino acids coiled into a triple helix. These triple helix coils are then woven into a right-handed cable. As the collagen matures, cross-links form between the chains and the collagen becomes progressively more insoluble and resistant to lysis. When properly formed, collagen has a greater tensile strength than steel. Not surprisingly, when the body builds new tissue collagen provides the extracellular structural framework such that the deposition of hard collagen in the lesion can result in duct obstruction.
[0009] Benign biliary stricture results in obstruction of the flow of bile from the liver and can result in jaundice and hepatic dysfunction. If untreated, biliary obstruction can result in hepatic failure and death. Biliary strictures can form after duct injury during cholecystectomy. They can also from at biliary anastomoses after liver transplantation and other biliary reconstructive surgeries (Vitale, Am. J. Surgery (1996) 171:553-7; Lilliemoe, Annals of Surgery (1997) 225).
[0010] Historically, benign biliary stricture has been treated surgically by removing the diseased duct segment and reconnecting the duct end-to-end, or connecting the duct to the bowel via a hepaticojejunostomy loop (Lilliemoe, Annals of Surgery (1997) 225). These long and difficult surgeries have significant morbidity and mortality due to bleeding, infection, biliary leak, and recurrent biliary obstruction at the anastomosis. Post-operative recovery takes weeks to months. More recently, minimally invasive treatments such as percutaneous balloon dilation have been utilized, yielding good initial biliary patency results (Vitale, Am. J. Surgery (1996) 171:553-7, Lilliemoe, Annals of Surgery (1997) 2250). However, balloon dilation causes a localized injury, inducing a healing response that often results in restenosis (Pauletto, Clinical Science , (1994) 87:467-79). Long-term stenting at the common bile duct with flexible biliary drainage catheters is another minimally invasive alternative to surgery (Vitale, Am. J. Surgery (1996) 171:553-7). However, these indwelling biliary drainage catheters often become infected, or clogged with debris, and must be changed frequently. At present, long-term treatment of biliary stricture remains a difficult clinical problem.
[0011] Patients with chronic, end-stage renal failure may require replacement of their kidney function in order to survive. In the United States, long-term hemodialysis is the most common treatment method for end stage chronic renal failure. In 1993, more than 130,000 patients underwent long term hemodialysis (Gaylord, J. Vascular and Interventional Radiology (1993) 4:103-7); more than 80% of these patients implement hemodialysis through the use of a synthetic arteriovenous graft (Windus, Am. J. Kidney Diseases (1993) 21:457-71). In a majority of these patients, the graft consists of a 6 mm Gore-Tex tube that is surgically implanted between an artery and a vein, usually in the forearm or upper arm. This high flow conduit can then be accessed with needles for hemodialysis sessions.
[0012] Nearly all hemodialysis grafts fail, usually within two years, and a new graft must be created surgically to maintain hemodialysis. These patients face repeated interruption of hemodialysis, and multiple hospitalizations for radiological and surgical procedures. Since each surgical graft revision consumes more available vein, eventually they are at risk for mortality from lack of sites for hemodialysis access. One estimate placed the cost of graft placement, hemodialysis, treatment of complications, placement of venous catheters, hospitalization costs, and time away from work at as much as $500 million, in 1990 alone (Windus, Am. J. Kidney Diseases (1993) 21:457-71).
[0013] The most frequent cause of hemodialysis graft failure is thrombosis, which is often due to development of a stenosis in the vein just downstream from the graft-vein anastomosis (Safa, Radiology (1996) 199:653-7. Histologic analysis of the stenosis reveals a firm, pale, relatively homogeneous lesion interposed between the intimal and medial layers of the vein which thickens the vessel wall and narrows the lumen (Swedberg, Circulation (1989) 80:1726-36). This lesion, which has been given the name intimal hyperplasia is composed of vascular smooth muscle cells surrounded by an extensive extracellular collagen matrix (Swedberg, Circulation (1989) 80:1726-36; Trerotola, J. Vascular and Interventional Radiology (1995) 6:387-96). Balloon angioplasty is the most common initial treatment for stenosis of hemodialysis grafts and yields excellent initial patency results (Safa, Radiology (1996) 199:653-7). However, this purely mechanical method of stretching open the stenosis causes an injury which induces another round of cell proliferation, cell migration toward the lumen and synthesis of more extracellular matrix. Consequently, balloon angioplasty is associated with restenosis in nearly all patients (Safa, Radiology (1996) 199:653-7). There is currently no treatment which can sustain the patency of synthetic arteriovenous hemodialysis grafts over the long term.
[0014] Intimal hyperplasia research has focused largely on the cellular component of the lesion. The use of radiation and pharmaceutical agents to inhibit cell proliferation and migration are active areas of research (Hirai, ACTA Radiologica (1996) 37:229-33; Reimers, J. Invasive Cardiology (1998) 10:323-31; Choi, J. Vascular Surgery (1994) 19:125-34). To date, the results of these studies have been equivocal, and none of these new treatments has gained wide clinical acceptance. This matrix is composed predominantly of collagen and previous work in animals has demonstrated that systemic inhibition of collagen synthesis decreases the production of intimal hyperplasia (Choi, Archives of Surgery (1995) 130:257-261).
[0015] During normal tissue growth and remodeling, existing collagen matrices must be removed or modified. This collagen remodeling is carried out by macrophages and fibroblasts, two cell types which secrete a distinct class of proteases called “collagenases” (Swedberg, Circulation (1989) 80:1726-36; Trerotola, J. Vascular and Interventional Radiology (1995) 6:387-96; Hirai, ACTA Radiologica (1996) 37:229-33). These collagenases rapidly degrade insoluble collagen fibrils to small, soluble peptide fragments, which are carried away from the site by the flow of blood and lymph.
[0016] See also U.S. Pat. Nos. 5,981,568; 5,409,926; and 6,074,659.
[0017] It thus would be desirable to provide new methods to relieve obstructions blocking flow through biological conduits.
SUMMARY OF THE INVENTION
[0018] I have now found new methods and systems for relieving an obstruction in a biological conduit, e.g. mammalian vasculature. Methods of the invention include administration to an obstruction site of a therapeutic agent that can preferably degrade (in vivo) the extracellular matrix of the obstructing tissue, particularly collagen and/or elastin. Preferred methods of the invention include administration to an obstruction of an enzyme or a mixture of enzymes that are capable of degrading key extracellular matrix components (including collagen and/or elastin) resulting in the solubilization or other removal of the obstructing tissue.
[0019] Methods and systems of the invention can be applied to a variety of specific therapies. For example, methods of the invention include treatment of biliary stricture with the use of exogenous collagenase, elastase or other agent, whereby an enzyme composition comprising collagenase, elastase or other agent is directly administered to or into (such as by catheter injection) the wall of the lesion or other obstruction. The enzyme(s) dissolves the collagen and/or elastin in the extracellular matrix, resulting in the solubilization of fibrous tissue from the duct wall near the lumen, and a return of duct flow or opening.
[0020] Methods of the invention also include pretreating an obstruction (e.g. in a mammalian duct) with collagenase, elastase or other agent to facilitate dilation such that if treatment under enzymatic degradation conditions alone is insufficient to reopen a conduit, then conventional treatment with e.g. balloon dilation is still an option. It has been found that enzymatic degradation pre-treatment in accordance with the invention can improve the outcome of balloon dilation since enzyme treatment partially digests the collagen fibrils. Therefore, the overall effect will be a softening of the remaining tissue. The softened tissue is more amenable to balloon dilation at lower pressures, resulting in less mechanical trauma to the duct during dilation.
[0021] Preferably, the therapeutic agent is delivered proximately to a targeted site, e.g. by injection, catheter delivery or the like.
[0022] A variety of therapeutic agents may be employed in the methods of the invention. Suitable therapeutic agents for use in the methods and systems of the invention can be readily identified, e.g. simply by testing a candidate agent to determine if it reduces an undesired vasculature obstruction in a mammal, particularly a coronary obstruction in a mammalian heart. Preferred therapeutic agents comprise one or more peptide bonds (i.e a peptidic agent), and typically contain at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 or more amino acids, preferably one or more of the natural amino acids. Preferred therapeutic agents include large molecules, e.g. compounds having a molecular weight of at least about 1,000, 2,000, 5,000 or 10,000 kD, or even at least about 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000 or 100,000 kD.
[0023] Specifically preferred therapeutic agents for use in the methods and systems of the invention include proteases and other enzymes e.g. a collagenase such as Clostridial collagenase, a proteolytic enzyme that dissolves collagen, and/or an elastase such as a pancreatic elastase, a proteolytic enzyme that dissolves elastin. Preferred delivery of collagenase and other therapeutic agents of the invention include directly injecting the agent into the target lesion or other obstruction. Preferably, a homogeneous distribution of a therapeutic enzyme or enzyme mixture is administered to a target site with a drug delivery catheter. The therapeutic agent can then dissolve the key extracellular collagen components necessary to solubilize the obstructing tissue from the vessel wall near the lumen.
[0024] Treatment methods of the invention provide significant advantages over prior treatment methodologies. For example, enzymatic degradation of one or more key components of the extracellular matrix gently removes the tissue obstructing the lumen. Additionally, collagenolysis or other therapeutic administration is relatively atraumatic. Moreover, collagenase also can liberate intact, viable cells from tissue. Therefore, treatment methods of the invention can remove both the source of mechanical obstruction and a source of cytokines and growth factors, which stimulate restenosis.
[0025] A single or combination of more than one distinct therapeutic agents may be administered in a particular therapeutic application. In this regard, a particular treatment protocol can be optimized by selection of an optimal therapeutic agent, or optimal “cocktail” of multiple therapeutic agents. Such optimal agent(s) for a specific treatment method can be readily identified by routine procedures, e.g. testing selected therapeutic agents and combinations thereof in in vivo or in vitro assays.
[0026] In another aspect of the invention, treatment compositions and treatment kits are provided. More particularly, treatment compositions of the invention preferably contain one or more enzymatic agents such as collagenase preferably admixed with a pharmaceutically acceptable carrier. Such compositions can be suitable packaged in conjunction with an appropriate delivery tool such as an injection syringe or a delivery catheter. The delivery device and/or treatment solution are preferably packaged in sterile condition. The delivery device and treatment composition can be packaged separately or in combination, more typically in combination. The delivery device preferably is adapted for in situ, preferably localized, delivery of the therapeutic agent directly into the targeted biological conduit obstruction.
[0027] Typical subjects for treatment in accordance with the invention include mammals, particularly primates, especially humans. Other subjects may be treated in accordance with the invention such as domesticated animals, e.g. pets such as dogs, cats and the like, and horses and livestock animals such as cattle, pigs, sheep and the like. Subjects that may be treated in accordance with the invention include those mammals suffering from or susceptible to biliary stricture including benign biliary stricture, stenosis of hemodialysis graft, intimal hyperplasia, and/or coronary obstruction, and the like. As discussed above, methods of the invention may be administered as a pre-treatment protocol before another therapeutic regime such as a balloon angioplasty; during the course of another therapeutic regime, e.g. where a therapeutic composition of the invention is administered during the course of an angioplasty or other procedure; or after another treatment regime, e.g. where a therapeutic composition of the invention is administered after an angioplasty or administration of other therapeutic agents.
[0028] Other aspects of the invention are disclosed infra.
BRIEF DESCRIPTION OF THE DRAWING
[0029] FIG. 1 shows a common bile duct in a dog with a high grade stricture;
[0030] FIG. 2 shows a common bile duct in a dog with a high grade stricture after treatment;
[0031] FIG. 3 is a histology picture of a normal common bile duct from a dog;
[0032] FIG. 4 is a histology picture of a common bile duct stricture from a dog with a high grade stricture before treatment;
[0033] FIG. 5 is a histology picture of a common bile duct stricture from a dog after treatment with collagenase wherein the arrows denote the outer limit of collagen breakdown; and
[0034] FIG. 6 shows a normal common bile duct in a dog.
DETAILED DESCRIPTION OF THE INVENTION
[0035] The present invention provides methods of introducing a therapeutic agent that is capable of degrading an extracellular matrix component to thereby facilitate the reopening of a constricted biological conduit. In particular, the invention provides for introduction to an obstructed biological conduit of a therapeutic agent that degrades collagen and/or elastin. The present invention further provides methods of dilating a biological conduit by introducing a therapeutic agent into a biological conduit, preferably an isolated segment of the conduit.
[0036] In one embodiment of the present invention, the degradation of a stricture, lesion or other obstruction is accomplished by introducing one or more therapeutic agents that are capable of degrading one or more extracellular matrix components thereby facilitating the reopening of the constricted segment of the conduit. Major structural components of the extracellular matrix include collagen and elastin.
[0037] Preferred therapeutic agents for use in accordance with the invention are able to interact with and degrade either one or both of collagen and elastin.
[0038] As discussed above, a variety of compositions may be used in the methods and systems of the invention. Preferred therapeutic compositions comprise one or more agents that can solubilize or otherwise degrade collagen or elastin in vivo. Suitable therapeutic agents can be readily identified by simple testing, e.g. in vitro testing of a candidate therapeutic compound relative to a control for the ability to solubilize or otherwise degrade collagen or elastin, e.g. at least 10% more than a control.
[0039] More particularly, a candidate therapeutic compound can be identified in the following in vitro assay that includes steps 1) and 2):
[0040] 1) contacting comparable mammalian tissue samples with i) a candidate therapeutic agent and ii) a control (i.e. vehicle carrier without added candidate agent), suitably with a 0.1 mg of the candidate agent contacted to 0.5 ml of the tissue sample; and
[0041] 2) detecting digestion of the tissue sample by the candidate agent relative to the control. Digestion can be suitably assessed e.g. by microscopic analysis. Tissue digestion is suitably carried out in a water bath at 37° C. Fresh pig tendon is suitably employed as a tissue sample. The tissue sample can be excised, trimmed, washed blotted dry and weighed, and individual tendon pieces suspended in 3.58 mg/ml HEPES buffer at neutral pH. See Example 1 which follows for a detailed discussion of this protocol. Such an in vitro protocol that contains steps 1) and 2) is referred to herein as a “standard in vitro tissue digestion assay” or other similar phrase.
[0042] Preferred therapeutic agents for use in accordance with the invention include those that exhibit digestion activity in such a standard in vitro tissue digestion assay at least about 10 percent greater relative to a control, more preferably at least about 20% greater digestion activity relative to a control; still more preferably at least about 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% greater digestion activity relative to a control.
[0043] Appropriate therapeutic agents can comprise at least one and frequently several enzymes such that the therapeutic agent is capable of degrading both significant matrix components of tissue obstruction. Particularly preferable therapeutic agents will comprise either a collagenase or elastase or both. Specifically preferred are therapeutic agents comprising a highly purified, injectable collagenase preparation such as that produced from cultures of Clostridium histolyticum by BioSpecifics Technologies Corporation (Lynbrook, N.Y.). This enzyme preparation is composed of two similar but distinct collagenases. The Clostridial collagenases cleave all forms of collagen at multiple sites along the helix, rapidly converting insoluble collagen fibrils to small, soluble peptides. Also preferable are therapeutic agents comprising elastase, particularly pancreatic elastase, an enzyme capable of degrading elastin. Trypsin inhibitors also can be suitably employed as the therapeutic agent in the methods of the invention.
[0044] In a further aspect of the present invention, the methods further include means to prevent damage to tissue that is not associated with conduit obstruction. Preferred enzymes incorporated in the therapeutic agents are large (>100,000 kD) and diffuse slowly in the extracellular compartment after injection. Further, collagenases comprise a domain (in addition to the active site) which binds tightly to tissue. Consequently, these enzymes remain largely contained within collagen-rich target tissues after injection. Also, the enzyme's activity is quickly extinguished in the blood pool by circulating inhibitors. Therefore, injected collagenase, which diffuses from the interstitial compartment into the blood pool, will be rapidly inhibited, preventing systemic side effects.
[0045] Fragments of therapeutic agents also can be administered to a patient in accordance with the invention. For example, fragments of the above-mentioned collagenases and elastases can be administered to a patient provided such fragments provide the desired therapeutic effect, i.e. degradation of obstruction of a biological conduit. As referred to herein, a collagenase, elastase or other enzyme includes therapeutically effective fragments of such enzymes.
[0046] In certain preferred aspects of the invention, the therapeutic agent(s) that are administered to a patient are other than a cytostatic agent; cytoskeletal inhibitor; an aminoquinazolinone, particularly a 6-aminoquinazolinone; a vascular smooth muscle protein such as antibodies, growth hormones or cytokines.
[0047] In specific embodiments, the degradation of elastin, an extracellular matrix component that contributes to tissue elasticity, is not desirable. Therapeutic agents comprising only enzymes, which do not degrade elastin, such as collagenases, can be employed. Therefore, the elastic properties of the conduit wall will likely be preserved after treatment.
[0048] In a preferred aspect of the invention, a therapeutic agent comprising at least one enzyme capable of degrading elastin, collagen or both is delivered to the targeted obstruction site with a catheter. Preferred catheters are capable of directly localizing a therapeutic agent directly into the extracellular matrix of the obstruction. Particularly preferable catheters are capable of delivering accurate doses of the therapeutic agent with an even distribution over the entire obstructed area of the conduct. One particularly preferred example of a catheter for use in the method of the present invention is the Infiltrator® catheter produced by InterVentional Technologies Corporation (IVT) (San Diego, Calif.), which delivers a precisely controlled dosage of a drug directly into a selected segment of vessel wall ( FIG. 1 ) (Reimers, J. Invasive Cardiology (1998) 10:323-331; Barath, Catheterization and Cardiovascular Diagnosis (1997) 41:333-41; Woessner, Biochem. Cell Biol . (1996) 74: 777-84). Using this preferred catheter a therapeutic agent can be delivered at low pressure via a series of miniaturized injector ports mounted on the balloon surface. When the positioning balloon is inflated, the injector ports extend and enter the vessel wall over the 360° surface of a 15 mm segment of vessel. Each injector port is less than 0.0035 inch in size. Drug delivery can be performed in less than 10 seconds, with microliter precision and minimal immediate drug washout. The injected drug is delivered homogeneously in the wall of the vessel or duct ( FIG. 2 ). The triple lumen design provides independent channels for guidewire advancement, balloon inflation and drug delivery. Trauma associated with injector port penetration is minimal and the long-term histologic effects are negligible (Woessner, Biochem. Cell Biol . (1996) 74: 777-84). In addition, the device has been engineered such that the injector ports are recessed while maneuvering in the vessel. Additionally, the Infiltrator® catheter is capable of balloon inflation with sufficient force for angioplasty applications. The excellent control of drug delivery observed with Infiltrator® can be significant since preferred therapeutic agents of the present invention potentially can degrade collagen and/or elastin in nearly all forms of tissue in a non-specific manner.
[0049] In yet another embodiment of the present invention, a therapeutic dose is employed which will restore conduit flow while maintaining conduit wall integrity. Several parameters need to be defined to maximize method efficiency, including the amount of enzyme to be delivered, and the volume of enzyme solution to be injected so that the reopening of the conduit occurs with a single dose protocol. Ideally repeat or multiple dosing is reserved only for patients who have an incomplete response to the initial injection.
[0050] In regards to the volume of therapeutic agent solution delivered, preferably the conduit wall is not saturated completely, as this can lead to transmural digestion and conduit rupture. Instead, the optimal dose is determined by targeting the thickness of the wall (from the outside in) which needs to be removed in order to restore adequate flow, while leaving the remaining wall intact. An overly dilute solution will be ineffective at collagen lysis while an overly concentrated solution will have a higher diffusion gradient into the surrounding tissues, thereby increasing the risk of transmural digestion and rupture.
[0051] Collagenase doses are generally expressed as “units” of activity, instead of mass units. Individual lots of collagenase are evaluated for enzymatic activity using standardized assays and a specific activity (expressed in units/mg) of the lot is determined. BTC uses an assay that generates “ABC units” of activity. The specific activity of other collagenase preparations are sometimes expressed in the older “Mandel units”. One ABC unit is roughly equivalent to two Mandel units.
[0052] Preferable doses and concentrations of enzyme solution are between 1000 and 20000 ABC units, more preferable are between 2500 and 10000 ABC units and enzyme doses of 5,000 ABC units in 0.5 ml of buffer are most preferred.
[0053] It will be appreciated that actual preferred dosage amounts of other therapeutic agents in a given therapy will vary according to e.g. the specific compound being utilized, the particular composition formulated, the mode of administration and characteristics of the subject, e.g. the species, sex, weight, general health and age of the subject. Optimal administration doses for a given protocol of administration can be readily ascertained by those skilled in the art using dosage determination tests, including those described above and in the examples which follow.
[0054] Therapeutic agents of the invention are suitably administered as a pharmaceutical composition with one or more suitable carriers. Therapeutic agents of the invention are typically formulated in injectable form, e.g. with the therapeutic agent dissolved in a suitable fluid carrier. See the examples which follow for preferred compositions.
[0055] As discussed above, the methods and systems of the invention can be employed to treat (including prophylactic treatment) a variety of diseases and disorders. In particular, methods and systems of the invention can be employed to relieve or otherwise treat a variety of lesions and other obstructions found in common bile ducts or vascular systems. Methods of the invention are also useful to relieve lesions and other obstructions in other biological conduits including e.g. ureterer, pancreatic duct, bronchi, coronary and the like.
[0056] The invention also includes prophylactic-type treatment, e.g. methods to dilate a biological conduit whereby the increased conduit diameter obviates the potential of obstruction formation with a conduit. Temporary and partial degradation of the elastin component of a conduit wall reduces the elasticity of the conduit, thereby facilitating modifications of the size and shape of the conduit. Introducing a dose of therapeutic agent in accordance with the invention into the lumen of an isolated conduit or some section thereof results in complete or partial diffusion of the therapeutic agent into the wall of the isolated conduit during a specified period of time. Subsequent pressurization of the treated region, either while the region is still isolated or after removing the means of isolation, increases the lumen diameter by dilation. Regeneration of the conduit elastin framework results in a conduit with a larger lumen diameter without compromising the structural integrity.
[0057] Arteriovenous hemodialysis grafts are frequently placed in the arm of the patient such that blood can be withdrawn and purified blood returned through the graft. Frequently the lumenal diameter of the venous outflow is smaller than the graft lumenal diameter. Development of a stenosis due to intimal hyperplasia can further reduce the lumenal diameter of the venous outflow such that an insufficient volume of blood passes through the venous outflow. To prevent intimal hyperplasia and stenosis formation, dilating the venous outflow vein using the above described method of partially degrading the elastin component of the vascular wall downstream of the site of graft implantation such that the lumenal diameter of the venous outflow is similar to or larger than the diameter of the interposed loop graft reduces the likelihood of forming a stenosis due to intimal hyperplasia. Venous dilation can be performed either before or after interposing a graft between the artery and vein.
[0058] All documents mentioned herein are incorporated herein by reference. The present invention is further illustrated by the following non-limiting examples.
EXAMPLE 1
Tissue Digestion Analysis
[0059] The protocol of the following example is a detailed description of a “standard in vitro tissue digestion assay” as referred to herein.
[0060] The rate of tissue digestion, which is composed mostly of collagen, by a mixture of collagenase and elastase, proteolytic enzymes with activity respectively against collagen and elastin, was determined. Trypsin inhibitor was added to negate the effect of any residual trypsin activity. Briefly, fresh pig tendon was excised, trimmed, washed, blotted dry and weighed. Individual tendon pieces were suspended in 3.58 mg/ml HEPES buffer at neutral pH and various concentrations of enzymes were added. Iodinated radiographic contrast was added in various concentrations to some of the enzyme solutions. The tissue digestion was carried out in a water bath at 37° C. At various time points, the tendon pieces were removed from the enzyme solution, washed, blotted dry and weighed. Each time point was derived from the average of three samples. The effect of enzyme concentration on tissue digestion rates was studied. As expected, increasing the concentration of enzymes in vitro increased the rate of tissue digestion ( FIG. 3 ). Buffer alone had no effect on the tissue. Extrapolating digestion rates in vitro to an in vivo situation has proven difficult. For Dupuytren's contractures, the effective dose for transecting fibrous cords in vitro was 500 ABC units. However, the effective in vivo dose was 10,000 ABC units.
[0061] The effect of iodinated radiographic contrast material on tissue digestion rates was also studied ( FIG. 4 ). This study was performed to monitor enzyme delivery by mixing it with contrast prior to injection. These results demonstrate that Omnipaque 350 iodinated contrast material inhibits enzyme activity at radiographically visible (35%) concentrations, but not at lower (1-5%) concentrations ( FIG. 4 ). Similar results were observed with Hypaque 60 contrast.
EXAMPLE 2
Determining Dose Dependent In Vitro Activity of a Therapeutic Agent Including Collagenase, Elastase, and a Trypsin Inhibitor
[0062] The effect of enzyme concentration on tissue digestion rates was studied ( FIG. 3 ). The “1×” tissue sample was treated with collagenase 156 Mandel units/ml+elastase 0.125 mg/ml+trypsin inhibitor 0.38 mg/ml. The “2×” sample was treated with collagenase 312 Mandel units/ml+elastase 0.25 mg/ml+trypsin inhibitor 0.76 mg/ml. The “5×” sample was treated with collagenase 780 Mandel units/ml+elastase 0.625 mg/ml+trypsin inhibitor 1.9 mg/ml. All digestion volumes were 0.5 ml. Increasing the concentration of enzymes in vitro increased the rate of tissue digestion ( FIG. 3 ). Buffer alone had no effect on the tissue. An effective in vivo dose was found to be 10,000 ΛBC units.
EXAMPLE 3
Determining the Effect of Iodinated Radiographic Contrast Material on Tissue Digestion Rates to Facilitate Monitoring Enzyme Delivery Prior to Injection of a Therapeutic Agent Comprising a Contrast Material into a Patient
[0063] The “35% Omnipaque” tissue sample was treated with collagenase 156 Mandel units/ml+elastase 0.125 mg/ml+0.38 trypsin inhibitor with 35% Omnipaque 350 contrast (volume:volume). The “5% Omnipaque” sample was treated with collagenase 312 Mandel units/ml+elastase 0.25 mg/ml+0.76 trypsin inhibitor with 5% Omnipaque 350 (volume:volume). The “1% Omnipaque” sample was treated with collagenase 312 Mandel units/ml+elastase 0.25 mg/ml+0.76 trypsin inhibitor with 1% Omnipaque 350. All digestion volumes were 0.5 ml. These results demonstrate that Omnipaque 350 iodinated contrast material inhibits enzyme activity at radiographically visible (35%) concentrations, but not at lower (1-5%) concentrations ( FIG. 4 ). Similar results were observed with Hypaque 60 contrast.
EXAMPLE 4
Creating a Stricture in the Common Bile Duct of Dogs and Treatment of the Resulting Stricture with Transcatheter Intramural Collagenase Therapy
[0064] Right subcostal laparotomy was performed in dogs to expose the gallbladder, which was then affixed to the anterior abdominal wall of 11 dogs (n=11). After 2 weeks, a single focal thermal injury was made in the common bile duct (CBD) using a catheter with an electrocoagulation tip placed through the gallbladder access. A 4.8 Fr biliary stent was placed to prevent complete duct occlusion in 7 animals. Stricture development was monitored with percutaneous cholangiography over five weeks. Collagenase was then directly infused into the wall of the strictured CBD using an Infiltrator drug delivery catheter (n=3). The Infiltrator has three arrays of microinjector needles mounted on a balloon which extend and enter the duct wall over the 360-degree surface. After treatment, internal plastic stents were placed in 2 animals. Explants of the CBD were obtained the following day. H&E, trichrome, and elastin staining were used for histopathologic analysis.
[0065] CBD strictures were successfully created in 7/11 animals as determined by cholangiography ( FIG. 1 ). Failures were due to gallbladder leak (n=2) and perforation at the site of thermal injury (n=2). Histologic analysis of an untreated stricture demonstrated a thickened wall with a circumferential network of collagen bundles and associated lumenal narrowing ( FIG. 4 ). Strictures treated with collagenase demonstrated a circumferential lysis of collagen at the treatment site, with sparing of the normal duct, arteries and veins ( FIGS. 2 and 5 ). All three animals developed bile leaks after treatment, two from the gallbladder access site and one from the treatment site. There was vascular congestion and inflammation in portions of the small bowel mucosa and peritoneum after treatment in all animals, to varying degrees.
EXAMPLE 5
Relief of Strictures in the Common Bile Duct of a Patient
[0066] A large dog was used as the patient such that under general anesthesia a cholecystostomy tract was created and the gallbladder was “tacked” to the abdominal wall with retention sutures. A cholangiogram was performed with Hypaque-60, using a marker catheter, in order to define the anatomy. Then, a flexible catheter with a bipolar electrode tip was constructed as previously described (Becker, Radiology (1988) 167:63-8). This catheter was inserted through the gallbladder ( FIG. 5 ) and positioned with its “hot” tip (arrow) in the distal common bile duct such that the catheter was pulled back and the treatment was repeated until a 1.0 cm length of duct was injured ( FIG. 6 ). Immediately after delivering the current there was a mild-moderate amount of smooth narrowing of the treated segment of duct (arrow), possibly due to spasm or edema. A pigtail nephrostomy drainage catheter was then inserted through the fresh cholecystostomy tract into the gallbladder. The distal end was closed with an IV cap and buried in the subcutaneous tissue. The surgical wounds were then closed in a two-layer fashion.
[0067] After 7 days, a follow-up cholangiogram was performed to evaluate the thermally induced stenosis. A 20 gauge needle was used to percutaneously access the drainage catheter through the IV cap. A cholangiogram was performed demonstrating moderate-marked dilation of the biliary tree ( FIG. 1 ). There was a high-grade stricture of the mid common bile duct, where the thermal injury had been made.
[0068] Strictures are created in five large dogs using the methods described above and in Example 4. In addition, an objective measurement of biliary patency (the Whitaker study) is made of the common bile duct, both before and after making a stricture. The Whitaker study is performed by injecting normal saline through a catheter positioned in the common bile duct. Flow rates are increased and pressure measurements are taken until a peak pressure of 40 mmHg is reached.
[0069] The thermal lesions mature into fibrous strictures over a six week period. One animal is then sacrificed and a histologic assessment is made of the extrahepatic biliary tree. Samples are taken of the duct proximal to the lesion, the mid portion of the lesion ( FIG. 4 ), the lesion edge, and the duct distal to the lesion. Assessments of 1) duct morphology. 2) cell type and number, 3) the extent and appearance of the extracellular matrix, and 4) extent of epithelialization are made. A second animal is sacrificed after an additional 6 weeks after thermal injury and a similar analysis carried out.
[0070] A cholangiogram is performed to visually assess the stricture ( FIG. 1 ) and a Whitaker test is also performed on the remaining 3 dogs. Then, the Infiltrator catheter is then deployed within the lesion and 0.5 mL of collagenase preparation (10,000 Units/ml) is injected into the wall of the lesion. On post-treatment day 1, a follow-up cholangiogram and Whitaker test are performed.
[0071] In cases where incomplete response is noted, a second treatment can be given and a second follow-up cholangiogram and Whitaker test is performed the following day. Hepatic enzyme levels will be drawn to assess the effect of stricture and then treatment on hepatic function. Alternatively, incomplete response from collagenase can be followed up with subsequent angioplasty or a combined collagenase/angioplasty treatment.
[0072] After treatment with collagenase, a final cholangiogram is taken after 1 week ( FIG. 2 ). At this time, the animal is sacrificed and the extrahepatic biliary tree harvested. Histologic assessments are made of the bile duct proximal to the treated lesion, the mid portion of the treated lesion ( FIG. 5 ), the treated lesion edge, and the duct distal to the lesion. Assessments of 1) duct morphology, 2) cell type and number, 3) the extent and appearance of the extracellular matrix, and 4) extent of epithelialization were made. FIG. 5 is a histology image of a common bile duct stricture after treatment. The arrows denote the outer limit of collagen breakdown. The histological examination of the treated common bile duct stricture demonstrates a circumferential lysis of collagen at the treatment site, while sparing damage to the normal duct, arteries and veins.
EXAMPLE 6
Relief of Stenosis Due to Intimal Hyperplasia of a Synthetic Hemodialysis Graft
[0073] Standard, untapered 5 mm diameter polytetrafluoroethylene (PFTE) loop grafts were interposed between the femoral artery and the femoral vein in the hind limbs of 25-35 kg dogs, as described previously (Trerotola, J. Vascular and Interventional Radiology (1995) 6:387-96). An end-to-end configuration had been selected to facilitate optimal positioning of the catheter drug delivery balloon during treatment of a stenosis. Standard, cut-film angiography is performed one week after surgery to assess the arterial inflow, the artery-graft anastomosis, the vein-graft anastomosis, and the venous outflow. After this, routine physical examination of the grafts will be carried out to screen for patency. Twenty weeks after surgery, standard, cut-film angiography is performed to assess the lumenal diameter of the grafts and their venous outflow. At this time, a stenosis due to intimal hyperplasia is seen in the venous outflow with an associated pressure gradient (Trerotola, J. Vascular and Interventional Radiology (1995) 6:387-96). Then, using the first animal, the therapy delivery catheter is deployed within a graft and 5000 ABC units of collagenase in 0.5 ml is infiltrated into the wall of the lesion at the venous outflow. The catheter is flushed and the contralateral lesion receives 1 ml of saline, delivered in an identical manner. Nearly all collagenase activity is extinguished after 1-2 days such that the grafts are re-examined with angiography after 3 days. Repeat measurements of lumenal diameter and invasive pressure measurements across the lesion are also taken. The animals are sacrificed and the grafts excised, pressure-fixed, and examined histologically. Assessments are made of the distal graft, the venous anastomosis, the mid-portion of the treated lesion, the lesion edge, and the normal vein downstream from the graft. Additional assessments of 1) cell type, morphology and number, 2) extent of extracellular matrix, 3) overall adventitial, medial, and intimal thickness, 4) extent of intimal hyperplasia, and 5) extent of endothelialization are made.
EXAMPLE 7
[0074] Four dogs are used for a controlled study of collagenase treatment. Bilateral grafts are created as described previously and standard, cut-film angiography is performed one week after surgery to access the arterial inflow, the artery-graft anastomosis, the vein-graft anastomosis, and the venous outflow. After this, routine physical examination of the grafts is carried out to screen for patency. Then, twenty weeks after surgery, standard, cut-film angiography is performed to assess the lumenal diameter of the grafts and their venous outflow. An obvious stenosis due to intimal hyperplasia is usually seen in the venous outflow with an associated pressure gradient (Trerotola, J. Vascular and Interventional Radiology (1995) 6:387-96). The Infiltrator catheter is then deployed within the lesion and the selected dose of collagenase is infiltrated into the wall of the lesion. The contralateral, control graft is treated in an identical manner, except that saline is delivered instead of collagenase. Three days after treatment, the grafts are restudied with angiography and invasive pressure measurements to determine the acute effects of collagenase treatment. Changes in lumenal diameter and pressure gradients are calculated for both the collagenase-treated group and the saline-treated group and ten days after collagenase treatment, the grafts are studied a final time. The animals are sacrificed and the grafts are excised, pressure-fixed, and examined histologically, as described above.
[0075] The invention has been described in detail with reference to preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of this disclosure, may make modifications and improvements within the spirit and scope of the invention as set forth in the following claims. | The invention provides methods for treating an obstructed biological conduit that include administering to the conduit an agent that can degrade extracellular matrix of obstructing tissue. Particular methods include delivery of an enzyme or a mixture of several enzymes to the area or region of obstruction wherein the enzyme(s) have the capability to degrade extracellular matrix components within the obstruction thereby restoring the normal flow of transported fluid through the conduit. The invention also includes prophylactically dilating a section of conduit to minimize the risk of obstruction formation. | 8 |
This application is a 371 of PCT/US97/01552, filed Jan. 31, 1997.
FIELD OF INVENTION
The present invention relates to pyridines, pyrimidines, pyrazines, pyridazines and triazines, pharmaceutical compositions containing these compounds and their use as endothelin receptor antagonists.
Endothelin (ET) is a highly potent vasoconstrictor peptide synthesized and released by the vascular endothelium. Endothelin exists as three isoforms, ET-1, ET-2 and ET-3. [Unless otherwise stated "endothelin" shall mean any or all of the isoforms of endothelin]. Endothelin has profound effects on the cardiovascular system, and in particular, the coronary, renal and cerebral circulation. Elevated or abnormal release of endothelin is associated with smooth muscle contraction which is involved in the pathogenesis of cardiovascular, cerebrovascular, respiratory and renal pathophysiology. Elevated levels of endothelin have been reported in plasma from patients with essential hypertension, acute myocardial infarction, subarachnoid hemorrhage, atherosclerosis, and patients with uraemia undergoing dialysis.
In vivo, endothelin has pronounced effects on blood pressure and cardiac output. An intravenous bolus injection of ET (0.1 to 3 nmol/kg) in rats causes a transient, dose-related depressor response (lasting 0.5 to 2 minutes) followed by a sustained, dose-dependent rise in arterial blood pressure which can remain elevated for 2 to 3 hours following dosing. Doses above 3 nmol/kg in a rat often prove fatal.
Endothelin appears to produce a preferential effect in the renal vascular bed. It produces a marked, long-lasting decrease in renal blood flow, accompanied by a significant decrease in GFR, urine volume, urinary sodium and potassium excretion. Endothelin produces a sustained antinatriuretic effect, despite significant elevations in atrial natriuretic peptide. Endothelin also stimulates plasma renin activity. These findings suggest that ET is involved in the regulation of renal function and is involved in a variety of renal disorders including acute renal failure, cyclosporine nephrotoxicity, radio contrast induced renal failure and chronic renal failure.
Studies have shown that in vivo, the cerebral vasculature is highly sensitive to both the vasodilator and vasoconstrictor effects of endothelin. Therefore, ET may be an important mediator of cerebral vasospasm, a frequent and often fatal consequence of subarachnoid hemorrhage.
ET also exhibits direct central nervous system effects such as severe apnea and ischemic lesions which suggests that ET may contribute to the development of cerebral infarcts and neuronal death.
ET has also been implicated in myocardial ischemia (Nichols et al. Br. J. Pharm. 99: 597-601, 1989 and Clozel and Clozel, Circ. Res., 65: 1193-1200, 1989) coronary vasospasm (Fukuda et al., Eur. J. Pharm. 165: 301-304, 1989 and Luscher, Circ. 83: 701, 1991) heart failure, proliferation of vascular smooth muscle cells, (Takagi, Biochem & Biophys. Res. Commun.; 168: 537-543, 1990, Bobek et al., Am. J. Physiol. 258:408-C415, 1990) and atherosclerosis, (Nakaki et al., Biochem. & Biophys. Res. Commun. 158: 880-881, 1989, and Lerman et al., New Eng. J. of Med. 325: 997-1001, 1991). Increased levels of endothelin have been shown after coronary balloon angioplasty (Kadel et al., No. 2491 Circ. 82: 627, 1990).
Further, endothelin has been found to be a potent constrictor of isolated mammalian airway tissue including human bronchus (Uchida et al., Eur J. of Pharm. 154: 227-228 1988, LaGente, Clin. Exp. Allergy 20: 343-348, 1990; and Springall et al., Lancet, 337: 697-701, 1991). Endothelin may play a role in the pathogenesis of interstitial pulmonary fibrosis and associated pulmonary hypertension, Glard et al., Third International Conference on Endothelin, 1993, p. 34 and ARDS (Adult Respiratory Distress Syndrome), Sanai et al., Supra, p. 112.
Endothelin has been associated with the induction of hemorrhagic and necrotic damage in the gastric mucosa (Whittle et al., Br. J. Pharm. 95: 1011-1013, 1988); Raynaud's phenomenon, Cinniniello et al., Lancet 337: 114-115, 1991); Crohn's Disease and ulcerative colitis, Munch et al., Lancet, Vol. 339, p. 381; Migraine (Edmeads, Headache, February 1991 p 127); Sepsis (Weitzberg et al., Circ. Shock 33: 222-227, 1991; Pittet et al., Ann. Surg. 213: 262-264, 1991), Cyclosporin-induced renal failure or hypertension (Eur. J. Pharmacol., 180: 191-192, 1990, Kidney Int, 37: 1487-1491, 1990) and endotoxin shock and other endotoxin induced diseases (Biochem. Biophys. Res. Commun., 161: 1220-1227, 1989, Acta Physiol. Scand. 137: 317-318, 1989) and inflammatory skin diseases. (Clin Res. 41:451 and 484, 1993).
Endothelin has also been implicated in preclampsia of pregnancy. Clark et al., Am. J. Obstet. Gynecol. March 1992, p. 962-968; Kamor et al., N. Eng. J. of Med., Nov. 22, 1990, p. 1486-1487; Dekker et al., Eur J. Ob. and Gyn. and Rep. Bio. 40 (1991) 215-220; Schiff et al., Am. J. Ostet. Gynecol. February 1992, p. 624-628; diabetes mellitus, Takahashi et al., Diabetologia (1990) 33:306-310; and acute vascular rejection following kidney transplant, Watschinger et al., Transplantation Vol. 52, No. 4, pp. 743-746.
Endothelin stimulates both bone resorption and anabolism and may have a role in the coupling of bone remodeling. Tatrai et al. Endocrinology, Vol. 131, p. 603-607.
Endothelin has been reported to stimulate the transport of sperm in the uterine cavity, Casey et al., J. Clin. Endo and Metabolism, Vol. 74, No. 1, p. 223-225, therefore endothelin antagonists may be useful as male contraceptives. Endothelin modulates the ovarian/menstrual cycle, Kenegsberg, J. of Clin. Endo. and Met., Vol. 74, No. 1, p. 12, and may also play a role in the regulation of penile vascular tone in man, Lau et al., Asia Pacific J. of Pharm., 1991, 6:287-292 and Tejada et al., J. Amer. Physio. Soc. 1991, H1078-H1085. Endothelin also mediates a potent contraction of human prostatic smooth muscle, Langenstroer et al., J. Urology, Vol. 149, p. 495-499.
Thus, endothelin receptor antagonists would offer a unique approach toward the pharmacotherapy of hypertension, renal failure, ischemia induced renal failure, sepsis-endotoxin induced renal failure, prophylaxis and/or treatment of radio-contrast induced renal failure, acute and chronic cyclosporin induced renal failure, cerebrovascular disease, myocardial ischemia, angina, heart failure, asthma, pulmonary hypertension, pulmonary hypertension secondary to intrinsic pulmonary disease, atherosclerosis, Raynaud's phenomenon, ulcers, sepsis, migraine, glaucoma, endotoxin shock, endotoxin induced multiple organ failure or disseminated intravascular coagulation, cyclosporin-induced renal failure and as an adjunct in angioplasty for prevention of restenosis, diabetes, preclampsia of pregnancy, bone remodeling, kidney transplant, male contraceptives, infertility and priaprism and benign prostatic hypertrophy.
SUMMARY OF THE INVENTION
This invention comprises compounds represented by Formula (I) and pharmaceutical compositions containing these compounds, and their use as endothelin receptor antagonists which are useful in the treatment of a variety of cardiovascular and renal diseases including but not limited to: hypertension, acute and chronic renal failure, cyclosporine induced nephrotoxicity, benign prostatic hypertrophy, pulmonary hypertension, migraine, stroke, cerebrovascular vasospasm, myocardial ischemia, angina, heart failure, atherosclerosis, and as an adjunct in angioplasty for prevention of restenosis.
This invention further constitutes a method for antagonizing endothelin receptors in an animal, including humans, which comprises administering to an animal in need thereof an effective amount of a compound of Formula (I).
DETAILED DESCRIPTION OF THE INVENTION
The compounds of this invention are represented by structural Formula (I): ##STR1## wherein D, E, F and G may be N, or CR 1 provided no more than three are nitrogens;
P is tetrazol-5-yl, CO 2 R 6 or C(O)N(R 6 )S(O) q R 10 ;
R a is independently hydrogen or C 1-6 alkyl;
R 1 is independently hydrogen, Ar or C 1-6 alkyl;
R 2 is Ar, C 1-8 alkyl, C(O)R 14 or ##STR2## R 3 and R 5 are independently R 13 OH, C 1-8 alkoxy, S(O) q R 11 , N(R 6 ) 2 , Br, F, I, Cl, CF 3 , NHCOR 6 R 13 CO 2 R 7 , --X--R 9 --Y or --X(CH 2 ) n R 8 wherein each methylene group within --X(CH 2 ) n R 8 may be unsubstituted or substituted by one or two --(CH 2 ) n Ar groups;
R 4 is independently R 11 , OH, C 1-5 alkoxy, S(O) q R 11 , N(R 6 ) 2 , Br, F, I, Cl or NHCOR 6 , wherein the C 1-5 alkoxy may be unsubstituted or substituted by OH, methoxy or halogen;
R 6 is independently hydrogen or C 1-8 alkyl;
R 7 is independently hydrogen, C 1-10 alkyl, C 2-10 alkenyl or C 2-8 alkynyl, all of which may be unsubstituted or substituted by one or two OH, N(R 6 ) 2 , CO 2 R 12 , halogen or XC 1-10 alkyl; or R 7 is (CH 2 ) n Ar;
R 8 is independently R 11 , CO 2 R 7 , CO 2 C(R 11 ) 2 O(CO)XR 7 , PO 3 (R 7 ) 2 , SO 2 NR 7 R 11 , NR 7 SO 2 R 11 , CONR 7 SO 2 R 11 , SO 3 R 7 , SO 2 R 7 , P(O)(OR 7 )R 7 , CN, CO 2 (CH 2 ) m C(O)N(R 6 ) 2 , C(R 11 ) 2 N(R 7 ) 2 , C(O)N(R 6 ) 2 , NR 7 C(O)NR 7 SO 2 R 11 , tetrazole or OR 6 ;
R 9 is independently a bond, C 1-10 alkylene, C 1-10 alkenylene, C 1-10 alkylidene, C 1-10 alkynylene, all of which may be linear or branched, or phenylene, all of which may be unsubstituted or substituted by one or two OH, N(R 6 ) 2 , COOH or halogen;
R 10 is independently C 1-10 alkyl, N(R 6 ) 2 or Ar;
R 11 is independently hydrogen, Ar, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, all of which may be unsubstituted or substituted by one or two OH, CH 2 OH, N(R 6 ) 2 or halogen;
R 12 is independently hydrogen, C 1-6 alkyl, C 2-6 alkenyl or C 2-7 alkynyl;
R 13 is independently divalent Ar, C 1-10 alkylene, C 1-10 alkylidene, C 2-10 alkenylene, all of which may be unsubstituted or substituted by one or two OH, CH 2 OH, N(R 6 ) 2 or halogen;
R 14 is independently hydrogen, C 1-10 alkyl, XC 1-10 alkyl, Ar or XAr;
R 15 is independently C 1-6 alkyl or phenyl substituted by one or more C 1-6 alkyl, OH, C 1-5 alkoxy, S(O) q R 6 , N(R 6 ) 2 , Br, F, I, Cl, CF 3 or NHCOR 6 ;
X is independently (CH 2 ) n , O, NR 6 or S(O) q ;
Y is independently CH 3 or X(CH 2 ) n Ar;
Ar is independently: ##STR3## naphthyl, furyl, oxozolyl, indolyl, pyridyl, thienyl, oxazolidinyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl, tetrazolyl, imidazolyl, imidazolidinyl, thiazolidinyl, isoxazolyl, oxadiazolyl, thiadiazolyl, morpholinyl, piperidinyl, piperazinyl, pyrrolyl, or pyrimidyl; all of which may be unsubstituted or substituted by one or more Z 1 or Z 2 groups;
A is independently C═O, or (C(R 6 ) 2 ) m ;
B is independently --CH 2 -- or --O--;
Z 1 and Z 2 are independently hydrogen, XR 6 , C 1-8 alkyl, (CH 2 ) q CO 2 R 6 , C(O)N(R 6 ) 2 , CN, (CH 2 ) n OH, NO 2 , F, Cl, Br, I, N(R 6 ) 2 , NHC(O)R 6 , O(CH 2 ) m C(O)NR a SO 2 R 15 , (CH 2 ) m OC(O)NR a SO 2 R 15 , O(CH 2 ) m NR a C(O)NR a SO 2 R 15 , or tetrazolyl which may be substituted or unsubstituted by C 1-6 alkyl, CF 3 or C(O)R 6 ;
Ar' is naphthyl, furyl, oxozolyl, indolyl, pyridyl, thienyl, oxazolidinyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl, tetrazolyl, imidazolyl, imidazolidinyl, thiazolidinyl, isoxazolyl, oxadiazolyl, thiadiazolyl, morpholinyl, piperidinyl, piperazinyl, pyrrolyl, or pyrimidyl; all of which may be unsubstituted or substituted by one or two XR 9 --Y, X(CH 2 ) n R 8 , Z 1 or Z 2 groups;
m is independently 1 to 3;
n is independently 0 to 6;
q is independently 0, 1 or 2;
provided R 3 , R 4 and R 5 are not O--O--(CH 2 ) n Ar;
or a pharmaceutically acceptable salt thereof.
All alkyl, alkenyl, alkynyl and alkoxy groups may be straight or branched.
The compounds of the present invention may contain one or more asymmetric carbon atoms and may exist in racemic and optically active form. All of these compounds and diastereoisomers are contemplated to be within the scope of the present invention.
The preferred compounds are:
E-3-[3-n-Propoxy-4-[(7-carboxy-4-methoxy)naphthyl]pyridyl-5-yl]-2-[(2-methoxy-4,5-methylenedioxyphenyl)methyl]-2-propenoic acid
E-3-[3-n-Propoxy-4-[4-(2-carboxyphenyl)methoxy-2-methoxypyrimidyl]pyridyl-5-yl]-2-[(2-methoxy-4,5-methylenedioxyphenyl)methyl]-2-propenoic acid
E-3-[3-n-Propoxy-4-[1-(2carboxyphenyl)methyl-4-methoxypyrrol]pyridyl-5-yl]-2-[(2-methoxy-4,5-methylenedioxyphenyl)methyl]-2-propenoic acid
E-3-[4-n-Propoxy-5-[4-(2-carboxyphenyl)methoxy-2-methoxypyrimidyl]pyrimidyl-6-yl]-2-[(2-methoxy-4,5-methylenedioxyphenyl)methyl]-2-propenoic acid
The present invention provides compounds of Formula (I). ##STR4## which may be prepared by a process comprising: treating an aryl halide of Formula (2)
Ar'--X (2)
with an appropriate alkyllithium reagent such as n-butyllithium in tetrahydrofuran followed by addition of a borate such as triisopropyl borate and acidic work up affords a boronic acid of Formula (3).
Ar'--B(OH).sub.2 (3)
Reaction of boronic acid of Formula (3) with a compound of Formula (4) ##STR5## wherein X is Halogen in the presence of a suitable base such as potassium carbonate with a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0) in a mixture of toluene, ethanol and water at approximately 80-100° C. provides a compound of Formula (5) ##STR6## A compound of Formula (4) may be prepared from an aryl alcohol of Formula (6) ##STR7## by deprotonation with an appropriate alkyllithium reagent such as s-butyllithium in tetrahydrofuran and subsequent addition of a suitable electrophile such as 1,2-dibromoethane followed by oxidation and alkylation (when Ra=alkyl)
Knoevenagel condensation of an aldehyde of Formula (5) with a half acid of Formula (7) ##STR8## in a solvent such as benzene at reflux, in the presence of piperidium acetate with azeotropic removal of water using a Dean-Stark apparatus, affords an ester of Formula (8). ##STR9## Saponification of an ester of Formula (8) using aqueous sodium hydroxide in a solvent such as ethanol provides, after acidification with aqueous hydrochloric acid, an acid of Formula (1), wherein P═COOH.
In order to use a compound of the Formula (I) or a pharmaceutically acceptable salt thereof for the treatment of humans and other mammals it is normally formulated in accordance with standard pharmaceutical practice as a pharmaceutical composition.
Compounds of Formula (I) and their pharmaceutically acceptable salts may be administered in a standard manner for the treatment of the indicated diseases, for example orally, parenterally, sub-lingually, transdermally, rectally, via inhalation or via buccal administration.
Compounds of Formula (I) and their pharmaceutically acceptable salts which are active when given orally can be formulated as syrups, tablets, capsules and lozenges. A syrup formulation will generally consist of a suspension or solution of the compound or salt in a liquid carrier for example, ethanol, peanut oil, olive oil, glycerine or water with a flavouring or colouring agent. Where the composition is in the form of a tablet, any pharmaceutical carrier routinely used for preparing solid formulations may be used. Examples of such carriers include magnesium stearate, terra alba, talc, gelatin, agar, pectin, acacia, stearic acid, starch, lactose and sucrose. Where the composition is in the form of a capsule, any routine encapsulation is suitable, for example using the aforementioned carriers in a hard gelatin capsule shell. Where the composition is in the form of a soft gelatin shell capsule any pharmaceutical carrier routinely used for preparing dispersions or suspensions may be considered, for example aqueous gums, celluloses, silicates or oils and are incorporated in a soft gelatin capsule shell.
Typical parenteral compositions consist of a solution or suspension of the compound or salt in a sterile aqueous or non-aqueous carrier optionally containing a parenterally acceptable oil, for example polyethylene glycol, polyvinylpyrrolidone, lecithin, arachis oil, or sesame oil.
Typical compositions for inhalation are in the form of a solution, suspension or emulsion that may be administered as a dry powder or in the form of an aerosol using a conventional propellant such as dichlorodifluoromethane or trichlorofluoromethane.
A typical suppository formulation comprises a compound of Formula (1) or a pharmaceutically acceptable salt thereof which is active when administered in this way, with a binding and/or lubricating agent, for example polymeric glycols, gelatins, cocoa-butter or other low melting vegetable waxes or fats or their synthetic analogues.
Typical transdermal formulations comprise a conventional aqueous or non-aqueous vehicle, for example a cream, ointment, lotion or paste or are in the form of a medicated plaster, patch or membrane.
Preferably the composition is in unit dosage form, for example a tablet, capsule or metered aerosol dose, so that the patient may administer to themselves a single dose.
Each dosage unit for oral administration contains suitably from 0.1 mg to 500 mg/Kg, and preferably from 1 mg to 100 mg/Kg, and each dosage unit for parenteral administration contains suitably from 0.1 mg to 100 mg, of a compound of Formula (I) or a pharmaceutically acceptable salt thereof calculated as the free acid. Each dosage unit for intranasal administration contains suitably 1-400 mg and preferably 10 to 200 mg per person. A topical formulation contains suitably 0.01 to 1.0% of a compound of Formula (I).
The daily dosage regimen for oral administration is suitably about 0.01 mg/Kg to 40 mg/Kg, of a compound of Formula (I) or a pharmaceutically acceptable salt thereof calculated as the free acid. The daily dosage regimen for parenteral administration is suitably about 0.001 mg/Kg to 40 mg/Kg, of a compound of the Formula (I) or a pharmaceutically acceptable salt thereof calculated as the free acid. The daily dosage regimen for intranasal administration and oral inhalation is suitably about 10 to about 500 mg/person. The active ingredient may be administered from 1 to 6 times a day, sufficient to exhibit the desired activity.
No unacceptable toxicological effects are expected when compounds of the invention are administered in accordance with the present invention.
The biological activity of the compounds of Formula (I) are demonstrated by the following tests:
I. Binding Assay
A) CHO cell membrane preparation.
CHO cells stably transfected with human ET A and ET B receptors were grown in 245 mm--245 mm tissue culture plates in Dulbecco's modified Eagle's medium supplemented with 10% fetal bovine serum. The confluent cells were washed with Dulbecco's phosphate-buffered saline containing a protease inhibitor cocktail (5 mM EDTA, 0.5 mM PMSF, 5 ug/ml of leupeptin and 0.1 U/ml of aprotinin) and scraped in the same buffer. After centrifugation at 800×g, the cells were lysed by freezing in liquid nitrogen and thawing on ice followed by homogenization (30 times using a glass dounce homogenizer) in lysis buffer containing 20 mM Tris HCI, pH 7.5, and the protease inhibitor cocktail. After an initial centrifugation at 800×g for 10 min to remove unbroken cells and nuclei, the supernatants were centrifuged at 40,000×g for 15 min and the pellet was resuspended in 50 mM Tris HCI, pH 7.5, and 10 mM MgCl 2 and stored in small aliquots at -70° C. after freezing in liquid N 2 . Protein was determined by using the BCA method and BSA as the standard.
(B) Binding studies.
[ 125 I]ET-1 binding to membranes prepared from CHO cells was performed following the procedure of Elshourbagy et al. (1993). Briefly, the assay was initiated in a 100 ul volume by adding 25 ul of [ 125 I]ET-1 (0.2-0.3 nM) in 0.05% BSA to membranes in the absence (total binding) or presence (nonspecific binding) of 100 nM unlabeled ET-1. The concentrations of membrane proteins were 0.5 and 0.05 ug per assay tube for ET A and ET B receptors, respectively. The incubations (30° C., 60 min) were stopped by dilution with cold buffer (20 mM Tris HCI, pH 7.6, and 10 mM MgCl 2 ) and filtering through Whatman GF/C filters (Clifton, N.J.) presoaked in 0.1% BSA. The filters were washed 3 times (5 ml each time) with the same buffer by using a Brandel cell harvester and were counted by using a gamma counter at 75% efficiency.
The following example is illustrative and are not limiting of the compounds of this invention.
EXAMPLE 1
Formulations for pharmaceutical use incorporating compounds of the present invention can be prepared in various forms and with numerous excipients. Examples of such formulations are given below.
Inhalant Formulation
A compound of Formula I, (1 mg to 100 mg) is aerosolized from a metered dose inhaler to deliver the desired amount of drug per use.
______________________________________Tablets/Ingredients Per Tablet______________________________________1. Active ingredient 40 mg (Cpd of Form. I)2. Corn Starch 20 mg3. Alginic acid 20 mg4. Sodium Alginate 20 mg5. Mg stearate 1.3 mg 2.3 mg______________________________________
Procedure for tablets:
Step 1 Blend ingredients No. 1, No. 2, No. 3 and No. 4 in a suitable mixer/blender.
Step 2 Add sufficient water portion-wise to the blend from Step 1 with careful mixing after each addition. Such additions of water and mixing until the mass is of a consistency to permit its conversion to wet granules.
Step 3 The wet mass is converted to granules by passing it through an oscillating granulator using a No. 8 mesh (2.38 mm) screen.
Step 4 The wet granules are then dried in an oven at 140° F. (60° C.) until dry.
Step 5 The dry granules are lubricated with ingredient No. 5.
Step 6 The lubricated granules are compressed on a suitable tablet press.
Parenteral Formulation
A pharmaceutical composition for parenteral administration is prepared by dissolving an appropriate amount of a compound of formula I in polyethylene glycol with heating. This solution is then diluted with water for injections Ph Eur. (to 100 ml). The solution is then steriled by filtration through a 0.22 micron membrane filter and sealed in sterile containers. | Novel pyridines, pyrimidines, pyrazines, pyridazines and triazines, pharmaceutical compositions containing these compounds and their use as endothelin receptor antagonists are described. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved semiconductor device and method for increasing semiconductor device density. In particular, the present invention relates to a device and method utilizing a leads-between-chip leadframe.
2. State of the Art
High performance, low cost, increased miniaturization of components, and greater packaging density of integrated circuits have long been goals of the computer industry. As a general matter, semiconductor substrate assemblies, such as motherboards or function cards to be placed in a motherboard expansion bus slot, comprise a multitude of integrated circuit chips which are coupled to each other in order to make the assembly functional. For example, a central processing unit ("CPU") or microprocessor and a plurality of memory devices or chips may be electrically coupled to each other in order to provide operational control for the semiconductor substrate assembly. Ordinarily, the CPU and the memory devices are proximate to each other on one surface or on opposing surfaces of the motherboard or function card. The terminals of the integrated circuit chips (CPU and memory chips) are coupled to each other by means of circuit traces disposed on or in the motherboard or function card and extending from one individual chip (bare or packaged) to another. However, this standard chip arrangement requires substantial surface area or "real estate" for positioning each integrated circuit chip on the circuit board. Thus, integrated circuit density on a circuit board or other carrier, for any given level of component and internal conductor density, is substantially limited by the space available for die mounting.
In order to maximize real estate utilization, vertical stacking or superimposition of integrated circuit chips or dice has become common practice. U.S. Pat. No. 5,012,323 issued Apr. 30, 1991 to Farnworth ("Farnworth") teaches combining a pair of dice mounted on opposing sides of a leadframe. An upper die is back-bonded to the upper surface of the leads of the leadframe via a first adhesively coated, insulative layer. The lower die is face-bonded to the lower leadframe die-bonding region via a second, adhesively coated, insulative, film layer. The wirebonding pads on both upper and lower dice are interconnected with the ends of their associated lead extensions with gold or aluminum wires. The lower die needs to be slightly larger than the upper die in order that the lower die bonding pads are accessible from above through an aperture in the leadframe, such that gold wire connections can be made to the lead extensions. However, this arrangement has a major disadvantage from a production standpoint, since the different size dice require that different equipment produce the different dice and assemble some with the lead frame or that the same equipment be switched over in different production runs to produce and assemble the different dice and leadframe. Moreover, the leadframe design employed by Farnworth employs long conductor runs between the die and the exterior of the package, and the leadframe configuration is specialized and rather complex.
U.S. Pat. No. 5,291,061 issued Mar. 1, 1994 to Ball ("Ball") teaches a multiple stacked die device that contains up to four dice, which device does not exceed the height of then current single die packages. The low profile of the device is achieved by close-tolerance stacking which is made possible by a low-loop-profile wirebonding operation and thin-adhesive layers between the stack dice. However, Ball secures all of the dice to the same (upper) side of the leadframe, necessarily increasing bond wire length, even if some of the leads are bent upwardly, as disclosed. Moreover, Ball employs a die paddle to support the die stack, a technique which may require an extra die-attach step, and which increases the distance between the inner lead ends and even the lowermost die in the stack, resulting in longer bond wires.
U.S. Pat. No. 5,323,060 issued Jun. 21, 1994 to Fogal et at. ("Fogal") teaches a multichip module that contains stacked die devices, the terminals or bond pads of which are wirebonded to a substrate or to adjacent die devices. However, the stacked configuration of Fogal results in relatively long bond wires and requires a supporting substrate carrying conductor traces.
Each of the stacked die configurations disclosed in the above references uses bond wires which give rise to a common problem of bond wire sweep. When encapsulating a bare die assembly, the die assembly is generally placed in a mold wherein a molten filled-polymer encapsulate material is injected into the mold to surround the die assembly as it conforms to the mold. However, the encapsulant flow front attendant to this process causes stresses on the bond wires. Since the molten capsulating material is viscous, it tends to place forces transverse to at least some of the bond wires as the encasing material is injected into the mold. These directional forces cause the bond wires to flex which can, in turn, cause the bond wires to short with adjacent bond wires or bond pads.
An alternate method for lead attachment in a stacked die arrangement is the "leads over chip" ("LOC") configuration. U.S. Pat. No. 4,862,245 issued Aug. 29, 1989 to Pashby discloses an LOC configuration, wherein the inner lead ends of a standard dual in-line package ("DIP") leadframe configuration extend over and are secured to an upper or active surface of the die through a dielectric layer. The bond wire length is thus shortened by placing the inner lead ends in close proximity to a central row of die bond pads, and the lead extensions purportedly enhance heat transfer from the die. However, the Pashby LOC configuration as disclosed relates to mounting and bonding only a single die.
U.S. Pat. No. 5,438,224 issued Aug. 1, 1995 to Papageorge et al. ("Papageorge") discloses an integrated circuit package with a stacked integrated circuit chip arrangement placed on a circuit substrate. The stacked arrangement comprises a first flip chip and a second flip chip positioned face to face with a substrate interposed between the chips to provide electrical connection among the terminals of the flip chips and external circuitry. However, the Papageorge stacked arrangement uses a TAB or flex circuit substrate between the facing flip chips, and thus requires a separate mechanical support, such as a printed circuit board for the assembly. The design also renders fabrication more difficult due to the lack of rigid support for the chips.
FIG. 1 of the drawings schematically illustrates a typical prior art leadframe 100. The leadframe 100 comprises a plurality of lead fingers 102 and a die-attach paddle 104. The shaded areas 106 are removed in the post-encapsulation trim and form process. FIG. 2 illustrates the leadframe 100 utilized in a wire-bonded bare die assembly 200. Components common to both FIGS. 1 and 2 retain the same numeric designation. The assembly 200 comprises a semiconductor die 202 having a plurality of bond pads 204 on an upper surface 206 of the semiconductor die 202. The semiconductor die 202 is adhered by its back side (not shown) to the leadframe paddle 104 with an appropriate adhesive, such as a solder or an epoxy as known in the art. The semiconductor die 202 achieves an electrical connection with the leadframe 100 with a plurality of bond wires 208 connected between each bond pad 204 and its respective lead finger 102. In wirebonding, a plurality of bond wires are attached, one at a time, to each bond pad on the semiconductor die and extend to a corresponding lead or trace end on the printed circuit board. The bond wires are generally attached through one of three industry-standard wirebonding techniques: ultrasonic bonding--using a combination of pressure and ultrasonic vibration bursts to form a metallurgical cold weld; thermocompression bonding--using a combination of pressure and elevated temperature to form a weld; and thermosopic bonding--using a combination of pressure, elevated temperature, and ultrasonic vibration bursts.
With the wirebonding process, it is possible to attach the lead fingers of a leadframe to bond pads in a variety of locations on a semiconductor die. However, effective bond wire lengths are limited, and wires cannot cross or lie in too-close proximity without shorting. Further, the use of bond wires has the disadvantage of bond sweep when encapsulating a bare die, as discussed above. The problem of bond sweep is exacerbated with longer bond wires, and by bond wires which are too closely spaced. Finally, even automated wire bonding is a time-consuming process in relative terms.
FIG. 3 illustrates one type of prior art LOC-attached, bare die assembly 300. The assembly 300 comprises a semiconductor die 302 having a plurality of bond pads 304 (shown in shadow lines) on an upper surface 306 of a semiconductor die 302. The semiconductor die 302 is electrically connected to a leadframe 308 though a plurality of lead fingers 310 which extend over the die upper surface 306 to directly electrically contact and attach to their respective bond pads 304. TAB or flex circuit-type lead frames are commonly employed for such an assembly. The aforementioned wire-bonded LOC arrangement as illustrated in the Pashby patent is, however, a more common LOC structure.
Therefore, it would be advantageous to develop a technique and assembly for increasing integrated circuit density and eliminating bond sweep using non-customized die configurations in combination with commercially-available, widely-practiced die support structures and semiconductor device fabrication techniques.
SUMMARY OF THE INVENTION
The present invention relates to a device and method for increasing integrated circuit density. The device comprises a pair of superimposed dice with a plurality of leads disposed between the dice. The device is produced by providing a leadframe with variable or non-uniform length, orientation and configuration of lead fingers. The variable lead finger length and configuration leadframe is disposed between the pair of facing, superimposed dice in a variable-leads-between-chips arrangement ("VLBC"). In one preferred embodiment, the VLBC leadframe comprises a paddle and a plurality of lead fingers of a variety of lengths, orientations and configurations. The assembly of the present invention preferably comprises a pair of flip chips (dice) with a plurality of solder or other conductive bumps on an active surface of each flip chip, wherein the flip chips are attached on and in electrical communication with both sides of the VLBC leadframe. This assembly provides a very compact and efficient method of providing multiple dice in the same package using a single VLBC leadframe.
The upper die and the lower die each have a plurality of bond pads on a face side or active surface thereof. The die bond pads can be in any positions or locations across the respective active surfaces. The bond pad patterns of the upper die and the lower die need not match. One advantage of the present invention is that no on-die electrical traces are necessary to route signals to a specific external connection site, such as along an edge of a semiconductor die. Thus, in the present invention, no additional die real estate is taken up by traces routing the signals to specific external connection sites. Furthermore, the steps of designing customized trace routes or forming the routes on the dice are eliminated, thereby reducing the cost of producing the semiconductor die.
In the present invention, the VLBC leadframe achieves the routing of the integrated circuit input and output signals to an appropriate lead. This system is both flexible and cost effective, because the VLBC leadframe design may easily be computer generated. Thus, the VLBC leadframe lead fingers can be quickly rearranged and optimized for specific bond pad patterns using computer software. The customized VLBC leadframe can then be quickly produced by existing computerized leadframe fabrication equipment. Therefore, every change of the dice in the pair and/or every bond pad reconfiguration of one of the dice can be rapidly accommodated without requiring a die redesign to alter on-die traces.
In practice, a passivation layer is preferably disposed between the upper and lower dice and the lead fingers of the VLBC leadframe. The passivation layer is particularly important to prevent potential shorting between the lead fingers and the upper die and/or the lower die under flow front forces imposed upon the assembly during encapsulation, and when a filler material contained within the polymer-based encapsulating material used to encapsulate the assembly has the potential of conducting any significant electric charge or current, or penetrating the on-die passivation layers on the active surfaces of the die.
Furthermore, the paddle of the VLBC leadframe (which need not be configured in a traditional paddle shape) may also be utilized as a signal-bearing lead finger, a power source lead, a common ground, or the like by either or both the upper die and the lower die.
It is, of course, understood that the lead fingers or finger segments do not necessarily have to extend from the bare die package. A lead finger or segment may be designed exchange signal(s) internal to the assembly between the upper die and the lower die.
In a preferred embodiment of the present invention, the upper and lower dice are identical in function, such as a pair of facing 2 Meg VRAMs. Thus, the above discussed arrangement would achieve a 4 Meg VRAM, yielding more memory in a low-profile, small, relatively inexpensive package consuming minimal real estate on the carrier substrate. Alternately, 8 MEG memory may be achieved by using two face-to-face 4 MEG DRAMS while 32 MEG memory may be achieved by using two 16 MEG DRAMS. The present invention is also particularly useful with chips which are staged, such as the output from one microprocessor and cache to another microprocessor and cache, since the conductive paths between the cooperating dice can be considerably shortened.
Although the upper die and the lower die do not have to be identical in size or type, it is preferable that both the upper die and the lower die and other materials of the assembly have compatible coefficients of thermal expansion. Similar coefficients of thermal expansion minimize any stress on the assembly induced by the uneven thermal expansion and contraction of the components.
As noted above, the dice of an assembly can have differing bond pad arrangements. However, when a pair of dice share a single signal, power source or ground, the single lead finger conducting the single signal should, of course, be configured to contact the required bond pad locations on each of the upper dice and the lower dice.
The present invention also has an additional benefit of reducing trace inductance. As semiconductor assemblies become smaller, inductance effects become more significant because the conductive paths become more densely packed and, in stacked die configurations, longer as a result of increasing bond wires lengths from the leadframe or printed circuit board to the elevated dice of the stack. The present invention has the effect of reducing inductance by shortening conductive paths in general when doubling the number of dice in a single space (superimposing the dice), sharing signals on a common conductor where possible, and eliminating wirebonding. Inductance is also substantially reduced between dice where signals are shared internal to the assembly between bond pads on superimposed dice, since only a short lead finger segment is necessary to connect the bond pads of the superimposed dice. In contrast, with prior art single-die packaging, a signal travelled to a companion die through traces on a circuit board or other carrier supporting both dice adjacently.
It is, of course, understood that the present invention is not limited to only superimposing two dice or to only a single die pair in a semiconductor assembly. A multitude of various arrangements with a plurality of dice can be constructed utilizing the concept of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming that which is regarded as the present invention, the advantages of this invention can be more readily ascertained from the following description of the invention when read in conjunction with the accompanying drawings, in which:
FIG. 1 is a top plan view of a prior art leadframe;
FIG. 2 is a top plan view of a prior art wirebonded leadframe semiconductor assembly;
FIG. 3 is a top plan view of a prior art leads over chip semiconductor assembly;
FIG. 4 is a top plan view of a leadframe of the present invention;
FIG. 5 is a side cross-sectional view of a chip assembly of the present invention;
FIG. 6 is a side cross-sectional view of a chip assembly of the present invention illustrating a between chip lead finger;
FIG. 7 is a side cross-sectional view of a multiple chip assembly of the present invention;
FIG. 8 is a side cross-sectional view of a multiple chip assembly of the present invention illustrating a two stacked chip pair with one leadframe assembly; and
FIG. 9 is a side cross-sectional view of a multiple chip assembly of the present invention illustrating a two stacked chip pair with two leadframes assembly.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 4 schematically shows a variable-leads-between-chips ("VLBC") leadframe 400 of the present invention. The VLBC leadframe 400 comprises a "paddle" 402 and a plurality of lead fingers 404 of a variety of shapes and configurations. The shaded leadframe areas 406 are removed in the trim and form process. As noted previously, paddle 402, if employed, may assume a variety of non-traditional shapes, and even extend from one side of the leadframe to another via a zig-zag path as shown in FIG. 4, it being understood that the term "paddle" is one of convenience and does not conform to the requirements of a prior art die-attach paddle, since multiple leads extending within the "footprints" of the dice of the assembly provide the required physical support.
FIG. 5 illustrates a cross sectional view of a die assembly 500 of the present invention. Components common to FIG. 4 and FIG. 5 retain the same numeric designation. The die assembly 500 comprises a pair of superimposed dice, an upper die 502 and a lower die 504, with the plurality of lead fingers 404 and the paddle 402 (as illustrated in FIG. 4) from a leadframe (remainder not shown) disposed between the upper die 502 and the lower die 504. The die assembly 500 is constructed by providing the lower die 504 which has a plurality of bond pads 506 on a face side or active surface 508 thereof. The plurality of lead fingers 404 from the remainder of leadframe (not shown) extends to their respective bond pads 506. The lower die bond pads 506 are attached to a lower surface 510 of the lead fingers 404 with solder bumps, conductive epoxy, a conductor-filled polymer, or other such conductive connective material elements 512, shown here for simplicity in pillar form. The lower die conductive connective material elements 512 can either be located initially (before attachment) on the bond pads 506 or the lead fingers 404. Physical attachment of the lower dice 504 to lead fingers 404 may be enhanced, as known in the art, by use of a screened-on adhesive or of a dielectric tape (such as polyimide) bearing adhesive on both sides. After the lower die 504 has been attached to the lead fingers 404 and paddle 402, a layer of passivation film 514 may be deposited over and between the lead fingers 404 and the lower die face side 508. Film 514 may comprise a polyimide, silicon dioxide, silicon nitride, Baron Phosphorous Silicon Glass (BPSG) or any of various photo-resists known in the art.
The upper die 502, which also carries a plurality of bond pads 516 on a face side or active surface 518, is also provided. The upper die bond pads 516 are attached to an upper surface 522 of the lead fingers 404 with solder bumps, conductive epoxy, conductor-filled polymer, or other such connective conductive material elements 520. The upper die connective conductive material 520 can also either be initially located on the bond pads 506 or the lead fingers 404. However, prior to the attachment of the upper die 502, the passivation film 514 is etched by any known industry technique to form vias (not shown) therein to expose selected areas of the upper surface 522 of the lead fingers 404 when the conductive material elements 520 are initially formed on bond pads 516 on the face side 518 of die 502, or etched to expose the upper die conductive connective material elements 520 when the conductive material elements 520 are initially formed on the lead fingers 404.
Rather than etching the passivation film 514, a selective deposition technique could be employed, such as a silk screen, over the upper surface 522 of the lead fingers 404 when applying the passivation film 514. A photoresist might also be employed, either positive or negative, followed by masking, exposure and development. It is also understood that the upper die 502 and the lower die 504 could be first attached to the lead fingers 404, then the passivation material 514 could be injected between the upper die 502 and the lower die 504, or the assembly dip-coated prior to encapsulation.
Additionally, the paddle 402 may also be utilized as a signal-bearing lead finger, a common power source lead, common ground, or the like by either or both the upper die 502 and the lower die 504. FIG. 5 shows electrical connection of the paddle 402 to a centrally-located upper die bond pad 516 with an upper die conductive connective material element 520. A similar, offset connection might be made to a bond pad 506 of lower die 504 as shown in broken lines so that, for example, both dice might share a common power input through "paddle" 402. Paddle 402 may also extend to the exterior of leadframe 400 at only one location instead of multiple locations as illustrated.
Once the upper die 502 and lower die 504 are adhered to the lead fingers 404, an encapsulant 524 is used to envelope the assembly, usually by transfer-molding techniques as well known in the art.
All of the lead fingers 404 do not necessarily have to extend out of the bare die package. FIGS. 4 and 6 show a lead finger segment 408 which serves only to exchange signal(s) between the upper die 502 and the lower die 504, rather than electrically communicating circuitry external to the assembly. Components common to the FIGS. 4, 5 and 6 retain the same numeric designation. FIG. 6 shows the lead finger segment 408 connected between the upper die bond pad 516 and the lower die bond pad 506 by upper die conductive connective material element 520 and lower die conductive connective material element 512. The lead finger segment 408 is preferably detached near the edge of the bare die assembly in the trim and form process after dice 502 and 504 are assembled to leadframe 400.
The concept of the present invention can also be utilized in a multiple chip assembly including more than two chips. FIG. 7 illustrates a cross-sectional view of a multiple die assembly 700 of the present invention. The multiple die assembly 700 comprises an upper die 702 partially superimposed over a first lower die 704 and a second lower die 706, with a plurality of lead fingers 708 and a paddle 710 from a leadframe (not shown), similar to the leadframe illustrated in FIG. 4, disposed between the upper die 702 and the first lower die 704 and the second die 706. The die assembly 700 is constructed by placing the first lower die 704 and the second lower die 706 face-up in side-by-side relationship. Both the first lower die 704 and the second lower die 706 each have a plurality of bond pads 712, 714 on a face side or active surface 716, 718, respectively. The plurality of lead fingers 708 from the leadframe extends to their respective bond pads 712, 714. The first lower die bond pads 712 and the second lower die bond pads 714 are electrically connected to a lower surface 720 of the lead fingers 708 with solder bumps, conductive epoxy, a conductor-filled polymer or other such conductive connective material elements 722. As shown in broken lines, bond pads of both lower dice are connected to paddle 710, as for a common ground. The lower dice pair conductive connective material elements 722 may either be initially formed and located on the bond pads 712, 714 or the lead fingers 708. After the first lower die 704 and the second lower die 706 have been attached to the lead fingers 708 and/or paddle 710, a layer of passivation material 724 is deposited over and between the lead fingers 708 and the first lower die face side 716 and the second lower die face side 718.
An upper die 702, which also has a plurality of bond pads 726 on a face side or active surface 728, is also provided. The upper die bond pads 726 are attached to an upper surface 730 of the lead fingers 708 with a solder bump, conductive epoxy, a conductor-filled polymer, or other such connective conductive material elements 732. The upper die connective conductive material elements 732 can also either be initially formed on the upper die bond pads 726 or the lead fingers 708. However, prior to the attachment of the upper die 702 to lead fingers 708, the passivation layer 724 is etched by any known industry technique to form vias (not shown) to expose the upper surface 730 of the lead fingers 708 when the upper die conductive material elements 732 are initially formed on the upper die face side 728, or etched to expose the upper die conductive connective material elements 732 when the conductive material elements 732 are initially formed on the lead fingers 708. The assembly is then encased in an encapsulation material 734.
As with the prior embodiment and as depicted in broken lines with respect to lower dice 704 and 706, the paddle 710 may also be utilized as a signal-bearing lead finger, a power source lead, common ground, or the like by the upper die 702, the first lower die 704, and/or the second lower die 706.
FIG. 8 illustrates a cross sectional view of an alternative multiple (four) die assembly 800 of the present invention. The die assembly 800 comprises two pair of superimposed dice, a first dice pair 802 and a second dice pair 804. The first dice pair 802 comprises a first upper die 806 and a first lower die 808, with a first portion of a plurality of lead fingers 810 from a leadframe 811 disposed between the first upper die 806 and the first lower die 808. The first dice pair 802 is constructed in a manner previously discussed, wherein a plurality of bonds pads 818 of an active surface 820 of the first upper die 806 is connected by conductive material elements 822 to their respective lead fingers 810 and a plurality of bonds pads 824 of an active surface 826 of the first lower die 808 is connected by conductive material elements 822 to their respective lead fingers 810.
The second dice pair 804 comprises a second upper die 812 and a second lower die 814, with a second portion of a plurality of lead fingers 816 from leadframe 811 disposed between the second upper die 812 and the second lower die 814. The second dice pair 804 is constructed in a manner previously discussed, wherein a plurality of bonds pads 828 of an active surface 830 of the second upper die 812 is connected by conductive material elements 832 to their respective lead fingers 816 and a plurality of bonds pads 834 of an active surface 836 of the second lower die 814 is connected by conductive material elements 832 to their respective lead fingers 816.
Preferably, a back side 840 of the first lower die 808 is attached to a back side 842 of the second upper die 812 with a layer of adhesive 844 to further stabilize the assembly. An encapsulant 846 is used to encase the assembly.
FIG. 9 illustrates a cross sectional view of another alternative multiple die assembly 900 of the present invention. The multiple die assembly 900 of FIG. 9 is similar to the multiple die assembly 800 of FIG. 8; therefore, components common to FIG. 8 and FIG. 9 retain the same numeric designation. The multiple die assembly 900 differs substantially from the multiple die assembly 800 of FIG. 8 only in the respect that two separate leadframes 901, 903 are used. Thus, a plurality of lead fingers 902 from a first leadframe 901 extends between the first upper die 806 and the first lower die 808 and a plurality of lead fingers 904 from a second leadframe 903 extends between the second upper die 812 and the second lower die 814.
Additionally, a first leadframe paddle 906 may also be utilized as a signal-bearing lead finger, power source lead, common ground, or the like by the first upper die 806 and/or first lower die 808. A second leadframe paddle 908 may also be utilized in similar fashion by the second upper die 812 and/or second lower die 814.
Having thus described in detail preferred embodiments of the present invention, it is to be understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope thereof. | A device and method for increasing integrated circuit density comprising at least a pair of superimposed dice, wherein at least one of the superimposed dice has at least one bond pad variably positioned on an active surface of the die. A plurality of lead fingers from a leadframe extend between the dice. The leadframe comprises at least one lead with leads of non-uniform length and configuration to attach to the differently positioned bond pads of the multiple dice. An advantage of the present invention is that it allows dice with differing bond pad arrangements to be used in a superimposed configuration to increase circuit density, while eliminating the use of bond wires in such a configuration. | 7 |
This is a Rule 60 Divisional of application Ser. No. 08/778,637, filed Jan. 3, 1997, now U.S. Pat. No. 5,726,318, which is a Rule 60 Divisional of application Ser. No. 08/411,690, filed Apr. 5, 1995, now U.S. Pat. No. 5,621,121, filed as PCT/FR93/00969 on Oct. 4, 1993.
DESCRIPTION OF THE INVENTION
The present invention relates to a new process for the preparation of taxane derivatives of general formula: ##STR2## which have notable antileukaemic and antitumour properties.
In the general formula (I), R represents a hydrogen atom or an acetyl radical, R 1 represents a benzoyl radical or a radical R 2 --O--CO-- in which R 2 represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, phenyl or nitrogen-containing heterocyclyl radical, and Ar represents an aryl radical.
More particularly, R represents a hydrogen atom or an acetyl radical and R 1 represents a benzoyl radical or a radical R 2 --O--CO-- in which R 2 represents:
a straight or branched alkyl radical containing 1 to 8 carbon atoms, an alkenyl radical containing 2 to 8 carbon atoms, an alkynyl radical containing 3 to 8 carbon atoms, a cycloalkyl radical containing 3 to 6 carbon atoms, a cycloalkenyl radical containing 4 to 6 carbon atoms or a bicycloalkyl radical containing 7 to 10 carbon atoms, these radicals optionally being substituted by one or a number of substituents chosen from the halogen atoms and the hydroxyl radical, alkyloxy radical containing 1 to 4 carbon atoms, dialkylamino radical, each alkyl part of which contains 1 to 4 carbon atoms, piperidino radical, morpholino radical, 1-piperazinyl radical (optionally substituted in the 4-position by an alkyl radical containing 1 to 4 carbon atoms or by a phenylalkyl radical, the alkyl part of which contains 1 to 4 carbon atoms), cycloalkyl radical containing 3 to 6 carbon atoms, cycloalkenyl radical containing 4 to 6 carbon atoms, phenyl radical, cyano radical, carboxyl radical or alkyloxycarbonyl radical, the alkyl part of which contains 1 to 4 carbon atoms,
or a phenyl radical optionally substituted by one or a number of atoms or radicals chosen from the alkyl radicals containing 1 to 4 carbon atoms or the alkyloxy radicals containing 1 to 4 carbon atoms,
or a saturated or unsaturated nitrogen-containing heterocyclyl radical containing 5 or 6 members, optionally substituted by one or a number of alkyl radicals containing 1 to 4 carbon atoms, it being understood that the cycloalkyl, cycloalkenyl or bicycloalkyl radicals may optionally be substituted by one or a number of alkyl radicals containing 1 to 4 carbon atoms, and Ar represents a phenyl or α- or β-naphthyl radical optionally substituted by one or a number of atoms or radicals chosen from the halogen atoms (fluorine, chlorine, bromine or iodine) and the alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkoxy, alkylthio, aryloxy, arylthio, hydroxyl, hydroxyalkyl, mercapto, formyl, acyl, acylamino, aroylamino, alkoxycarbonylamino, amino, alkylamino, dialkylamino, carboxyl, alkoxycarbonyl, carbamoyl, dialkylcarbamoyl, cyano and trifluoromethyl radicals, it being understood that the alkyl radicals and the alkyl portions of the other radicals contain 1 to 4 carbon atoms, that the alkenyl and alkynyl radicals contain 3 to 8 carbon atoms and the aryl radicals are phenyl or α- or β-naphthyl radicals.
The products of general formula (I) in which R represents a hydrogen atom or an acetyl radical, R 1 represents a benzoyl or t-butoxycarbonylamino radical and Ar represents a phenyl radical are very particularly advantageous.
The products of general formula (I) in which R 1 represents a benzoyl radical correspond to taxol and to 10-deacetyltaxol and the products of general formula (I) in which R 1 represents a t-butoxycarbonyl radical correspond to those which form the subject of European Patent EP 0,253,738.
According to the process which is described in International Application PCT WO 92/09589, the derivatives of general formula (I) can be obtained by:
condensation of a derivative of the oxazolidine of general formula: ##STR3## in which Ar is defined as above, Boc represents the t-butoxycarbonyl radical and R' 2 and R' 3 , which are identical or different, represent an alkyl radical containing 1 to 4 carbon atoms, optionally substituted by one or a number of aryl radicals, or an aryl radical, or else R' 2 and R' 3 form, together with the carbon atom to which they are bonded, a ring having from 4 to 7 members, with the protected baccatin III or 10-deacetylbaccatin (III of general formula: ##STR4## in which G 1 represents a protective group of the hydroxyl functional group and G 2 represents an acetyl radical or a protective group of the hydroxyl functional group, to produce a product of general formula: ##STR5## in which Ar, R' 2 , R' 3 , G 1 , G 2 and Boc are defined as above,
treatment in acidic medium of the product of general formula (IV) under conditions which are without effect on G 1 and G 2 to produce the product of general formula: ##STR6## in which Ar, G 1 and G 2 are as defined above, treatment of the product of general formula (V) with a reagent suitable for introducing a radical R 1 , that is to say a benzoyl or R 2 --O--CO-- radical, to produce a product of general formula: ##STR7## in which Ar, R 1 , G 1 and G 2 are defined as above, and replacement of the protective groups G 1 and G 2 of the product of general formula (VI) by hydrogen atoms to produce the product of general formula (I).
It has now been found, and it is this which forms the subject of the present invention, that the products of general formula (I) can be obtained:
1) by esterifying the protected baccatin III or 10-deacetylbaccatin III of general formula (III), in which G 1 and optionally G 2 represent a protective group of the hydroxyl functional group, using an acid of general formula: ##STR8## in which Ar is defined as above, R 3 represents a trihalomethyl, preferably trichloromethyl, radical or a phenyl radical substituted by a trihalomethyl, preferably trichloromethyl, radical, or of a derivative of this acid, and R 4 represents a hydrogen atom or is identical to R 1 defined as above, to produce a product of general formula: ##STR9## in which Ar, R 3 , R 4 , G 1 and G 2 are defined as above, 2) by replacing protective groups of the hydroxyl and amino functional groups of the product of general formula (VIII) by hydrogen atoms to produce the product of formula: ##STR10## 3) by treating the product obtained of general formula (IX) with a reagent which makes it possible to introduce a substituent R 1 onto the amino functional group to produce a product of general formula (I).
According to the present invention, estorification of the protected baccatin III or of the protected 10-deacetylbaccatin III of general formula (III) with an acid of general formula (VII), in which R 4 preferably represents a hydrogen atom, can be carried out in the presence of a condensation agent such as a diimide, such as dicyclohexylcarbodiimide, or a reactive carbonate such as di-2-pyridyl ketone and of an activating agent such as an aminopyridine, such as 4-dimethylaminopyridine or 4-pyrrolidinopyridine, the reaction being carried out in an organic solvent chosen from ethers such as tetrahydrofuran, diisopropyl ether, methyl t-butyl ether or dioxane, ketones such as methyl isobutyl ketone, esters such as ethyl acetate, isopropyl acetate or n-butyl acetate, nitriles such as acetonitrile, aliphatic hydrocarbons such as pentane, hexane or heptane, halogenated aliphatic hydrocarbons such as dichloromethane or 1,2-dichloroethane and aromatic hydrocarbons such as benzene, toluene, xylenes, ethylbenzene, isopropylbenzene or chlorobenzene, at a temperature between -10° and 90° C. It is particularly advantageous to carry out the esterification in an aromatic hydrocarbon at a temperature in the region of 20° C.
The esterification can also be carried out by using the acid of general formula (VII) in the anhydride form of general formula: ##STR11## in which Ar, R 3 and R 4 are defined as above, in the presence of an activating agent such as an amino-pyridine, such as 4-dimethylaminopyridine or 4-pyrrolidinopyridine, the reaction being carried out in an organic solvent chosen from ethers such as tetrahydrofuran, diisopropyl ether, methyl t-butyl ether or dioxane, ketones such as methyl isobutyl ketone, esters such as ethyl acetate, isopropyl acetate or n-butyl acetate, nitriles such as acetonitrile, aliphatic hydrocarbons such as pentane, hexane or heptane, halogenated aliphatic hydrocarbons such as dichloromethane or 1,2-dichloroethane and aromatic hydrocarbons such as benzene, toluene, xylenes, ethylbenzene, isopropylbenzene or chlorobenzene, at a temperature between 0° and 90° C.
The esterification can also be carried out by using the acid of general formula (VII) in the halide form or mixed anhydride form of general formula: ##STR12## in which Ar, R 3 and R 4 are defined as above, R 4 preferably representing a hydrogen atom, and X represents a halogen atom or an acyloxy or aroyloxy radical, optionally prepared in situ, in the presence of a base which is preferably a nitrogenous organic base such as a tertiary aliphatic amine, a pyridine or an aminopyridine such as 4-dimethylaminopyridine or 4-pyrrolidinopyridine, the reaction being carried out in an inert organic solvent chosen from ethers such as tetrahydrofuran, diisopropyl ether, methyl t-butyl ether or dioxane, ketones such as methyl t-butyl ketone, esters such as ethyl acetate, isopropyl acetate or n-butyl acetate, nitriles such as acetonitrile, aliphatic hydrocarbons such as pentane, hexane or heptane, halogenated aliphatic hydrocarbons such as dichloromethane or 1,2-dichloroethane and aromatic hydrocarbons such as benzene, toluene, xylenes, ethylbenzene, isopropylbenzene or chlorobenzene, at a temperature between 10° and 80° C., preferably in the region of 20° C.
Preferably, an activated derivative of general formula (XI) is used in which X represents a halogen atom or an acyloxy radical containing 1 to 5 carbon atoms or an aryloxy radical in which the aryl part is a phenyl radical optionally substituted by 1 to 5 atoms or radicals, which are identical or different, chosen from halogen atoms (chlorine, bromine) and nitro, methyl or methoxy radicals.
Replacement by hydrogen atoms of the protective groups of the hydroxyl and amino functional groups of the product of general formula (VIII), in which, preferably, G 1 and optionally G 2 represent a 2,2,2-trichloroethoxycarbonyl or 2-(2-(trichloromethyl)propoxy)carbonyl radical, is generally carried out by treatment with zinc, optionally in combination with copper, in the presence of acetic acid at a temperature between 20° and 60° C. or using an inorganic or organic acid, such as hydrochloric acid or acetic acid in solution in an aliphatic alcohol containing 1 to 3 carbon atoms or in an aliphatic ester (ethyl acetate, isopropyl acetate, n-butyl acetate) in the presence of zinc, optionally in combination with copper.
Replacement of the protective groups of the product of general formula (VIII) by hydrogen atoms can also be carried out by electrolytic reduction.
The introduction of a substituent R 1 onto the amino functional group of the product of general formula (IX) is carried out by reacting with benzoyl chloride or with the reactive derivative of general formula:
R.sub.2 --O--CO--Y (XII)
in which R 2 is defined as above and Y represents a halogen atom or a residue --O--R 2 or --O--CO--R 2 , the reaction being carried out in an organic solvent such as an aliphatic ester, such as ethyl acetate, or an alcohol, such as methanol, ethanol, isopropanol or n-butanol, or a halogenated aliphatic hydrocarbon, such as dichloromethane, in the presence of an inorganic or organic base, such as sodium bicarbonate. Generally, the reaction is carried out at a temperature between 0° and 50° C., preferably in the region of 20° C.
The acid of general formula (VII) can be obtained by saponification in basic medium of the ester of general formula: ##STR13## in which Ar, R 1 and R 4 are defined as above and R 5 represents an alkyl radical containing 1 to 4 carbon atoms optionally substituted by a phenyl radical.
Generally, the saponification is carried out using an inorganic base such as an alkali metal hydroxide (lithium, potassium, sodium) or an alkali metal carbonate or bicarbonate (sodium bicarbonate, potassium carbonate or potassium bicarbonate) in aqueous/alcohol medium, such as a methanol/water mixture, at a temperature between 10° and 40° C., preferably in the region of 20° C.
The ester of general formula (XIII) can be obtained by reacting an aldehyde of general formula:
R.sub.3 --CHO (XIV)
in which R 3 is defined as above, optionally in the form of a dialkyl acetal, with a phenylisoserine derivative of general formula: ##STR14## in which Ar, R 4 and R 5 are defined as above, in the racemic form or, preferably, in the 2R,3S form, the reaction being carried out in an inert organic solvent in the presence of a strong inorganic acid, such as sulphuric acid, or organic acid, such as p-toluenesulphonic acid, optionally in the pyridinium salt form, at a temperature between 0° C. and the boiling temperature of the reaction mixture. Solvents which are particularly well suited are aromatic hydrocarbons.
The product of general formula (XV) can be prepared under the conditions described or by adaptation of the methods described in International Application PCT WO 92/09589.
The anhydride of general formula (X) can be obtained by reacting a dehydrating agent, such as dicyclohexylcarbodiimide, with the acid of general formula (VII), the reaction being carried out in an organic solvent chosen from ethers, such as tetrahydrofuran, diisopropyl ether, methyl t-butyl ether or dioxane, ketones such as methyl isobutyl ketone, esters such as ethyl acetate, isopropyl acetate or n-butyl acetate, nitriles such as acetonitrile, aliphatic hydrocarbons such as pentane, hexane or heptane, halogenated aliphatic hydrocarbons such as dichloromethane-or 1,2-dichloroethane, and aromatic hydrocarbons such as benzene, toluene, xylenes, ethylbenzene, isopropylbenzene or chlorobenzene, at a temperature between 0° and 30° C.
The activated acid of general formula (XI) can be obtained by reacting a sulphuryl halide, preferably the chloride, or a product of general formula:
R.sub.6 --CO--Z (XVI)
in which R 6 represents an alkyl radical containing 1 to 4 carbon atoms or a phenyl radical optionally substituted by 1 to 5 atoms or radicals, which are identical or different, chosen from halogen atoms and nitro, methyl or methoxy radicals and Z represents a halogen atom, preferably a chlorine atom, with an acid of general formula (VII), the reaction being carried out in a suitable organic solvent, such as tetrahydrofuran, in the presence of an organic base, such as a tertiary amine such as triethylamine, at a temperature between 0° and 30° C.
EXAMPLES
The following example illustrates the present invention.
Example
0.21 g of dicyclohexylcarbodiimide is added, at a temperature in the region of 20° C., to a solution of 0.33 g of (4S,5R)-4-phenyl-2-trichloromethyl-1,3-oxazolidine-5-carboxylic acid, of 0.49 g of 4-acetoxy-2α-benzoyloxy-5β, 20-epoxy-1,13α-dihydroxy-9-oxo-7β,10β-bis(2,2,2-trichloroethoxy)carbonyloxy-11-taxene and of 0.013 g of 4-dimethylaminopyridine in 2.77 cm 3 of anhydrous toluene. The solution is stirred at 25° C. for 2-3 hours and the dicyclohexylurea formed is then filtered through a sintered glass. The precipitate is rinsed with 20 cm 3 of ethyl acetate and the organic phase is washed successively with 20 cm 3 of a molar aqueous hydrochloric acid solution, 20 cm 3 of a saturated aqueous sodium bicarbonate solution and 10 cm 3 of a saturated aqueous sodium chloride solution. The organic phase is dried over sodium sulphate and concentrated to dryness under reduced pressure to give 0.78 g of crude product which is purified by filtration through 20 g of silica gel, the eluent being an ethyl acetate/n-hexane (v/v=4/6) mixture. After concentrating to dryness under reduced pressure, there is obtained 0.70 g of 4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1-hydroxy-9-oxo-7β,10.beta.-bis(2,2,2-trichloroethoxy)carbonyloxy-11-taxene-13α-yl (4R, 5S)-4-phenyl-2-trichloromethyl-1,3-oxazolidine-5-carboxylate in the form of a mixture of two diastereoisomers whose characteristics are the following:
infrared spectrum (as a pellet with KBr): main characteristic absorption bands at 1760, 1730, 1600, 1585, 1490, 1450, 1250, 1065, 980, 810, 760, 725-700 cm -1
proton nuclear magnetic resonance spectrum (400 MHz; CDCl 3 ; chemical shifts δ in ppm; coupling constants J in Hz) (mixture of diastereoisomers in the proportions 70/30); 1.15 to 1.30 (mt, 6H), 1.84 (s, 1H), 1.86 (s, 1H), 2.07 (s, 1H), 2.00 to 2.10 (mt, 1H), 2.15 (s, 1H), 2.10 to 2.30 (mt, 2H), 2.55 to 2.70 (mt, 1H), 3.20 (large unresolved peak, 1H), 3.32 (large unresolved peak, 1H), 3.87 (d, J=7, 1H), 3.94 (d, J=7, 1H), 4.10 (d, J=8, 1H), 4.13 (d, J=8, 1H), 4.27 (d, J=8, 1H), 4.30 (d, J=8, 1H), 4.58 (d, J=7.5, 1H), 4.61 (d, J=12, 1H), 4.63 (d, J=12, 1H), 4.70 (d, J=8, 1H), 4.80 (AB, 2H), 4.80 (mt, 1H), 4.85 to 5.00 (mt, 2H), 5.13 (d, J=7.5, 1H), 5.53 (broad s, 1H), 5.56 (dd, J=11 and 7, 1H), 5.60 (dd, J=11 and 7, 1H), 5.66 (d, J=7, 1H), 5.68 (d, J=7, 1H), 6.20 to 6.35 (mt, 1H), 6.24 (s, 1H), 6.27 (s, 1H), 7.30 to 7.50 (mt, 3H), 7.30 to 7.70 (mt, 3H), 7.60 (d, 2H), 8.03 (d, J=7.5, 2H).
0.27 g of zinc powder and 1.07 cm 3 of acetic acid are added to a solution of 0.50 g of 4-acetoxy-2α-benzoyoxy-5β,20-epoxy-1-hydroxy-9-oxo-7β, 10β-bis(2,2,2-trichloroethoxy)carbonyloxy-11-taxen-13α-yl (4S,5R)-4-phenyl-2-trichloromethyl-1,3-oxazolidine-5-carboxylate in 5 cm 3 of ethyl acetate. The solution is stirred at a temperature in the region of 20° C. for 15 hours and then filtered through a sintered glass. The precipitate is washed with ethyl acetate (20 cm 3 ) and the organic phase is washed successively with water (15 cm 3 ) and with a saturated aqueous sodium bicarbonate solution (2 times 15 cm 3 ) and then dried over sodium sulphate. The solution is then concentrated to dryness under reduced pressure at 35° C. to give 0.33 g of an amorphous solid. Quantitative determination by high performance liquid chromatography shows that 4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β, 10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-amino-3-phenyl-2-hydroxypropionate, assaying at 50%, is obtained with a yield of 65%.
The characteristics of the product obtained are the following:
proton nuclear magnetic resonance spectrum (400 MHz; d 6 -DMSO; chemical shifts δ in ppm; coupling constants J in Hz): 0.99 (s, 3H), 1.03 (s , 3H), 1.53 (s, 3H), 1.65 (mt, 1H), 1.75 (s, 3H), 1.70 to 1.90 (mt, 2H), 2.12 (s, 3H), 2.28 (mt, 1H), 3.65 (d, J=7, 1H), 4.02 (AB, J=8, 2H), 4.00 to 4.15 (mt, 3H), 4.56 (s, 1H), 4.90 (broad d, J=10, 1H), 4.99 (broad s, 1H), 5.05 (large unresolved peak, 1H), 5.10 (s, 1H), 5.42 (d, J=7, 1H), 5.88 (t, J=9, 1H), 7.15 to 7.45 (mt, 5H), 7.65 (t, J=7.5, 2H), 7.73 (t, J=7.5, 1H), 7.98 (d, J=7.5, 2H).
0.11 g of di-tert-butyl dicarbonate is added to a solution of 0.30 g of crude 4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-amino-3-phenyl-2-hydroxypropionate, obtained above, in 5 cm 3 of methanol. The reaction mixture is stirred at a temperature in the region of 20° C. for 15 hours, and then 20 cm 3 of water are added. The solution is extracted three times with 15 cm 3 of methylene chloride. The combined organic phases are dried over sodium sulphate and then concentrated to dryness under reduced pressure. 0.395 g of crude product is thus obtained. Quantitative determination by high performance liquid chromatography shows that the 4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-phenyl-2-hydroxypropionate yield is 70%.
(4S,5R)-4-Phenyl-2-trichloromethyl-1,3-oxazolidine-5-carboxylic acid can be prepared in the following way:
A solution of 3.0 g of methyl (2R,3S)-3-(tert-butoxycarbonylamino)-2-hydroxy-3-phenylpropionate, of 5 cm 3 of chloral and of 0.05 g of pyridinium p-toluenesulphonate in 40 cm 3 of anhydrous toluene is heated at reflux with distillation of the solvent. 15 cm 3 of solvent are distilled and then 5 cm 3 of chloral and 0.05 g of pyridinium p-toluenesulphonate are added. 20 cm 3 of solvent are distilled and then 5 cm 3 of chloral as well as 30 cm 3 of anhydrous toluene are added. 25 cm 3 of solvent are distilled and 5 cm 3 of chloral and 35 cm 3 of anhydrous toluene are added. 25 cm 3 of solvent are distilled and then the solution is cooled to a temperature in the region of 20° C. The organic solution is washed with water (2 times 50 cm 3 ), dried over sodium sulphate and concentrated to dryness under reduced pressure at approximately 50° C. The residue obtained is purified by liquid chromatography on silica gel, the eluent being an ethyl acetate/cyclohexane (1/3 by volume) mixture. There are thus obtained, with a yield of 91%, 3.0 g of (4S,5R)-5-methoxycarbonyl-4-phenyl-2-trichloromethyl-1,3-oxazolidine whose characteristics are the following:
infrared spectrum (CCl 4 ): characteristic absorption bands at 3400, 3100, 3075, 3040, 2960, 1755, 1605, 1590, 1495, 1460, 1440, 1205 and 700 cm -1
proton nuclear magnetic resonance spectrum (200 MHz; d 6 -DMSO; chemical shifts δ in ppm; coupling constants J in Hz) (mixture of diastereoisomers in the proportion 65/35): 3.62 (s, 3H), 3.72 (s, 3H), 4.50 (d, J=7.5 1H), 4.50 to 4.70 (large unresolved peak, 1H), 4.62 (broad d, J=7.5, 1H), 4.66 (limit AB, 2H), 5.22 (large unresolved peak, 1H), 5.40 (s, 1H), 5.43 (s, 1H), 7.30 to 7.70 (mt, 5H).
A solution of 1.49 g of lithium hydroxide monohydrate in 40 cm 3 of water is added to a solution of 10.48 g of (4S,5R)-5-methoxycarbonyl-4-phenyl-2-trichloromethyl-1,3-oxazolidine in 120 cm 3 of methanol. The solution is stirred at a temperature in the region of 20° C. for 1 hour and the methanol is then evaporated under reduced pressure at 40° C. The residual aqueous phase is then acidified with 35 cm 3 of 1M aqueous hydrochloric acid solution. 80 cm 3 of ethyl acetate are then added with vigorous stirring. The aqueous phase is withdrawn and extracted again with 80 cm 3 of ethyl acetate. The organic phases are combined, dried over sodium sulphate and concentrated to dryness under reduced pressure. The residue obtained is dried overnight at reduced pressure at a temperature in the region of 20° C. There are thus obtained 10.03 g of (4S,5R)-4-phenyl-2-trichloromethyl-1,3-oxazolidine-5-carboxylic acid whose characteristics are the following:
infrared spectrum (CHBr 3 ): characteristic bands at 3380, 3325-2240, 1730, 1600, 1495, 1455, 810 and 760 cm -1
proton nuclear magnetic resonance spectrum (200 MHz; d 6 -DMSO; chemical shifts δ in ppm; coupling constants J in Hz): 4.39 (d, J=7.5, 1H), 4.40 to 4.70 (mt, 2H), 5.13 (mt, 1H), 5.37 (s, 1H), 5.41 (s, 1H), 7.10 to 7.60 (mt, 5H).
Although the invention has been described in conjunction with specific embodiments, it is evident that many alternatives and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, the invention is intended to embrace all of the alternatives and variations that fall within the spirit and scope of the appended claims. The above references are hereby incorporated by reference. | This invention relates to a method of preparing taxane derivatives of formula (VIII) by esterification of protected baccatin III or 10-deacetylbaccatin III by means of an acid of formula (VII), elimination of protection groupings and acylation of the amine function of the side chain. In formulae (VIII) and (VII): Ar stands for aryl, R 3 is a trihalomethyl radical or phenyl substituted by a trihalomethyl radical, R 4 is a hydrogen atom or is the same as R 1 . G 1 and G 2 are hydroxy protecting groups. ##STR1## | 2 |
The invention relates to a nonwoven fabric that has the appearance of apertured, ribbed terry cloth, and to a process and apparatus for producing it.
BACKGROUND OF THE INVENTION
The fluid rearrangement and entangling of fibers to produce nonwoven fabrics has been commercially practiced for many years. See for instance, Kalwaites, U.S. Pat. Nos. 2,862,251 and 3,033,721; Griswold et al., U.S. Pat. No. 3,081,500; Evans, U.S. Pat. No. 3,485,706; and Bunting et al., U.S. Pat. No. 3,493,462. This basic technology has been used to produce a wide variety of nonwoven fabrics. The present invention utilizes fluid rearrangement and entanglement to provide a novel nonwoven fabric having the appearance of ribbed terry cloth, by carrying out the fluid rearrangement/entanglement on a particular type of carrier belt.
SUMMARY OF THE INVENTION
The nonwoven fabric provided by the invention is characterized by a repeating pattern of spaced, parallel, raised ribs which extend continuously in one fabric direction, with the ribs being interconnected by spaced bundles of straight, substantially parallel fiber segments, with said bundles being substantially parallel to one another and substantially perpendicular to said ribs. Adjacent bundles and the ribs they interconnect form apertures. The fibers in the ribs are almost wholly entangled throughout. On the macroscopic scale when viewing the fabric as a whole, the ribs are uniform and substantially non-patterned.
The fabric of the invention is produced by a process which comprises:
(a) supporting a layer of fibrous starting material whose individual fibers are in mechanical engagement with one another but which are capable of movement under applied liquid forces, on a liquid pervious support member adapted to move in a predetermined direction and on which fiber movement in directions both in and at an angle to the plane of said layer is permitted in response to applied liquid forces, said support member having alternating liquid impervious deflecting zones and liquid pervious entangling zones extending transversely to said predetermined direction, said deflecting zones including spaced deflecting means adapted to deflect liquid in a direction transverse to said predetermined direction;
(b) moving the supported layer in said predetermined direction through a fiber rearranging zone within which streams of high pressure, fine, essentially columnar jets of liquid are projected directly onto said layer; and
(c) passing said stream of liquid through said layer and said support member in said fiber rearranging zone to effect movement of fibers such that (1) spaced bundles of straight, substantially parallel fiber segments are formed in said deflecting zones, said bundles being oriented generally in said predetermined direction, (2) spaced, parallel ribs are formed in said entangling zones, said ribs extending in a direction transverse to said predetermined direction, and said ribs comprising entangled fibers that are substantially wholly entangled throughout said ribs, and (3) said spaced bundles interconnect said ribs and are locked into said ribs at the ends of said bundles by fiber entanglement.
The apparatus for producing the fabric of the invention comprises:
(a) liquid pervious forming means for supporting a layer of fibrous starting material whose individual fibers are in mechanical engagement with one another but which are capable of movement under applied liquid forces;
(b) means for projecting streams of high pressure, fine, essentially columnar jets of liquid; and
(c) means for passing said layer of fibrous starting material directly under said streams while said layer is supported on said liquid pervious forming means,
wherein said liquid pervious forming means comprises a woven belt having first fine threads in one fabric direction, and heavier threads and second fine threads in the other fabric direction, the belt having a topography such that there are raised parallel ridges alternating with depressions, wherein each raised ridge comprises one of said heavier threads, wherein said first fine threads pass over said heavier threads at spaced intervals, and wherein said depressions include said first fine threads interlaced with said second fine threads. The belt is relatively tightly woven so that the fibers in said layer will not tend to wash through the belt and so that the ribs which form in the depressions are non-apertured and, at least macroscopically, are substantially uniform and substantially non-patterned.
THE PRIOR ART
In Evans et al., U.S. Pat. No. 3,498,874, there is disclosed entangled nonwoven fabrics produced by fluid rearrangement/entanglement on a woven carrier belt having heavier wires in one direction and three to five times as many finer wires in the other direction. The fabrics produced by Evans et al. bear a certain resemblance to the fabrics of this invention, but differ therefrom in at least the following respects
(a) The ribs of the fabrics of this invention appear macroscopically to be uniform and non-patterned. This does not appear to be the case with the majority of the Evans et al. fabrics, as evidenced by FIGS. 19, 20, and 30 of Evans et al. The fabrics shown in these photographs appear to have the fiber bands "cut into" by the apertures between the connecting bundles of fibers, which gives the longitudinal edges of the bands a serrated effect. FIG. 5 of Evans et al. shows a fabric wherein the fiber bands may appear macroscopically to be uniform (it is difficult to determine this feature from this photograph), but the photomacrographs of the fabric of FIG. 5, shown in Evans et al. as FIGS. 6 and 8, show the fiber bands to have a definite and conspicuous patterned appearance;
(b) The ribs of the fabric of this invention are almost wholly entangled, whereas the bands of the Evans et al. fabric contain an interstitial array of generally parallelized (i.e. unentangled) fibers; and
(c) The interconnecting bundles of fibers in the fabric of this invention are straight and are almost wholly unentangled. Many of the interconnecting bundles in the Evans et al. fabric are curved (e.g., see FIGS. 6-11, and 14-18), and in some of the other Evans et al. fabrics the interconnecting bundles appear to contain substantial fiber entanglement (e.g., see FIGS. 21, 27, 29, and 31-35). There are some of the Evans et al. fabrics wherein the interconnecting bundles seem to be straight and substantially unentangled (e.g., FIG. 23), but with those fabrics there are other substantial contrasting characteristics when compared with the fabrics of this invention.
Evans et al., in U.S. Pat. No. 3,468,168, disclose nonwoven fabrics produced by rearranging/entangling fibers on a patterning member having a topography of parallel ridges alternating with depressions.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side elevation of an arrangement of apparatus that can be used to carry out the process of the invention;
FIG. 2 is a photograph of the fabric of Example 1, the original photograph showing the fabric at about actual size;
FIGS. 3-7 are photomacrographs of the fabric of FIG. 2, originally taken at about 10X, with the views differing from one another as follows.
FIG. 3--a view of the top side, illuminated from below;
FIG. 4--a view of the belt side, illuminated from below, and focused on the interconnecting bundles;
FIG. 5--a view similar to FIG. 4, but focused on the ribs;
FIG. 6--a view of the top side, illuminated from the top; and
FIG. 7--a view of the belt side, illuminated from the top.
FIG. 8 is a photograph of the fabric of Example 2, the original photograph showing the fabric at about actual size.
FIGS. 9-13 are photomacrographs of the fabric of FIG. 8, originally taken at about 10X, with the views differing from one another as follows.
FIG. 9--a view of the top side, illuminated from below;
FIG. 10--a view of the belt side, illuminated from below, and focused on the interconnecting bundles;
FIG. 11--a view of the belt side, illuminated from below, and focused on the ribs;
FIG. 12--a view of the top side, illuminated from above; and
FIG. 13--a view of the belt side, illuminated from above.
FIGS. 14 and 15 are photomacrographs of the top and bottom sides of the forming or carrier belt used in producing the fabric of Example 2;
FIGS. 16-18 are schematic cross-sections through four successive warps of the forming belts used in Examples 1, 2, and 3 respectively;
FIGS. 19-22 are photomacrographs taken 10X of the fabric of Example 3(a), with the views differing from one another as follows
FIG. 19--A view of the top side, illuminated from above;
FIG. 20--A view of the belt side, illuminated from below;
FIG. 21--A view of the top side, illuminated from below; and
FIG. 22--A view of the belt side, illuminated from below.
FIGS. 23-26 are photomacrographs taken at 10X of the fabric of Example 3(b), with the views differing from one another as follows
FIG. 23--A view of the top side, illuminated from above;
FIG. 24--A view of the belt side illuminated from above;
FIG. 25--A view of the top side, illuminated from below; and
FIG. 26--A view of the belt side, illuminated from below.
FIGS. 27-30 are photomacrographs taken at 10X of the fabric of Example 3(c), with the views differing from one another as follows
FIG. 26--A view of the top side, illuminated from above;
FIG. 28--A view of the belt side, illuminated from above;
FIG. 29--A view of the top side, illuminated from below; and
FIG. 30--A view of the belt side, illuminated from below.
DETAILED DESCRIPTION OF THE INVENTION
The nonwoven fabric of this invention is produced by the fluid rearrangement/entanglement of a web comprising a loose array of fibers, on a liquid pervious woven forming belt of special construction which is described fully construction which is described fully below. For instance referring first to FIG. 1 a carded or randon laid web 10 of staple fibers can be passed onto an endless belt 12, which is the said woven forming belt. The belt 12 carries the web of fibers 10 under a series of high pressure fine, essentially columnar jets of water 14. The high pressure water is supplied from a manifold 16. The jets 14 are arranged in rows disposed transversely across the path of travel of the forming belt 12. Preferably, there is a vacuum slot (not shown) pulling a vacuum of, e.g., 5 to 15 inches of mercury, beneath the forming belt 12, directly under each row of jets 14, in order to optimize durability of the fabric product. The fibers in the web 10 are rearranged and entangled by the jets 14 as the liquid from the jets 14 passes through the fibrous web 10 and then through the belt 12, to form the fabric 18 of the invention. The fabric 18 is carried by the belt 12 over a vacuum dewatering station 20, and then proceeds to a series of drying cans 22, and from there to a windup 24.
Evans, in U.S. Pat. No. 3,485,706, describes a process and apparatus for rearranging/entangling fibrous webs by carrying such webs on a woven belt under a series of high pressure, fine, columnar jets of liquid. The disclosure of Evans of incorporated herein by reference.
The invention can use a wide variety of staple fibers, including rayon, polyester, nylon, polypropylene, bicomponent fibers, cotton, and the like, including mixtures thereof. Staple fibers are used, that is, fibers having lengths of up to about three inches. The belt speeds, water jet pressures, and number of rows of jets have not been found to be narrowly critical. Representative conditions are the following:
Belt speed: about 30 to 300 feet/minute
Jet pressure: about 500 to 2000 psi
Rows of jets: about 12 to 100
Carded or random laid webs can be used. Typical web weights are from about 11/2 to about 6 ounces per square yard.
As a general rule the heavier webs use slower belt speed and/or higher jet pressure and/or more rows of jets. Also, in order to achieve maximum durability of the heavier fabrics (e.g., fabrics weighing about 3 ounces or more per square yard), sequential entangling is often desirable.
"Sequential entangling" refers to the practice of first rearranging/entangling a web having a basis weight of a fraction (e.g., about one-half) of that of the final product, and without removing the rearranged/entangled web from the forming belt, adding another web of fibers on top of the first and subjecting the combined layers to the rearranging/entangling step. Sequential entangling is illustrated in the examples.
The principal novelty in the process and apparatus of the invention resides in the use of the special forming belt. An illustration of such a belt is shown in FIGS. 14 and 15. The belt is woven from fine warp monofilaments 36, which extend in the direction of travel of the belt, and fill monofilaments of two different sizes, a heavier fill monofilament 38 and finer fill monofilaments 34. The belt is woven in such a manner that the topography of the top surface of the belt, that is, the surface which the fibers will contact, has raised parallel ridges alternating with depressions. The raised ridges are formed by the heavier fill monofilaments 38. At spaced intervals along said heavier fill monofilaments 38, fine warp monofilaments 36 pass over the heavier fill monofilaments 38. The weave of the forming belt is such that at least two and up to four (with the belt shown, there are three) of the warp monofilaments 36 pass under each heavier fill monofilament 38 between each warp monofilament 36 that passes over the heavier fill monofilament 38. Therefore, the intervals between said fine wrap monofilaments 36 that pass over the heavier fill monofilaments 38 will usually vary from about two to about four diameters of the fine warp monofilaments 36. In said depressions, warp filaments 36 are interlaced with fine fill monofilaments 34, to provide a relatively tightly closed, but still liquid pervious, zone.
In the Examples, below, three different forming belts were used. Their description is as follows:
Forming Belt A--80 warps ends per inch by 26 picks per inch. Schematic cross-sections through four successive warps 40a, 40b, 40c, 40d are shown in FIG. 16. The pattern repeats after four warps. The warps were 0.01 inch polyester monofilaments, and the two different sized filling threads were 0.04 inch 42 and 0.016 inch 44 polyester monofilaments.
Forming Belt B--(Shown in FIGS. 14 and 15)--80 warp ends per inch by 24 picks per inch. Schematic cross-sections through four successive warps 46a, 46b, 46c, 46d are shown in FIG. 17. The pattern repeats after four warps. Warp--0.016 inch polyester monofilaments; fill--0.08 inch nylon 48 and 0.016 inch polyester 50 monofilaments.
Forming Belt C--60 warp ends per inch by 22 picks per inch. Schematic cross-sections through four successive warps 52a, 52b, 52c, 52d are shown in FIG. 18. The pattern repeats after four warps. Warp--0.016 inch polyester monofilaments; fill--0.04 inch 54 and 0.01 inch 56 polyester monofilaments.
EXAMPLE 1
Avtex SN1913 1.5 denier, 11/8 inch staple rayon was processed through an opener blender and fed to a random air laying unit which deposited a 2-ounce web of random formed fibers on the forming belt. The forming belt used was Forming Belt A. The web was passed under a water weir to wet the fiber and then processed under five manifolds, each manifold containing three orifice strips. The orifice strips contained a row of holes, 50 holes per inch, of 0.005 inch diameter, through which the water jetted. Under the manifolds, the web was exposed to water jets operating at the following pressures:
1st manifold 450 psig
2nd manifold 1000 psig
3rd manifold 1000 psig
4th manifold 1200 psig
5th manifold 1200 psig
Under the forming belt, directly under the row of holes in each orifice strip, there was located a series of vacuum slots. Each slot was 1/4-inch wide and pulled a vacuum of about 13 to 14 inches of mercury. The entangled web was dewatered and another 2 ounce web of the same rayon was added on top. The entangled web was not removed from the forming belt, but stayed in registry with it. The combined webs were processed under the same conditions as defined above.
The entire process was operated at 10 yards per minute.
The completed entangled fabric was dried over two stacks of steam cans operating at 60 lbs. and 80 lbs. steam, respectively, and was then rolled up.
EXAMPLE 2
This sample was processed from the same material and under the exact same conditions as Example 1. The only difference was the forming belt, which in this example was Forming Belt B.
EXAMPLE 3
Three samples were made using Forming Belt C. The rayon fiber described in Example 1 was used. The equipment described in Example 1 was used, except that only four manifolds were used. The manifold pressures were the following:
1st manifold 450 psig
2nd manifold 800 psig
3rd manifold 1300 psig
4th manifold 1300 psig
The line speed was 10 yards per minute. The steam cans were operated at 300° F. The three fabrics differed in grain weight, as follows.
A. 900 grains per square yard.
B. 1300 grains per square yard.
C. 2200 grains per square yard.
Samples A and B were each produced in a single pass. Sample C was produced by sequential entangling of two 1100 grain webs, as described in Example 1. With Samples A and B, the vacuum pulled on the slots beneath the rows of jets was about 7 to 8 inches of mercury. With Sample C, the vacuum was about 13 to 14 inches of mercury.
The fabrics prepared in Examples 1, 2 and 3 are shown in FIGS. 2-13 and 19-30. Referring first to FIGS. 2 and 8, the repeating pattern of raised, spaced, parallel ribs 26 interconnected by spaced bundles 28 of fibers is clearly visible. Viewed on this macroscopic scale, the ribs are seen to be uniform and substantially non-patterned. (By "substantially non-patterned" is meant that the only departure from a smooth, straight, uniform appearance is the presence of small, inconspicuous surface indentations on the belt side, as are seen in the ribs 26 in FIGS. 2 and 8. The "belt side" is the side of the fabric that is next to the forming belt during the rearrangement/entanglement step.)
The ribs 26 are almost wholly entangled. This can be seen best in FIGS. 6, 7, 12, 13, 19, 20, 23, 24, 27 and 28. That is, unlike the case with the bands in the fabrics of Evans et al. (U.S. Pat. No. 3,498,874), there appears to be no interstitial array of generally parallelized (i.e., unentangled) fibers.
The interconnecting bundles 28 are almost wholly unentangled. This is best seen in FIGS. 4, 7, 10, 22, and 19-30. Adjacent interconnecting bundles 28 and the ribs 26 which they interconnect form apertures 27 that are substantially congruent, that is, the apertures 27 in any given fabric of the invention are all about the same size and shape when viewed macroscopically.
The bands in the fabrics of Evans et al. (U.S. Pat. No. 3,498,874) exhibit a simple zig-zag pattern when viewed by transmitted light. To the extent that a pattern in the ribs is visible when the fabrics of this invention are viewed by transmitted light, such a pattern is much more complex than a simple zig-zag pattern. This is illustrated in FIGS. 4 and 5 as 30, and FIGS. 11 and 12 as 32, and with these two fabrics (Examples 1 and 2), no pattern was visible when viewing the other side.
The interconnecting bundles 28 are formed in the process of the invention in the intervals between the warp monofilaments 36 (see FIG. 14) that pass over the heavier fill monofilaments 38. The jets of liquid 14 (FIG. 1) strike these warp monofilamants 36 and are deflected transversely to first "wash" the fibers into the said intervals. The fibers are then oriented in a direction parallel to the warp monofilaments 36 by the action of the liquid as it is also deflected by the heavier fill monofilaments 38 in a direction generally parallel to the warp monofilaments 36. The spaces between the heavier fill monofilaments 38 are relatively free of significant raised deflecting means. As a result, the ribs 26 which form in these spaces are substantially wholly entangled throughout. This is a point of significant distinction over Evans et al., U.S. Pat. No. 3,498,874, wherein the finer wires that pass over the heavier wires have the effect of deflecting the entangling liquid laterally in the depressions between the heavier wires to cause the formation of Evans et al's "interstitial arrays of generally parallelized fibers." The Evans et al. "zig-zag pattern" of entangled fibers forms in the spaces between said finer wires. With the present invention, the ribs lack this interstitial array of generally parallelized (i.e., unentangled) fibers because of the substantial absence of any significant raised deflecting means in the depressions or spaces between the heavier fill monofilaments 38. Such raised deflecting means would cause the rearranging fibers to "wash over" the means and form parallelized fiber segments in the same way that the bundles 28 are formed over the heavier fill monofilaments 38. | A nonwoven fabric which has the appearance of apertured, ribbed terry cloth is produced by fluid entangling of fibers on a special forming belt. | 3 |
FIELD OF THE INVENTION
The invention relates to the field of ceiling and wall fixtures.
BACKGROUND OF THE INVENTION
Various types of ceiling and wall treatments such as stucco, paneling, tin ceiling tiles and drop ceilings are known in the art.
What is needed and provided by the present invention are new types of ceiling and wall fixtures.
SUMMARY OF THE INVENTION
One embodiment provides a lattice-configured fixture panel having an expansive horizontal dimension with a top side and a bottom side and a vertical height, said panel including:
a plurality of rods each having a first and second end and a length,
wherein at least some of the rods have different lengths,
wherein each rod is directly joined to at least two other rods,
wherein the intersection of rods in the horizontal dimensions occurs at a plurality of acute and obtuse angles. At least half of the rods, such as at least 80% or all of the rods, of the panel may be tilted such that their first ends and second ends are disposed at different vertical heights. The expansive horizontal dimension of the panel may have an at least substantially rectangular configuration with four sides and the vertical height of the panel may be at least 5-10 times, such as 6-8 times, smaller than the longest of the four sides of the substantially rectangular configuration. The fixture may further include a plurality of wire-hanging support brackets attached to the top side of the panel.
Another embodiment of the invention provides an automated manufacturing system for producing lattice-configured panel fixtures that includes:
a rod support jig comprising an expansive base and a plurality of rod support tabs extending upwardly from the base to predetermined heights at predetermined positions;
a computerized manufacturing control unit comprising at least one processor, processor-accessible tangible memory and processor-executable computer instructions stored in the processor-accessible memory;
a first articulated robot arm under control of the at least one processor, said arm comprising a grabbing tool; and
a second articulated robot arm under control of the at least one processor, said arm comprising a joining tool;
wherein the computer instructions are configured to direct the at least one processor to control the first and second robot arms to perform an ordered plurality of steps including placing rods of predetermined lengths in the jig and joining the rods together according to a predetermined pattern to form a lattice-configured panel fixture.
A related embodiment of the invention provides an automated method for manufacturing lattice-configured panel fixtures that includes the steps of:
providing a manufacturing system that includes:
a rod support jig comprising an expansive base and a plurality of rod support tabs extending upwardly from the base to predetermined heights at predetermined positions,
a computerized manufacturing control unit comprising at least one processor, processor-accessible tangible memory and processor-executable computer instructions stored in the processor-accessible memory,
a first articulated robot arm under control of the at least one processor, said arm comprising a grabbing tool, and
a second articulated robot arm under control of the at least one processor, said arm comprising a joining tool,
wherein the computer instructions are configured to direct the at least one processor to control the first and second robot arms to perform an ordered plurality of steps including placing rods of predetermined lengths in the jig and joining the rods together according to a predetermined pattern to form a lattice-configured panel fixture; and
the first and second robot arms placing rods of predetermined lengths in the jig and joining the rods together under control of the at least one processor according to a predetermined pattern and order to form the lattice-configured panel fixture. Each rod may be joined to at least two other rods to form the fixture.
The method may further include the steps of:
providing a plurality of support brackets for joining to some of the rods; and
joining the plurality of support brackets to different predetermined rods of the fixture panel at predetermined positions on the different predetermined rods. The joining of the brackets to the rods may be performed by the first and second robot arms.
Other objects and advantages of this invention will become apparent from the following description taken in conjunction with any accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of this invention. Any drawings contained herein 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
FIG. 1A shows a top plan view of a lattice-configured modular panel embodiment of the invention. FIG. 1B shows a side elevational view of the embodiment shown in FIG. 1A .
FIG. 2A is a density diagram in the horizontal plane (expansive dimension) for the embodiment shown in FIGS. 1A and 1B . FIG. 2B is a density diagram in the vertical plane for the embodiment shown in FIGS. 1A and 1B .
FIG. 3A shows the rectangular envelope and peripheral overlap zones for the modular panel embodiment shown in FIG. 1A . FIG. 3B shows a side elevational view of the embodiment.
FIG. 4A shows a perspective view of a hanger bracket attached to a rod and connected to a support wire. FIG. 4B shows a side view of the hanging hardware in more detail. FIG. 4C shows how a lattice-configured panel embodiment of the invention may be hung from four points.
FIG. 5 shows an embodiment of the invention that includes an array of six lattice-configured panel fixtures.
FIG. 6 shows an embodiment of an automated rod picking system including a rod storage rack and a robotic picking arm, which may be employed in the manufacture of lattice-configured panel fixtures according to the invention.
FIG. 7 shows a manufacturing system embodiment of the invention that includes a rod placement jig, a robotic picking/placing arm, a robotic welding arm and a partially constructed lattice-configured panel fixture.
FIG. 8 illustrates the stacking order of rods for the manufacture of a panel fixture embodiment of the invention.
FIG. 9 is table showing the lengths of rods in one panel embodiment of the invention.
FIG. 10A is a key diagram enumerating the four sides of the panel embodiment shown in FIG. 1A . Each of FIGS. 10B-10E shows an elevational view of one of the four sides. FIG. 10B shows side 1 , FIG. 10C shows side 2 , FIG. 10D shows side 3 , and FIG. 10E shows side 4 .
DETAILED DESCRIPTION OF THE INVENTION
The invention provides lattice-configured panel fixtures for ceilings and walls that are made of a plurality of rod elements joined to each other. The invention also provides automated systems and methods for manufacturing the fixtures.
The rod elements may, for example, be solid, hollow or tubular and may be metallic, such as but not limited to aluminum, or non-metallic, such as a synthetic polymer or wood. The cross-sectional profile of the rods may, for example, be oval, circular, rectangular, square, triangular or any shape. For a single panel fixture or group of panel fixtures, all of the rods may have the same cross-sectional shapes or a plurality of different shaped rods may be used. At least some of the rods in a single panel fixture may have different cross-sectional dimensions (different diameters) or they may all have the same cross-sectional dimensions (same diameters). Each panel fixture may be made from a plurality of rods wherein at least some of the rods, such as all of the rods, have different lengths. For example, each panel fixture may be made of rods having 2, 3, 4, 5, 6, 7, or 8 different lengths. For all of the different length rods used to make a panel fixture, at least two of the rods of each length may be included in the panel fixture.
The rods are arranged and joined in a three-dimensional lattice configuration having an expansive dimension and a thickness or height to provide the form of a panel. For each panel fixture, each component rod may touch (be joined to) at least one other rod via weldment or other fastening method (glue, fastener, etc.), creating the structural integrity of the module. In another variation, each of the rods may touch (be joined to) at least two, such as two or three, other rods of the module.
At least some of the rods may be straight such as all of the rods may be straight (as shown in the figures). In a variation, none of the rods in a single panel fixture are collinear. In a variation, none of the rods may be at a right angle to a rod it touches (is joined to). In a variation, none of the rods in a panel may be at a right angle to each other. At least some of the rods may be curved, such as all of the rods may be curved. With respect to the height (thickness) of the panel, at least some of the rods of the panel may be axially tilted in the z-plane (rather than level). The total number of rods in a panel may, for example, be in the range of 5-50, such as 5-35, such as 10-30, such as 10-20, such as 10-15. In one embodiment, for a panel having a 48″×48″ border, the rods may vary in length from 12 inches to 60 inches. In one variation, none of the rods in the panel are the same length. FIG. 9 is a table showing the rods lengths for a panel embodiment of the invention.
The entire grouping of rods in a panel may be contained within a rectilinear profile, such as a rectangular or square profile (of the expansive dimension) with varying heights possible in the z-plane envelope. The ratio of the longest dimension in the expansive plane to the height (thickness) of the panel may, for example, be in the range of 40:1 to 4:1. In one embodiment, the panel fixture has an approximate 48″L×48″W area in the expansive plane with varying heights of z plane envelope achieving a maximum of approximately 12″.
When viewed from above or below, the projection of the expansive dimension of a panel embodiment of the invention may, for example, have in the range of 60%-90% open area (area not blocked by the projection of area taken up by the rods). In the expansive dimension, the panel may, for example, consist of 50-120 open areas bounded by the projection of the rods making up the panel. The density of the rods in the area of the expansive dimension of a panel may be significantly less than the density of the rods viewed from the side of the panel.
There may, for example, be 2 to 4 attachments points on the same side of a panel fixture for hanging or otherwise attaching the panel to a ceiling or wall. A tab, i.e., a hanging plate, configured to reversibly attach to a support wire may be connected to a rod of the panel at each of the attachment points. A slot and/or hole may be formed in the tab which is configured to receive a ball end of a wire or other wire connection to a hole or hook in the tab. The other end of the wire may be fastened to the base building support structure above in a manner appropriate for the specific condition of that substrate. Multiple panel fixtures may be installed adjacent to each other as modules.
The manufacture of the panel fixtures according to the invention may be automated and performed, at least in part, by industrial robots. The rods are cut into a variety of required lengths from longer rods, or otherwise provided in the needed lengths, and then stocked in a picking rack with like sizes. A plurality of hanging plates may also be provided in the vicinity for use in the manufacturing process. The rods are then picked by a robotic claw and placed into a custom fixture (jig) to a specific location in a specific sequence. This assembly logic avoids lock outs or collisions among the rods. A robot arm then passes over the fixture touching and joining sticks at their points of intersection via welding, fastener or glue, etc. The hanging plates are then picked by the robotic claw, and held in place while the secondary robot fastens them with one of the methods mentioned above. Suitable programmable industrial robot systems including articulated robot arms with grasping and welding capabilities are commercially available and well known in the manufacturing art.
Various aspects of the invention are further described below with reference to the accompanying drawing.
FIG. 1A shows a top plan view of a lattice-configured modular panel embodiment of the invention. The rods are disposed within a square 48″×48″ imaginary border except that the ends of some rods extend slightly past the border on each side of the panel. Various angles between the rods are shown. Overall, there are 63% acute angles and 37% obtuse angles between the rods, in the perspective shown. Four support attachment points are shown by black dots. FIG. 1B shows a side elevational view of the embodiment shown in FIG. 1A . Various angles between the rods are shown for this perspective. Overall, there are 64% acute angles and 36% obtuse angles in this perspective. Two of the support wires attached to the panel are shown (the other two are obscured by those shown).
FIG. 2A is a density diagram in the horizontal plane (expansive dimension) for the embodiment shown in FIGS. 1A and 1B . The density of the rods in two dimensions varies across the panel. FIG. 2B is a density diagram for the vertical plane for the embodiment shown in FIGS. 1A and 1B . The density of the rods in the vertical plane as viewed from the side of the panel is much greater than that in the horizontal plane.
FIG. 3 shows the rectangular 48″×48″ envelope and peripheral overlap zones for the modular panel embodiment shown in FIG. 1A .
FIG. 4A shows a perspective view of a hanger element (tab, bracket, plate) embodiment of the invention attached to a rod and connected to a support wire. The attachment may, for example, include a weld, mechanical attachment such as with a fastener, and/or adhesive attachment. The hanger element may be formed from a bent metal plate. A hole and connected slot are formed in the hanger element so that a terminal ball member of a support wire can pass through the hole, which has a diameter wider than the width of the slot, and be captively retained by the slot while the panel hangs from the support wire. The terminal ball member and hole and slot of the hanger are mutually sized and configured so that the ball can pass through the hole from one side of the hanger plate to the other and vertically ride up the slot (as the wire connected to the ball member moves along the slot) whilst the width of the slot is smaller than the ball member thereby preventing it from passing through the slot itself to the other side of the hanger plate. In the embodiment shown, the ends of the hanger elements are curved to match the curvature of the rod to which they are attached (in this case, having a circular cross-section). FIG. 4B shows a side view of the hanging hardware in more detail. FIG. 4C shows how a lattice-configured panel embodiment of the invention may be hung from four points. The invention also provides hanger plates having a bend defining a vertex and a slot extending downward on each side of the bend, to a hole having a width/diameter larger than the width of the slot on each side. The slot on each side may be part of one continuous slot, or the slot on each side may be a separate, unconnected slot.
FIG. 5 shows an embodiment of the invention that includes an array of six lattice-configured panel fixtures (one labeled 501 ) disposed next to each other. The rod ends that extend into the overlap zone (beyond the 48″×48″ envelope in FIG. 3 ) for each panel overlap each other for the adjacent sides of neighboring panels. In this manner, the array of panels takes on a unitary appearance to the observer. The four support attachment points for each of the modules are shown by black dots in the figure.
FIG. 6 shows an embodiment of an automated rod picking system including a rod storage rack 601 and a robotic picker 602 , which may be employed in the manufacture of lattice-configured panel fixtures according to the invention.
FIG. 7 shows a manufacturing system embodiment of the invention that includes a robotic picking/placing arm 602 , robotic welding arm 703 , a rod placement jig 704 , and a partially constructed lattice-configured panel fixture 705 . Jig 704 includes a base from which upwardly extending support tabs are disposed. Each of the support tabs includes a notch at its top end which is sized and configured so that the rod stock can rest within the notch.
FIG. 8 illustrates the stacking order of rods for the manufacture of a panel fixture embodiment of the invention. A rod placement jig 804 is shown with the complete set of rods joined as a panel. The placement order of particular rods is correspondingly represented by the numbering of the projected rods represented above jig 804 (the first placed rod being number 1 , the second placed being number 2 , and so on). For any particular panel fixture embodiment of the invention, the placement order of the rods (and corresponding joining process(es)) may be programmed into the robotic systems.
FIG. 10A is a key diagram enumerating the four sides of the panel embodiment shown in FIG. 1A . Side 1 is the rear side; side 2 is the right side, side 3 is the front side; and side 4 is the left side. Each of FIGS. 10B-10E shows the corresponding elevational views of the four sides. In one aspect, the invention also provides the design and shape of a fixture panel as shown in any one of or combination of the figures, with or without the hangers and/or support wires.
Although the foregoing description is directed to the preferred embodiments of the invention, other variations and modifications may be made without departing from the spirit or scope of the invention. Moreover, features described in connection with one embodiment of the invention may be used in conjunction with other embodiments, even if not explicitly stated above. | The invention provides lattice-configured panel fixtures that include a plurality of rods joined together in a predetermined pattern, articles for supporting the panel fixtures from a support structure, and automated systems and methods for manufacturing the panel fixtures. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority to Korean Patent Application No. 10-2013-0155092 filed on Dec. 13, 2013, the entire contents of which is incorporated herein for all purposes by this reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a door opening prevention device in a broadside collision of a vehicle, and more particularly, to a device which restricts a door outside handle so as to prevent a door from being opened in a broadside collision of a vehicle.
[0004] 2. Description of Related Art
[0005] In general, when a door is opened in a broadside collision of a vehicle, an occupant catapults out of a vehicle and may be greatly injured.
[0006] In consideration of the aforementioned situation, a balance weight, which may give inertial resistance force to a door outside handle, is applied, so as to resolve the problem of the possibility of the door being opened during a broadside collision of a vehicle.
[0007] Typically, according to a mechanism for opening the door in a broadside collision of a vehicle, the door outside handle is pulled by inertial force that is generated when a collision occurs, and thereby, a door latch releases restriction of a striker such that the door is opened.
[0008] In order to prepare for the aforementioned problem, the balance weight is connected to a lever of the outside handle so as to prevent the outside handle from being opened due to inertial force that is generated when a collision occurs.
[0009] For example, as illustrated in FIG. 5 , an outside handle lever 120 , which is rotatable about a hinge shaft 110 in conjunction with an outside handle 100 , is installed inside the outside handle 100 , and a balance weight 130 is formed on the outside handle lever 120 .
[0010] Here, a reference numeral 140 , which has not been described, refers to a return spring for restoring the outside handle lever.
[0011] Therefore, immediately after a broadside collision of a vehicle, the outside handle is pulled by inertial force of the vehicle while receiving force that is directed toward the exterior of the vehicle, and when the outside handle is pulled by the positive inertia, the door may be opened as the outside handle lever is rotated.
[0012] In consideration of the aforementioned situation, the balance weight is mounted on the hinge shaft of the outside handle lever so as to offset the inertial force of the outside handle, thereby preventing the door from being opened.
[0013] However, the door opening prevention device in the related art has the following drawbacks.
[0014] Firstly, costs and weights are increased due to unnecessary components.
[0015] That is, the balance weight is present on the outside handle lever in order to merely prevent the door from being opened in a broadside collision, and needs to have a size, which corresponds to a handle size (weight), in order to provide inertial force that is sufficient for preventing the door from being opened in a broadside collision of a vehicle.
[0016] Accordingly, burdens of costs and weights are increased.
[0017] Secondly, a problem with the layout between the balance weight and peripheral components occurs.
[0018] That is, when an occupant pulls the handle and gets in an interior room, the outside handle lever is rotated and moved in a direction in which a gap with a glass becomes insufficient.
[0019] There is a disadvantage in terms of the layout in that if a sufficient space is not secured when performing an initial design in consideration of the aforementioned situation, a serious problem may occur in the future.
[0020] Thirdly, there is a problem in that the balance weight needs to be newly manufactured and tuned in accordance with the type of vehicle that is being developed.
[0021] That is, because sizes and designs of the handles are different for each type of vehicle, various balance weights also need to be applied for each type of vehicle, and thereby, various molds need to be manufactured for each type of vehicle, and tests need to be repeatedly performed over a number of times and to be tuned.
[0022] The information disclosed in this Background of the Invention section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
BRIEF SUMMARY
[0023] Various aspects of the present invention are directed to providing a door opening prevention device in a broadside collision of a vehicle which has a striker locking lever which is operated by inertia at a claw side, which catches a door striker, and restricts the striker, and implements a new type of door opening prevention structure in which a door latch instead of an outside handle may restrict the striker in a broadside collision of a vehicle, such that a weight balance applied to the existing outside handle may be omitted, thereby reducing costs and weights, and providing advantages in terms of layout.
[0024] In order to achieve the aforementioned object, the door opening prevention device in a broadside collision of a vehicle, which is provided in the present invention, has the following features.
[0025] In an aspect of the present invention, a door opening prevention device in a broadside collision of a vehicle, having a latch assembly which locks and unlocks a door side striker in conjunction with an operation of an outside handle when the outside handle is operated, may include a balance weight which is rotatably coupled to a side surface of a claw disposed in the latch assembly, wherein the balance weight is pivotable downward by inertia in the broadside collision of the vehicle, and a striker locking lever slidably engaged to the side surface of the claw and elastically biased upwards, wherein the striker locking lever is fitted between the side surface of the claw and the door side striker to jam the claw and the door side striker while being moved in a down direction by contact with the balance weight by the inertia in the broadside collision of the vehicle.
[0026] The balance weight may have a lower end which is rotatably supported by a hinge shaft that is formed on the side surface of the claw, and the balance weight receives restoring force of a return spring which is installed on the hinge shaft and connects the side surface of the claw and the balance weight, to maintain a vertical posture.
[0027] An upper portion of the balance weight is formed as a mass portion that is heavier than a remaining portion of the balance weight.
[0028] The striker locking lever is resiliently supported upward by a lever spring that may have an end supported at the side surface of the claw.
[0029] The striker locking lever may include a lower end portion extending from an upper end portion of the striker locking lever in a tapered shape such that a cross-sectional area of the striker locking lever gradually becomes smaller from the upper end portion toward the lower end portion.
[0030] The striker locking lever may further include a protrusion extending from the upper end portion, and a lever spring that may have an end supported at the side surface of the claw is positioned under the protrusion to elastically support the striker locking lever upwards.
[0031] The door opening prevention device may further include a bracket to slidably receive the striker locking lever therein.
[0032] The door opening prevention device in a broadside collision of a vehicle, which is provided in the present invention, may have the following advantages.
[0033] Firstly, the balance weight, which is much smaller than a balance weight that is applied to the existing outside handle, is applied, thereby reducing weights as well as costs.
[0034] Secondly, the door latch is commonly applied to various types of vehicles because the door latch is not a component for an external appearance, and thereby, problems of newly manufacturing components and tuning the components over a number of times may be resolved even though the door latch, which is once verified, is applied to another vehicle, thereby reducing working hours for tests and costs for tests.
[0035] Thirdly, the striker locking lever and the balance weight are installed in the latch assembly, and thus it is not necessary to consider interference with a door glass, thereby providing an advantage in terms of layout design.
[0036] Other aspects and preferred embodiments of the invention are discussed infra.
[0037] It is understood that the term “vehicle” or “vehicular” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g., fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.
[0038] The methods and apparatuses of the present invention have other features and advantages which will be apparent from or are set forth in more detail in the accompanying drawings, which are incorporated herein, and the following Detailed Description, which together serve to explain certain principles of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] FIG. 1 is a front view illustrating a latch assembly to which a door opening prevention device is installed according to an exemplary embodiment of the present invention.
[0040] FIGS. 2A and 2B are back perspective views illustrating the door opening prevention device according to an exemplary embodiment of the present invention.
[0041] FIGS. 3A and 3B are back perspective views illustrating an operational relationship of a striker locking lever in the door opening prevention device according to an exemplary embodiment of the present invention;
[0042] FIGS. 4A and 4B are back views illustrating an operational state of the door opening prevention device according to an exemplary embodiment of the present invention; and
[0043] FIG. 5 is a perspective view illustrating a door outside handle and a balance weight in the related art.
[0044] Reference numerals set forth in the Drawings includes reference to the following elements as further discussed below.
[0045] It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various preferred features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.
[0046] In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.
DETAILED DESCRIPTION
[0047] Reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.
[0048] Hereinafter, an exemplary embodiment of the present invention will be described with reference to the accompanying drawings so that those skilled in the Field of the Invention to which the present invention pertains may carry out the exemplary embodiment.
[0049] FIG. 1 is a front view illustrating a latch assembly to which a door opening prevention device is installed according to an exemplary embodiment of the present invention.
[0050] As illustrated in FIG. 1 , the latch assembly includes an outside handle opening lever 20 which is connected to an outside handle 10 , which is disposed at a door, through a cable 25 and is rotated by handle operational force, a pawl lever 21 and a pawl 22 which are rotated in conjunction with rotation of the outside handle opening lever 20 in a direction opposite to a rotation direction of the outside handle opening lever 20 , and are resiliently supported by a pawl spring 23 , a claw 13 which has one end that is caught by the pawl lever 21 side so as to maintain a positive posture (a posture which may catch a striker), and is rotatable when the striker 11 moves and pulls the claw 13 in a case in which the claw 13 is disengaged from the pawl lever 21 side, a claw spring 24 which maintains the positive posture of the claw 13 , and the like.
[0051] Therefore, when a user pulls the outside handle 10 in order to get in a vehicle, operations such as rotation of the outside handle opening lever 20 →rotations of the pawl lever 21 and the pawl 22 →disengagement between the pawl lever 21 and the claw 13 are performed, the door begins to open, the striker 11 is also pulled at the same time so as to escape while pushing the claw 13 , and as a result, the user may open the door.
[0052] Here, because constituent components of the latch assembly and operational relationships between the constituent components are identical to those of a latch assembly in the related art, a more specific description thereof will be omitted.
[0053] Further, in this latch assembly, the door opening prevention device of the present invention, that is, the door opening prevention device which is configured by a combination of a striker locking lever, a balance weight, and the like, is provided at the claw 13 side of the latch assembly, and prevents the door from being opened in a broadside collision of a vehicle by using a jamming structure with the striker side.
[0054] FIG. 2A and 2B are back perspective views illustrating the door opening prevention device according to an exemplary embodiment of the present invention, and FIG. 3 is a back perspective view illustrating an operational relationship of a striker locking lever in the door opening prevention device according to an exemplary embodiment of the present invention.
[0055] As illustrated in FIGS. 2A , 2 B, 3 A and 3 B, the door opening prevention device includes a balance weight 14 which is tilted by inertia in a broadside collision of a vehicle, and a striker locking lever 15 which is operated in conjunction with the balance weight 14 , and jams the claw 13 and the striker 11 .
[0056] The balance weight 14 is formed in a bar shape, and an upper end portion of the bar is formed as a mass portion 18 that is heavier than the remaining portion.
[0057] The balance weight 14 is installed to have a structure in which the balance weight 14 is rotatably supported by a hinge shaft 16 formed on one side surface (claw back surface portion) of the claw 13 through a lower end portion of the balance weight 14 , in a vertical posture in which the heavy mass portion 18 is directed upward.
[0058] The balance weight 14 , which is installed as described above, is positioned toward an interior room based on a claw rotation center axis such that the balance weight 14 may be tilted toward the exterior of the interior room by inertia in a broadside collision of a vehicle, and then may strike the striker locking lever 15 .
[0059] Further, a return spring 17 , which has an end caught by the claw 13 , and the other end caught by the balance weight 14 side, is installed on the hinge shaft 16 to which the lower end portion of the balance weight 14 is fitted, and the return spring 17 serves to maintain the balance weight 14 in the vertical posture in a normal state when a broadside collision of a vehicle does not occur.
[0060] The striker locking lever 15 is a component that is tightly fitted between a side surface of the claw 13 and an inner surface of the striker 11 which is formed in a “ ” shape, and serves to jam the claw 13 and the striker 11 together.
[0061] The striker locking lever 15 is formed in a bar shape having an approximately “ ” shape, and is installed to have a structure in which the striker locking lever 15 is supported on the side surface of the claw 13 at a position between the rotation center axis of the claw 13 and the balance weight 14 .
[0062] In this case, the striker locking lever 15 is in tight contact with the side surface of the claw 13 , and may be moved in up and down directions while being guided by the side surface of the claw 13 . The striker locking lever 15 is supported in a guide bracket 50 , which may be installed on the side surface of the claw and has an approximately “ ” shape, and may be slidingly guided by the guide bracket when the striker locking lever 15 is moved in the up and down directions.
[0063] Further, a lever spring 19 , which has ends that are supported at the striker locking lever 15 and the claw 13 , is provided, and the lever spring 19 is positioned under a protrusion 151 of the locking lever, which is bent horizontally, so as to resiliently support upward the striker locking lever 15 .
[0064] A bar-shaped body of the striker locking lever 15 is formed in a tapered shape in which a cross-sectional area gradually becomes smaller from an upper end portion 153 to which the protrusion 151 is formed to a lower end portion 155 , such that the striker locking lever 15 may be tightly fitted between the side surface of the claw and the inner surface of the striker by a wedge effect while the striker locking lever 15 is moved downward to be fitted between the side surface of the claw and the inner surface of the striker.
[0065] In addition, the weight balance 14 is not involved in jamming the striker 11 , but is just involved in operating the striker locking lever 15 , such that a sufficient weight of the weight balance 14 is just needed, and the weight balance 14 needs not to be made of a particularly strong material, but the striker locking lever 15 may be made of a strong material. For example, the weight balance may be made of plastic or the like, and the striker locking lever may be made of steel or the like.
[0066] Therefore, an operational state of the door opening prevention device, which is configured as described above, will be described below.
[0067] FIGS. 4A and 4B are back views illustrating an operational state of the door opening prevention device according to an exemplary embodiment of the present invention.
[0068] As illustrated in FIGS. 4A and 4B , the door opening prevention device includes two inertia components (the balance weight and the striker locking lever) so as to be operated so as to restrict escape of the striker that determines the opening of the door, and uses a principle that the door is not opened if the striker does not escape even though other levers, which are involved in opening the door, are rotated.
[0069] That is, the door opening prevention device is operated so as to directly restrict the striker that finally determines the opening of the door, such that the door is not absolutely opened even though other levers, which are involved in opening the door, are rotated.
[0070] The two inertia components are configured as a mechanism by intersection of rectilinear motion and rotational motion, and may be operated in a manner in which the inertia components are tightly fitted between the striker side and the claw side so as to restrict motion of the striker which performs rectilinear motion instead of rotational motion.
[0071] Before a broadside collision of a vehicle, the striker locking lever 15 is positioned at a home position (a position where the striker locking lever 15 is not inserted into the striker) by force of the lever spring 19 , and the balance weight 14 is also forced to be positioned at a home position (a position where the balance weight 14 stands right) by force of the return spring 17 .
[0072] In this state, the striker 11 may escape from the claw 13 while tilting the claw 13 such that the user may normally open the door by operating the outside handle.
[0073] In a broadside collision of a vehicle, the balance weight 14 is instantaneously rotated toward a portion where the striker locking lever 15 is positioned, by inertial force that is applied to the balance weight 14 , and simultaneously pushes the striker locking lever 15 through the mass portion 18 , and the striker locking lever 15 is moved downward and tightly fitted between the side surface of the claw 13 and the inner surface of the striker 11 , and jams the claw 13 and the striker 11 .
[0074] Accordingly, the striker 11 is tightly fitted with the claw 13 so as not to be pulled, and as a result, the door is not opened.
[0075] As such, the present invention implements a technology in which the latch instead of the outside handle restricts the striker at the time of a collision, and thus a weight balance of the handle is omitted, thereby greatly reducing costs and weights.
[0076] In addition, because the weight balance of the handle needs to be tuned continuously whenever various types of vehicles are developed and in accordance with a tendency that the design of the handle also becomes various, costs for development and tests, and an M/H at the time of development are greatly consumed, but when the structure of the present invention is applied, since the door latch itself prevents the door from being opened at the time of a collision regardless of the door handle, the structure of the present invention may be commonly applied to the entire types of vehicles without additional development and tests once the structure of the present invention is developed, thereby reducing costs for tests, and reducing input of the M/H.
[0077] In addition, even when the design of the handle can be formed in any shape, the door is prevented from being opened, and thus a degree of design freedom is increased, thereby greatly improving marketability.
[0078] In addition, since the door is prevented from being opened regardless of the handle, the door is not opened even in various broadside collision modes that may occur at the time of actual traffic accidents.
[0079] For convenience in explanation and accurate definition in the appended claims, the terms “upper”, “lower”, “inner” and “outer” are used to describe features of the exemplary embodiments with reference to the positions of such features as displayed in the figures.
[0080] The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and their practical application, to thereby enable others skilled in the art to make and utilize various exemplary embodiments of the present invention, as well as various alternatives and modifications thereof. It is intended that the scope of the invention be defined by the Claims appended hereto and their equivalents. | A door opening prevention device in a broadside collision of a vehicle, having a latch assembly which locks and unlocks a door side striker in conjunction with an operation of an outside handle when the outside handle may be operated, may include a balance weight which may be rotatably coupled to a side surface of a claw disposed in the latch assembly, wherein the balance weight may be pivotable downward by inertia in the broadside collision of the vehicle, and a striker locking lever slidably engaged to the side surface of the claw and elastically biased upwards, wherein the striker locking lever may be fitted between the side surface of the claw and the door side striker to jam the claw and the door side striker while being moved in a down direction by contact with the balance weight by the inertia in the broadside collision of the vehicle. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a connector structure for connecting male and female connectors by a low insertion force using a lever, and more particularly, to an inexpensive connector-with-lever in which the number of parts is small and connecting operation is excellent.
2. Description of the Related Art
As shown in FIG. 1 (not prior art), there is a proposed connector-with-lever, which comprises a first connector 2 , a second connector 6 and a substantially U-shaped lever 4 . The lever 4 pivotally supported by opposite ends of a connector housing 3 of the first connector 2 . A torsion coil spring 5 is interposed between the connector housing 3 and the lever 4 . The lever 4 is biased in a direction X in FIG. 7 with respect to the connector housing 3 by the torsion coil spring 5 .
The lever 4 is temporarily locked by a temporary locking member (not shown) at the side of the connector housing 3 for holding the temporary locking state shown in FIG. 2 in a state in which the second connector 6 is not fitted to the connector housing 3 . When the second connector 6 is fitted to the connector housing 3 , the temporary locking member is unlocked.
When the second connector 6 having the above structure is fitted to the connector housing 3 , guide pins 6 A, 6 A projecting from opposite sides of the second connector 6 are inserted into insertion guide grooves 4 A, 4 A formed in the lever 4 , and when the temporary locking members are unlocked, the lever 4 is biased in an direction opposite from the X direction shown in FIG. 7, the second connector 6 is reliably fitted into the connector housing 3 , and connecting terminals disposed in both the members are connected to each other.
However, in the case of the connector-with-lever 1 , when the lever 4 is mounted to the connector housing 3 , the torsion coil spring 5 is incorporated. Therefore, the assembling operation becomes complicated, and skill is required for the assembling operation. Further, there are problems that the operability is inferior, the torsion coil spring 5 is expensive and thus, cost of the connector 1 having lever is high.
Further, in the case of the above-described connector 1 having lever, when the second connector 6 is not fitted to the connector housing 3 , since the lever 4 is temporarily locked by the connector housing 3 in a state in which the lever 4 is biased by the torsion coil spring 5 , the lever 4 turns in accordance with biasing forces of the torsion coil spring 5 due to unexpected external force, inlets of the insertion guide grooves 4 A, 4 A are turned upward, and the second connector 6 can not be fitted. Therefore, if the lever 4 was turned, it is necessary an assembling operator to return the lever 4 to it original positions against the biasing forces of the torsion coil spring 5 and then, to fit the second connector 6 . For this reason, there is a problem that when the fitting operation is carried out in a narrow space such as an engine room of an automobile, the assembling operability is largely lowered.
SUMMARY OF THE INVENTION
Thereupon, it is an object of the present invention to provide an inexpensive connector capable of easily mounting lever to a connector housing, and capable of easily connecting a first connector and a second connector.
To achieve the above object, according to a first aspect of the invention, there is provided a connector-with-lever comprising a first connector, a second connector and a lever turnably mounted to a connector housing of the first connector, in which the first connector and the second connector are connected to each other by operating the lever, wherein the connector-with-lever further comprises lever locking means for temporarily lock the lever with the connector housing before the first connector and the second connector are connected to each other, and unlocking means for unlocking the temporary locking state of the lever when the first connector and the second connector start being connected to each other.
With the first aspect, before the first connector and the second connector are connected to each other, since the connector housing and the lever are temporarily locked with each other by the lever locking means, it is possible to prevent the lever from moving unintentionally even in a connection-standby state, and the connected state between both the connectors can be held.
When the connection between the connectors is stated, the temporary locking state of the lever is unlocked for the first time, the temporary locking state of the lever is held unless the connectors are connected.
According to a second aspect of the invention, in the connector-with-lever of the first aspect, the lever locking means comprises a locking opening formed in the connector housing, and a locking projection piece which projects from the lever, the locking projection piece is inserted into and engaged with the locking opening, and the lever holds the temporary locking state with respect to the connector housing.
With the second aspect, in addition to the effect of the first aspect, the lever locking means comprises a locking opening formed in the connector housing, and a locking projection piece which projects from the lever, the locking projection piece is inserted into and engaged with the locking opening, and the lever is temporarily locked with respect to the connector housing. Therefore, it is possible to hold the lever in the temporary locking state with a simple structure without using a spring or the like.
According to a third aspect of the invention, in the connector-with-lever of the first aspect, the unlocking means comprises a projection formed on a connector housing of the second connector, the projection abuts against the locking projection piece to push the locking projection piece from the locking opening out of a housing, thereby unlocking the temporary locking state of the lever.
With the third aspect, in addition to the effect of the first aspect, since the unlocking means is merely a projection formed on a connector housing of the second connector, the connector structure is extremely simple, and the molding die for the connector can be produced inexpensively.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of proposed connectors;
FIG. 2 is a side view one of the proposed connectors;
FIG. 3 is an exploded perspective view showing an embodiment of a connector according to the present invention;
FIG. 4 is a side view showing a state in which a first connector and a second connector of the embodiment are not yet connected to each other;
FIG. 5 is a sectional view of an essential portion of a state in which the first connector and the second connector of the embodiment are initially fitted to each other;
FIG. 6 is a sectional view showing an essential portion of a state in which a temporary locking state between a locking projection piece and a locking opening are unlocked in the embodiment; and
FIG. 7 is a side view showing a state in which the first connector and the second connector are completely connected to each other in the embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A connector-with-lever according to the present invention will be explained in detail below based on an embodiment shown in the drawings.
<Structure of Connector-With-Lever>
FIG. 3 is an exploded perspective view showing a connector-with-lever of the embodiment. As shown in FIG. 3, a connector-with-lever 10 comprises a first connector 11 , a second connector 12 and a lever 14 rotatably mounted to the first connector 11 .
[First Connector]
The first connector 11 includes a substantially cylindrical connector housing 13 . The connector housing 13 has a front opening into which the second connector 12 is fitted. A plurality of female terminals 15 are arranged vertically and horizontally in the connector housing 13 . Electric wires are connected to the female terminals 15 from rear ends thereof.
Guide grooves (slits) 16 A are formed on opposite side walls 16 , 16 of the connector housing 13 in a back-and-forth direction (fitting direction). The guide grooves 16 A are notched from their front ends to their substantially central portions. A lever pivot shaft 17 projecting sideway is integrally formed on each of the side walls 16 , 16 at its location slightly rear from its central portion.
A rectangular locking opening 18 A is formed on a front side of an upper wall 18 of the connector housing 13 such as to pass through into the housing. To-be engaged portions 20 to which engaging portions 19 of the lever 14 (which will be described later) are engaged are formed on a rear portion of the upper wall 18 .
[Lever]
The lever 14 comprises a pair of left and right lever side plates 21 , 21 on which shaft holes 21 A are formed. Lever pivot shafts 17 projecting from the side walls 16 , 16 of the connector housing 13 are fitted into the shaft holes 21 A. The lever 14 further comprises a connecting plate 22 for connecting upper portions of the pair of left and right lever side plates 21 , 21 to each other.
The lever pivot shafts 17 are fitted into the shaft holes 21 A formed in the lever side plates 21 , and the lever 14 is movably assembled into the connector housing 13 . Each of engaging guide grooves (slits) 21 B is formed into such a shape that the engaging guide groove 21 B is curved rearward and downward from a front end edge of the lever side plate 21 . A reinforcing frame 21 C is formed on each of the lever side plates 21 astride the engaging guide groove 21 B from outside.
A locking projecting piece 23 projecting downward is integrally formed on a front portion of a center portion of a lower surface of the connecting plate 22 of the lever 14 . The locking projecting piece 23 is inserted into the locking opening 18 A formed in the upper wall 18 of the connector housing 13 , and a tip end 23 A of the locking projecting piece 23 is locked at the opening edge of the locking opening 18 A. The tip end 23 A of the locking projecting piece 23 is pushed from front side to back side in the connector housing 13 (in its fitting direction). With this operation the temporary locking state between the tip end 23 A and the opening edge of the locking opening 18 A is unlocked, and the tip end 23 A is pushed out from the connector housing 13 eventually.
The structure for pushing out and discharge the tip end 23 A of the locking projecting piece 23 from the locking opening 18 A is formed by appropriately setting shapes of the locking opening 18 A and the tip end 23 A. More specifically, the structure is set by a longitudinal length of the locking opening 18 A and a direction of turning locus of the locking projecting piece 23 which turns around the lever pivot shafts 17 .
The engaging portions 19 formed on the rear end of the connecting plate 22 of the lever 14 are set such that the engaging portions 19 engage the to-be engaged portions 20 formed on the rear portion of the upper wall 18 of the connector housing 13 .
[Second Connector]
The second connector 12 is formed into a cylindrical hood capable of fitting into the connector housing 13 . In the second connector 12 , male terminals 24 to be connected to the female terminals 15 in the connector housing 13 . Cylindrical guide projections 26 to be inserted into the guide grooves 16 A and the engaging guide grooves 21 B are projecting from opposite side walls 25 of the second connector 12 . When the guide projections 26 are fitted to the connector housing 13 , the guide projections 26 are inserted into the guide grooves 16 A and the engaging guide grooves 21 B. An unlocking projection 28 which is unlocking means for unlocking the temporary locking state of the lever 14 is formed on an upper wall 27 of the second connector 12 .
<Connecting Operation>
Next, operation of the connector-with-lever 10 having the above-described structure will be explained with reference to FIGS. 4 to 7 . First, as shown in FIG. 4, the locking projecting piece 23 of the lever 14 pivotally supported by the connector housing 13 is inserted into the locking opening 18 A formed in the upper wall 18 of the connector housing 13 , and the tip end 23 A is locked by the opening edge. In this state, the guide grooves 16 A of the connector housing 13 and the tip end of the engaging guide groove 21 B of the lever 14 are in their superposed positions. Then, as shown in FIG. 4, if the first connector 11 and the second connector 12 are approached and fitted to each other, the guide projections 26 enters into the guide grooves 16 A and the engaging guide groove 21 B.
Then, if the second connector 12 is fitted into the connector housing 13 by a predetermined length, as shown in FIG. 5, the front end of the unlocking projection 28 formed on the upper wall 27 of the second connector 12 abuts against the tip end 23 A of the locking projecting piece 23 which projects slightly into to the connector housing 13 , and the tip end 23 A pushes the locking projecting piece 23 rearward. At that time, as shown in FIG. 6, the tip end 23 A is gradually pushed out from the housing through the locking opening 18 A, and the locking state is eventually unlocked.
In a state in which the guide projections 26 enters the guide grooves 16 A and the engaging guide grooves 21 B, the lever 14 is turned in a direction Y shown in the drawing by turning the connecting plate 22 of the lever 14 . With this operation, the guide projections 26 of the second connector 12 are guided by the guide grooves 16 A and the engaging guide grooves 21 B in a direction for deeply fitting the connectors by a low insertion force. With this operation, the first connector 11 and the second connector 12 are sufficiently fitted to each other and electrical connection therebetween is reliably established. The engaging portions 19 formed on the rear portion of the connector housing 13 engage the to-be engaged portions 20 , thereby holding the fitting state between the first connector 11 and the second connector 12 .
According to the connector-with-lever 10 of the present embodiment, it is unnecessary to provide a spring member between the lever 14 and the connector housing 13 , and it is possible to easily assemble the lever 14 into the connector housing 13 . Since no spring member is used, there is merit that the cost of the first connector 11 with lever can be reduced. Before the second connector 12 is fitted to the first connector 11 , since the locking projecting piece 23 is temporality locked with the locking projecting piece 23 , the lever 14 does not fall unintentionally.
The embodiment has been described above, but the present invention is not limited to the embodiment, and various changes associated with the subject matter of the invention can be made. | A connector-with-lever comprising a first connector ( 11 ), a second connector ( 12 ) and a lever ( 14 ) turnably mounted to a connector housing ( 13 ) of the first connector ( 11 ), in which the first connector ( 11 ) and the second connector ( 12 ) are connected to each other by operating the lever ( 14 ), wherein the connector-with-lever further comprises lever locking means ( 18 A), ( 23 ) for temporarily lock the lever ( 14 ) with the connector housing before the first connector ( 11 ) and the second connector ( 12 ) are connected to each other, and unlocking means ( 28 ) for unlocking the temporary locking state of the lever ( 14 ) when the first connector ( 11 ) and the second connector ( 12 ) start being connected to each other. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to linear light-emitting diode (LED) lamps and more particularly to a linear LED lamp with two shock protection switches, one at each of two ends of the lamp.
[0003] 2. Description of the Related Art
[0004] Solid-state lighting from semiconductor light-emitting diodes (LEDs) has received much attention in general lighting applications today. Because of its potential for more energy savings, better environmental protection (no hazardous materials used), higher efficiency, smaller size, and much longer lifetime than conventional incandescent bulbs and fluorescent tubes, the LED-based solid-state lighting will be a mainstream for general lighting in the near future. Meanwhile, as LED technologies develop with the drive for energy efficiency and clean technologies worldwide, more families and organizations will adopt LED lighting for their illumination applications. In this trend, the potential safety concerns such as risk of electric shock, overheating, and fire become especially important and need to be well addressed.
[0005] LEDs have a long operating life of 50,000 hours. This is equivalent to 17 years of service period, assuming operating eight hours per day, every day. However, several factors may affect the operating life of an LED-based lamp. High operating temperature is most detrimental to both LEDs and the LED driver that powers the LEDs. While LEDs can operate 50,000 hours under a condition of good thermal management such as when using an efficient heat sink design, the lamp will not emit light when LED driver is broken, which happens if high-temperature air accumulates around the LED driver, and any of its electronic components fails. In spite of longevity of LEDs, the LED-based linear lighting system can operate only around 25,000 hours. Some issues related to system reliability during service life of an LED-based lighting system need also to be discussed.
[0006] In retrofit application of a linear LED tube (LLT) lamp to replace an existing fluorescent tube, one must remove the starter or ballast because the LLT lamp does not need a high voltage to ionize the gases inside the gas-filled fluorescent tube before sustaining continuous lighting. LLT lamps operating at AC mains, such as 110, 220, and 277 VAC, have one construction issue related to product safety and needed to be resolved prior to wide field deployment. This kind of LLT lamps always fails a safety test, which measures through lamp leakage current. Because the line and the neutral of the AC main apply to both opposite ends of the tube when connected, the measurement of current leakage from one end to the other consistently results in a substantial current flow, which may present risk of shock during re-lamping. Due to this potential shock risk to the person who replaces LLT lamps in an existing fluorescent tube fixture, Underwriters Laboratories (UL), use its standard, UL 935, Risk of Shock During Relamping (Through Lamp), to do the current leakage test and to determine if LLT lamps under test meet the consumer safety requirement.
[0007] Appliances such as toasters and other appliances with exposed heating filaments present this kind of hazard. When the line and the neutral wire reverse, the heating filaments can remain live even though the power switches to “off”. Another example is screw-in incandescent bulbs. With the line and the neutral wire reversed, the screw-in thread of the socket remains energized. These happen when the line and the neutral wires in the wiring behind the walls or in the hookup of sockets are somehow interchanged even with polarized sockets and plugs that design for safety. The reason why a consumer can widely use the appliances with heating filaments and screw-in light lamps without worrying about shock hazards is that they have some kinds of protections. The said appliances have protection grids to prevent consumers from touching the heating filaments even when they are cool. The screw-in light lamp receptacle has its two electrical contacts, the line and the neutral in proximity, recessed in the luminaire. When one screws an incandescent bulb in the receptacle, little shock risk exists.
[0008] As mentioned, without protection, shock hazard will occur for an LLT lamp, which is at least 2 feet long; it is very difficult for a person to insert the two opposite bi-pins at the two ends of the LLT lamp into the two opposite sockets at two sides of the fixture at the same time. Because protecting consumers from possible electric shock during re-lamping is a high priority for LLT lamp manufacturers, they need to provide a basic protection design strictly meeting the minimum leakage current requirement and to prevent any possible electric shock that users may encounter in actual usage, no matter how they instruct a consumer to install an LLT lamp in their installation instructions.
[0009] An easy solution to reducing the risk of shock is to connect electrically only one of two bi-pins at the two ends of an LLT lamp to AC mains, leaving the other dummy bi-pin at the other end of the LLT lamp insulated. In such a way, the line and the neutral of the AC main go into the LLT lamp through the bi-pin, one for the line and the other for the neutral. The electrically insulated dummy bi-pin at the other end only serves as lamp holder to support LLT lamp mechanically in the fixture. In this case, however, the retrofit of the existing fixture to enable LLT lamp becomes complicated and needs much longer time to complete, even for electrical professionals. The rewiring and installation costs will be too high for LLT lamp providers to replace conventional fluorescent tubes economically.
[0010] Referring to FIG. 1 and FIG. 2 , a conventional LLT lamp 100 without protection switches comprises a plastic housing 110 with a length much greater than its radius of 30 to 32 mm, two end caps 120 and 130 each with a bi-pin on two opposite ends of the plastic housing 110 , LED arrays 140 and 141 mounted on two PCBs 150 and 151 , electrically connected in series using a connector 145 , and an LED driver 160 used to generate a proper DC voltage and provide a proper current from the AC main and to supply to the LED arrays 140 and 141 such that the LEDs 170 and 171 on the two PCBs 150 and 151 can emit light. In some conventional LLT lamps, DIP (dual in-line package) rather than SMD (surface mount device) LEDs are used as lighting sources. Although SMD LEDs and the supporting PCB allow more efficient manufacturing, higher yield, higher lumen output and efficacy, and longer life than their DIP counterparts do, some LLT lamp providers still produce such DIP-based products. The two PCBs 150 and 151 are glued on a surface of the lamp using an adhesive with its normal parallel to the illumination direction. The bi-pins 180 and 190 on the two end caps 120 and 130 connect electrically to an AC main, either 110 V, 220 V, or 277 VAC through two electrical sockets located lengthways in an existing fluorescent tube fixture. The two sockets in the fixture connect electrically to the line and the neutral wire of the AC main, respectively. In some conventional LLT lamps, the LED driver wrapped by an insulation paper is inserted into the LLT lamp without being mechanically secured. Another drawback for this rough manufacturing process is poor heat dispersion, which may cause overheating over a certain period under high ambient-temperature operation and shorten the LED driver's life and the lamp's life as a whole due to poor air convection and heat accumulation inside the LLT lamp 100 . In another conventional model, the circuitry of the LED driver 160 mixes with the LED arrays 140 on the PCB 150 . Based on this configuration, there are two LED drivers: driver- 1 160 and driver- 2 161 as shown in FIG. 2 . The drawback for this is that no sufficient number of LEDs is on the LED PCB, thus affecting lumen output and efficacy of the lamp. Another conventional type of LLT lamps uses two or more LED PCBs connected electrically in series. By using hard wires, the connections may not be reliable enough. Furthermore, the LED PCBs in some conventional LLT lamps are glued on the platform using adhesives, which may present another reliability issue because the PCB may peel off from the platform under adverse operating environments such as high temperature and high humidity. This is critical when the LED lamp is expected to service for 17 years.
[0011] To replace a fluorescent tube with an LLT lamp 100 , one inserts the bi-pin 180 at one end of the LLT lamp 100 into one of the two electrical sockets in the fixture and then inserts the other bi-pin 190 at the other end of the LLT lamp 100 into the other electrical socket in the fixture. When the line power of the AC main applies to the bi-pin 180 through a socket, and the other bi-pin 190 at the other end is not in the socket, the LLT lamp 100 and the LED driver 160 are deactivated because no current flows through the LED driver 160 to the neutral. However, the internal electronic circuitry is still live. At this time, if the person who replaces the LLT lamp 100 touches the exposed bi-pin 190 , which is energized, he or she will get electric shock because the current flows to earth through his or her body—a shock hazard.
[0012] Almost all LLT lamps currently available on the market are without any protection for such electric shock. The probability of getting shock is 50%, depending whether the person who replaces the lamp inserts the bi-pin first to the line of the AC main or not. If he or she inserts the bi-pin 180 or 190 first to the neutral of the AC main, then the LLT lamp 100 is deactivated while the internal circuitry is not live—no shock hazard.
[0013] An LLT lamp supplier may want to use only one shock protection switch at one end of an LLT lamp in an attempt to reduce the risk of shock during re-lamping. However, the one-switch approach cannot eliminate the possibility of shock risk. As long as shock risk exists, the consumer product safety remains the most important issue.
SUMMARY OF THE INVENTION
[0014] The present invention uses shock protection switches at both ends of the LLT lamp, at least one at each end, to fully protect the person from possible electric shock during re-lamping.
[0015] A linear light-emitting diode (LED)-based solid-state device comprising a heat sink, an LED driver, an LED printed circuit board (PCB) with a plurality of LEDs, a lens, and at least two shock protection switches, is used to replace a fluorescent tube in an existing fixture. With these shock-protection switches—at least one each at the two ends of the device, the LLT lamp prevents electric shock from happening during re-lamping. The two shock-protection switches with actuation mechanisms are engaged separately to connect the line and neutral of an external AC main to two inputs of the LED driver used to power LEDs in the LLT lamp. In such a scheme, no line voltage will possibly appear at the exposed bi-pin during re-lamping and thus any leakage current will be eliminated.
[0016] Modular design can increase manufacturing efficiency and improve yields. In this aspect, the present invention has a housing, which is preferably metallic in material and forms a hollow space lengthways under a platform. In the hollow space, the LED driver is inserted. On top of the platform, the LED PCB with a plurality of surface mount or DIP LEDs and a lens along the length are mounted. With two protection switches connected to the bi-pins through a lamp base assembly on both ends of the housing and the two inputs of the LED driver, the device can safely replace a fluorescent tube in an existing fixture. With a proper AC main connected, the device can emit warm white, natural white, day white, or cool white light corresponding to correlated color temperatures of 2,700˜3,200 K, 4,000˜4,500 K, 5,500˜6,000 K, 7,000˜7,500 K, depending on the LEDs used. Various combinations of various white, red, green, and blue LEDs are possible for implementing these correlated color temperatures.
[0017] In the present invention, thermal management not only for LEDs but also for LED driver and mechanical security of LED PCB, lamp bases, and the driver enclosure are implemented in such a way that the LLT lighting system is robust enough to maintain longevity.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is an illustration of a conventional LLT lamp without shock protection switches.
[0019] FIG. 2 is a block diagram of a conventional LLT lamp with two LED drivers.
[0020] FIG. 3 is an illustration of an LLT lamp with shock protection switches according to the present invention.
[0021] FIG. 4 is an illustration of a lamp base with a shock protection switch in place according to the present invention.
[0022] FIG. 5 is an illustration of a lamp base PCB assembly for the LLT lamp according to the present invention.
[0023] FIG. 6 is an illustration of an end cover for the LLT lamp according to the present invention.
[0024] FIG. 7 is a block diagram of an LLT lamp with shock protection switches in the present invention.
[0025] FIG. 8 is a block diagram of two shock protection switches used in the present invention.
[0026] FIG. 9 is a cross-sectional view of the LLT lamp when the LED driver, the lamp base, and associated shock protection switches are omitted.
[0027] FIG. 10 is an illustration of a housing with a platform used to hold an LED PCB on one side.
[0028] FIG. 11 is an illustration of a driver enclosure for holding the LED driver.
[0029] FIG. 12 is an illustration of a single-piece LED PCB, having a plurality of LEDs arranged in arrays.
[0030] FIG. 13 is an illustration of a lens, made of plastic or other insulation materials.
DETAILED DESCRIPTION OF THE INVENTION
[0031] To protect consumers from possible electric shock during re-lamping, the present invention provides two special lamp bases, one for each end of the LLT lamp. Each lamp base contains a standard bi-pin and at least one shock protection switch, both mounted on a lamp base PCB, rather than on an end cover. This structure is different from that of the conventional LLT lamp, which uses two end caps in which the bi-pins are directly mounted.
[0032] FIG. 3 is an illustration of an LLT lamp according to the present invention. The LLT lamp 200 has a housing 201 , two lamp bases 260 and 360 , one at each end of the housing 201 , two shock protection switches 210 and 310 in the two lamp bases 260 and 360 , and an LED driver 400 . The housing 201 , preferably metallic in material, serves also as a heat sink with a toothed profile to increase the heat dispersion (see FIG. 9 ). Other types of projections can be formed on the outer surface of the housing for improved heat dispersion. On the top of the housing 201 is single-piece LED PCB 205 to support surface mount LEDs 206 arranged in arrays 214 . FIG. 4 is an illustration of the lamp base 260 , which comprises a lamp base PCB assembly 230 ( FIG. 5 ) and an end cover 235 ( FIG. 6 ). Similarly, a lamp base 360 comprises a lamp base PCB assembly 330 and an end cover 335 (not shown). In FIG. 5 , the lamp base PCB assembly 230 further comprises a standard bi-pin 250 and at least one shock protection switch 210 , mounted on a PCB 231 . The PCB 231 has etched conductors in two layers. One layer is used to connect between the two pins of the bi-pin 250 . The other one is used to connect one of the two electrical contacts of the protection switch to the bi-pin 250 through the soldering point 232 using a wire connection. FIG. 6 is an illustration of the end cover 235 used to hold and fix the lamp base PCB assembly 230 on an end of the LLT lamp 200 . When fixed on the housing 201 through two counter-bore screw holes 242 , the bi-pin 250 and the switch actuation mechanism 240 will protrude from the holes 251 and 243 , respectively. The lamp base 260 uses the bi-pin 250 to connect the AC mains to the LED driver 400 through the protection switch 210 , normally in “off” state. When pressed, the actuation mechanism 240 actuates the switch 210 and turns on the connection between the AC mains and the LED driver 400 . The lamp base 360 and the protection switch 310 have a similar structure and function in a similar manner and will not be repeated here. Although a metallic housing 201 is preferred for more effectively dispersing heat, the present invention is not limited to one having a metallic housing. Namely, the LLT lamp in the present invention may have a non-metallic housing or have no housing at all.
[0033] FIG. 7 is a block diagram of an LLT lamp 200 with protection switches 210 / 310 in the present invention. As shown, the LED driver 400 and the LED arrays 214 are individual modules. The modular design allows LLT lamps 200 to be produced more effectively while more numbers of LEDs 206 can be surface-mounted in the LED PCB 205 area that electronic components of the LED driver may otherwise occupy. The lamp using this design can provide a sufficiently high lumen output, thus improving the system efficacy required by Energy Star program. FIG. 8 is a block diagram of two shock protection switches used in the present invention. The shock protection switch 210 comprises two electrical contacts 220 and 221 and one actuation mechanism 240 . Similarly, a shock protection switch 310 comprises two electrical contacts 320 and 321 and one actuation mechanism 340 .
[0034] The shock protection switch 400 can be of a contact type (such as a snap switch, a push-button switch, or a micro switch) or of a non-contact type (such as electro-mechanical, magnetic, optical, electro-optic, fiber-optic, infrared, or wireless based). The proximity control or sensing range of the non-contact type protection switch is normally up to 8 mm.
[0035] FIG. 9 is a cross-sectional view of the LLT lamp 200 when the LED driver 400 and the lamp bases 260 / 360 and associated protection switches 210 / 310 are omitted. As shown, the housing 201 provides a platform 202 to hold an LED PCB 205 on top with a plurality of surface mount LEDs 206 . The housing 201 also provides a hollow space 207 under the platform 202 , which can accommodate a driver enclosure 410 that support the LED driver 400 physically. The housing 201 also serves as a heat sink with a toothed profile to increase the heat dispersion for LED PCB 205 and the LED driver 400 , preventing overheating. The driver enclosure 410 is mounted and secured in the hollow space 207 such that a heat dispersion channel 404 is formed between the platform 202 and the top of the driver enclosure 410 to help disperse the heat created by the LED driver 400 .
[0036] Referring to FIGS. 3 to 9 , one of the contacts 220 connects electrically to the bi-pin 250 in the lamp base 260 that connects to AC mains, and the other contact 221 connects to one of the inputs 270 of the LED driver 400 . One of the contacts 320 connects electrically to the bi-pin 350 in the lamp base 360 that connects to AC mains, and the other contact 321 connects to the other input 370 of the LED driver 400 . The switch is normally off. Only after actuated, will the switch turn “on” such that it connects the AC mains to the LED driver 400 that in turn powers the LED arrays 214 . Served as gate controllers between the AC mains and the LED driver 400 , the protection switch 210 and 310 connect the line and the neutral of the AC mains to the two inputs 270 and 370 of the driver 400 , respectively. The protection switch may have direct actuation or sensing mechanism that actuates the switch function.
[0037] If only one shock protection switch 210 is used at one lamp base 260 for one end of the LLT lamp 200 , and if the bi-pin 250 of this end happens to be first inserted into the live socket at one end of the fixture, then a shock hazard occurs because the shock protection switch 210 already allows the AC power to connect to the driver 400 electrically inside the LLT lamp when the bi-pin 250 is in the socket. Although the LLT lamp 200 is deactivated at the time, the LED driver 400 is live. Without the shock protection switch 310 at the other end of the LLT lamp 200 , the driver input 370 connects directly to the bi-pin 350 at the other end of the LLT lamp 200 . This presents a shock hazard. However, if the shock protection switch 310 is used as in accordance with this application, the current flow to the earth continues to be interrupted until the bi-pin 350 is inserted into the other socket, and the protection switch 310 is actuated. The switch redundancy eliminates the possibility of shock hazard for a person who installs an LLT lamp in the existing fluorescent tube fixture.
[0038] One-switch approach employed in an LLT lamp can reduce the probability of shock hazard by 50% in comparison with the LLT lamp without any shock protection switch. The present invention uses at least two protection switches, at least one at each end of an LLT lamp. It can reduce the probability of shock hazard to zero—no risk of electric shock at all, even when the power is “on”. With this invention implemented in an LLT lamp, a consumer can replace a fluorescent tube with the LLT lamp without having to worry about any shock hazard that may otherwise occur.
[0039] FIG. 10 is an illustration of a housing 201 used to hold an LED PCB 205 on top of the platform 202 and a driver enclosure 410 in the hollow space 207 under the platform 202 . Both the LED PCB 205 and the driver enclosure 410 are mechanically secured on the opposite sides of the platform 202 by using screws or rivets, through the tap holes 204 and the screw holes 203 on the platform 202 , respectively. This ensures that the LED and the driver modules will not become loose from their original positions during shipment when drastic vibrations and mechanical shocks may occur.
[0040] FIG. 11 is an illustration of a driver enclosure 410 used to hold the LED driver 400 (shown in FIG. 7 ) in the hollow space 405 . The tap or rivet holes 411 on the two flanges, corresponding to the screw holes 203 on the platform 202 , are used to secure the driver enclosure mechanically in place.
[0041] FIG. 12 is an illustration of a single-piece LED PCB 205 , having a plurality of SMD LEDs 206 connected in arrays and screw holes 208 for mechanical fixing of the LEDs 206 . In contrast to conventional LLT lamps using two or more PCBs connected in series, the present invention using a single-piece LED PCB to accommodate hundreds of LEDs has the advantage of enhanced reliability.
[0042] FIG. 13 is an illustration of a lens 500 along the length of the LLT lamp, with a radius the same as the housing 201 . The lens 500 is used not only for regulating the illumination angle but also for protecting the LEDs 206 from dust and accidental damage.
[0043] In the present invention, three main modules, the end covers 235 and 335 in the two lamp bases 260 and 360 , the driver enclosure 410 , and the lens 500 , use plastic or other insulating materials meeting standard, UL94-V1 rating. The plastic or other insulating materials for these modules must be flame-retarded. Moreover, the LLT lamps are not limited to any particular shapes, although a circular LLT lamp has been used to illustrate the present invention.
[0044] Furthermore, the linear LED tube lamp may include various combinations of white, red, green, and blue LEDs for implementing various warm white, natural white, day white, or cool white light at correlated color temperatures of 2,700˜3,200 K, 4,000˜4,500 K, 5,500˜6,000 K, 7,000˜7,500 K. | A linear light-emitting diode (LED)-based solid-state device comprising at least two shock protection switches, at least one each at the two ends of the device, fully protects a person from possible electric shock during re-lamping with LED lamps. | 5 |
PRIORITY CLAIM TO PREVIOUSLY FILED APPLICATION
This application claims benefit of Provisional appl. 60/179,500 filed Feb. 1, 2000 which is a continuation of and claims priority to application Ser. No. 09/774,519, filed Jan. 31, 2001 U.S. Pat. No. 6,585,039.
BACKGROUND OF THE INVENTION
The present invention relates generally to the cooling of heat generating surfaces and objects. More specifically, the present invention relates to apparatuses for dissipating heat generated by such objects. In addition, the present invention relates to cooling of heat generating objects by use of composite materials, phase change devices and apparatus without the use of external fans to assist in cooling while also shielding such devices from the harmful effects of electromagnetic interference (EMI) waves.
In industry, there are various parts and components that generate heat during operation. For example, in the electronics and computer industries, it is well known that computer components generate heat during operation. Various types of electronic device packages and integrated circuit chips, such as the PENTIUM central processing unit chip (CPU) manufactured by Intel Corporation and RAM (random access memory) chips are such devices that generate heat. These devices, particularly the CPU microprocessor chips, generate a great deal of heat during operation, which must be removed to prevent adverse effects on operation of the system into which the device is installed. For example, a PENTIUM microprocessor, containing millions of transistors, is highly susceptible to overheating which could destroy the microprocessor device itself or other components proximal to the microprocessor.
There are a number of prior art methods to cool heat generating components and objects to avoid device failure and overheating, as discussed above. A block heat sink or heat spreader is commonly placed into communication with the heat-generating surface of the object to dissipate the heat there from. Such a heat sink typically includes a base member with a number of individual cooling members, such as fins, posts or pins, to assist in the dissipation of heat. The geometry of the cooling members is designed to improve the surface area of the heat sink with the ambient air for optimal heat dissipation. The use of such fins, posts of pins in an optimal geometrical configuration greatly enhances heat dissipation compared to devices with no such additional cooling members, such as a flat heat spreader.
It is also known to employ heat pipes to improve the overall performance of a heat spreader or heat sink. A heat pipe is typically a closed ended tubular metal body that is charged with a phase change media, such as water or ammonia. One end of the heat pipe is placed in communication with a heat-generating object while the opposing end is placed in a heat-dissipating zone, such as exterior to a computer case or proximal to a fan assembly. The heat-generating object heats up the phase change media within the heat pipe to a vapor state. The heated media then naturally migrates toward a cooler region of the heat pipe, namely the end opposite to that affixed to the heat-generating object. As a result, the media within the pipe transfers heat from one point to another.
In the prior art, the construction of these heat pipes are very well known. However, due to their delicate tubular construction, the heat pipe outer surface is constructed from metallic tubing for added strength and heat dissipating properties. The drawback is that this construction also creates a very effective antenna for receiving and transmitting EMI waves. This property is undesirable because, since the heat pipe is generally in direct contact with sensitive electronic components, the EMI waves that are received can be transmitted directly to the electronic components, interfering with their operation. To address this problem, it has been known to employ an additional component for shielding the entire assembly from the effects of EMI waves. These EMI shields consist of a metallic shield installed over and in close proximity to the surface of the electronic components to be shielded. However, the addition of another component is expensive and time consuming and due as a result of its construction, restricts airflow around the electronic components further preventing effective cooling.
As an alternative to heat pipes and to further enhance airflow and resultant heat dissipation, active cooling in the form of electric fans has been used, either internally or externally. However, these external devices consume power and have numerous moving parts. As a result, heat sink assemblies with active devices are subject to failure and are much less reliable than a device that is solely passive in nature.
It has been discovered that more efficient cooling of electronics can be obtained through the use of passive devices that require no external power source and contain no moving parts. It is very common in the electronics industry to have many electronic devices on a single circuit board, such as a motherboard, EMI shield, modem, or “processor card” such as the Celeron board manufactured by Intel Corporation. Again, the EMI shields contribute to component overheating by retaining heat due to their proximity to the heat generating components and therefore need efficient and effective cooling as do the CPUs discussed above.
In the heat sink industries, it has been well known to employ metallic materials for thermal conductivity applications, such as heat dissipation for cooling semiconductor device packages and for constructing EMI shields. For these applications, the metallic material typically is tooled or machined from bulk metals into the desired configuration. However, such metallic conductive articles are typically very heavy, costly to machine and are susceptible to corrosion. Further, the geometries of machined metallic heat dissipating articles are very limited to the inherent limitations associated with the machining or tooling process. As a result, the requirement of use of metallic materials which are machined into the desired form, place severe limitations on heat sink design particular when it is known that certain geometries, simply by virtue of their design, would realize better efficiency but are not attainable due to the limitations in machining metallic articles.
In view of the foregoing, there is a demand for a heat pipe construction that is capable of dissipating heat. There is a demand for a heat pipe construction with no moving parts that can provide heat dissipation without the use of active components. In addition, there is a demand for a composite heat pipe construction that can provide greatly enhanced heat dissipation over prior art passive devices with the ability to also absorb and dissipate EMI waves to prevent their transmission back into the component being cooled. There is a further demand for a heat pipe construction that can provide heat dissipation in a low profile configuration while obviating the need for additional EMI shielding components.
SUMMARY OF THE INVENTION
The present invention preserves the advantages of prior art heat dissipation devices and heat pipes. In addition, it provides new advantages not found in currently available devices and overcomes many disadvantages of such currently available devices.
The invention is generally directed to the novel and unique composite heat pipe construction that is constructed by over molding a conventional heat pipe with a thermally conductive polymer composition having electromagnetic interference (EMI) absorptive properties. The present invention relates to a composite overmolded heat pipe for dissipating heat from a heat generating source, such as a computer semiconductor chip, electromagnetic interference (EMI) shield, or other electronic components.
The heat pipe construction of the present invention has many advantages over prior art heat pipe constructions in that additional overmolded heat dissipating structure can be employed to enhance the overall thermal conductive and performance of the heat pipe while absorbing potentially harmful EMI waves without transmitting them to the device being cooled. The composite heat pipe construction of the present invention includes a heat pipe with phase change media therein with a thermally conductive, EMI absorptive composition is molded about the heat pipe. Alternatively, EMI reflective compositions may also be used. The overmolded material, while completely encasing the heat pipe, may also be molded into flat surfaces at each end to provide better contact and thermal communication with the heat generating surface of the electronic component at one end and a heat dissipating surface of a heat sink device at the other.
Further, since the molded heat exchanger is injection molded, there is tremendous flexibility in the arrangement of the components over the known methods of interconnecting components as in prior art assemblies.
A single heat pipe is preferably employed but multiple heat pipes may be embedded within the construction of the present invention. The optional flat contact ends are thermally interconnected to the heat pipe by over molding a thermally conductive polymer material which achieves greatly improved results and its far less expensive than soldering a heat pipe to a heat spreader.
It is therefore an object of the present invention to provide an improved composite heat pipe construction that can provide enhanced heat dissipation for a heat generating component or object.
It is an object of the present invention to provide a heat pipe construction that can provide heat dissipation for semiconductor devices on a circuit board, such as a motherboard or video card.
It is a further object of the present invention to provide a heat pipe construction device that has no moving parts.
Another object of the present invention is to provide a heat pipe construction device that is completely passive and does not consume power.
A further object of the present invention is to provide a heat pipe construction that inexpensive to manufacture.
Another object of the present invention is to provide a heat pipe construction that has a thermal conductivity greater that conventional heat sink designs while providing EMI shielding to the components being cooled.
A further object of the present invention is to provide a composite heat pipe construction that is moldable and is easy to manufacture.
Yet another objective of the present invention is to provide a molded heat spreader construction that has a low profile configuration that provides EMI shielding without sacrificing thermal transfer efficiency.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features which are characteristic of the present invention are set forth in the appended claims. However, the invention's preferred embodiments, together with further objects and attendant advantages, will be best understood by reference to the following detailed description taken in connection with the accompanying drawings in which:
FIG. 1 is a perspective view of the composite heat pipe construction of the present invention;
FIG. 2 is a general cross-sectional view through line 2 — 2 of FIG. 1; and
FIG. 3 is a perspective view of an alternative embodiment of the composite heat pipe construction of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1 and 2, the composite heat pipe construction 10 of the present invention is shown. The construction 10 includes a heat pipe 12 , with phase change media 28 contained therein, that provides a centrally positioned heat transfer member that is overmolded with a layer of moldable thermally conductive material 14 , such as a thermally conductive polymer composite material. Preferably, the composite material is molded around the heat pipe 12 and completely encases the entire heat pipe 12 to provide a unitary net-shape molded heat pipe configuration 10 . As best seen in FIG. 2, the polymer composite material 14 is molded over the outer surface 18 of the outer metallic tube 16 of the heat pipe 12 to achieve a unitary composite heat pipe configuration 10 .
The thermally conductive material 14 is preferably a conductive polymer composition that includes a base polymer of, for example, a liquid crystal polymer that is loaded with a high aspect ratio conductive filler material, such as carbon fiber. Additionally, a second, low aspect ratio filler material, such as boron nitride grains may also be added to the base matrix to further enhance the thermally conductive properties of the composite. Other base materials and conductive fillers may be used and still be within the scope of the present invention.
The composite material 14 thus created has inherent properties that enable it to absorb EMI waves. This effect is desirable when the composite material 14 is employed for encasing the heat pipe 12 . Since the outer casing 16 of the heat pipe 12 is metallic, it acts as an antenna receiving and conducting EMI waves throughout its metallic casing 16 . This transmission of EMI waves throughout the heat pipe 12 can result in malfunction and damage to the electronic components being cooled by the heat pipe 12 . As a result of providing the composite coating 14 over the heat pipe 12 in the present invention, EMI waves are absorbed and harmlessly dissipated by the composite coating 14 . In certain applications, an EMI reflective composition may be employed for composite coating 14 .
Turning now to FIG. 3, an alternative embodiment 20 of the present invention is shown. The construction of the overmolded heat pipe 22 proceeds the same as in the preferred embodiment as described above providing a heat pipe 12 and over molding the outer surface 18 of the heat pipe 12 with a coating of thermally conductive polymer 14 . In addition, during the over molding process, contact pads 24 are integrally molded from a thermally conductive polymer with the integral coating 14 over the heat pipe 12 resulting in a net-shape over molded heat pipe 20 that can be immediately incorporated into the resulting device. Flat upper surfaces 26 are provided on the contact pads 24 which are intended to be installed in contact with heat generating surfaces of electronic components, such as microprocessor chips, on one end X and heat dissipating components, such as heat sinks, on the other end Y, allowing the free and passive thermal conduction from X to Y.
The heat pipe 20 of the present invention may be affixed to a surface to be cooled in a fashion similar to the way a conventional heat spreader is affixed to a surface to be cooled. The upper surface 26 of the contact pad 24 is mated with the surface to be cooled on one end X and the surface to dissipate the heat on the other end Y. Further, fasteners (not shown), such as threaded screws, may be provided to secure the heat pipe contact pads 24 to a surface. The heat pipe 20 may also be affixed to a surface with thermally conductive adhesive. Other different types of fasteners and connection methods may be employed for this purpose, such as spring clips and clamps.
Since the heat pipe construction 20 of the present invention is net-shape molded which means that after molding it is ready for use and does not require additional machining or tooling to achieve the desire configuration of the heat pipe part 20 . With the assistance of the heat pipe 12 and the overmolded thermally conductive composition 14 , the present invention provides an improved heat pipe where the heat is spread more evenly and effectively through the body of the heat pipe construction 20 .
A described above, the ability to injection mold a thermally conductive device rather than machine it has many advantages. Although not shown, additional fins or pins may be integrally molded into the side of the heat pipe construction 10 of thermally conductive material to further enhance cooling and heat dissipation of the construction.
It should be understood that the applications shown in FIGS. 1, 2 and 3 are merely an example of the many different applications of the present invention and are for illustration purposes only. The composite heat pipe of the present invention is shown in a straight configuration; however, any configuration may be employed to suit the application and device environment at hand, such as Z-shaped or meandering configuration.
It would be appreciated by those skilled in the art that various changes and modifications can be made to the illustrated embodiments without departing from the spirit of the present invention. All such modifications and changes are intended to be covered by the appended claims. | The present invention discloses a method of constructing a heat pipe that includes providing a heat pipe with phase change media therein and injection overmolding the heat pipe with a conductive composition. The thermally conductive composition absorbs or reflects electro magnetic interference waves and prevents their transmission into and through the heat pipe to the electronic components being cooled by the heat pipe. | 5 |
FIELD OF THE INVENTION
This invention relates to the field of migraine treatment.
BACKGROUND OF THE INVENTION
The prevalence of migraine is said to be approximately 6% of the male population and 18% of the female population. Treatment for many patients having the occasional migraine usually involves simple analgesics, non-steroidal anti-inflammatory agents, or specific agents such as ergotamines or triptans. Approximately 10% of migraine sufferers have three or more attacks per month and warrant prophylactic treatment. Preventative agents such as beta-blockers, tricyclic antidepressants and divalproex sodium can reduce but not eliminate migraine attacks in some patients. Thus, there remains a need for migraine specific medications such as sumatriptan. In the remaining population of migraine sufferers, and in those with intolerable side-effects from available drugs, there is a lack of conventional pharmaceutical preparations that exhibit therapeutic effect, without severe side-effects.
Droperidol presently is marketed by Akorn, Inc. under the trademark Inapsine, as an injectable formulation used in anesthesia for preoperative surgery. It has never been approved for use in the treatment or management of migraine attacks.
A limited, uncontrolled, non-blinded, use of droperidol lactate (2.5 mg/ml droperidol) to treat migraine attacks was attempted and the results published in Headache, Apr. 1996, p.280. In that publication it was reported that 20 patients received from 2.5 to 7.5 mg droperidol intravenously, in increments of 2.5 mg every 30 minutes until the patient was headache free or until a total of three doses had been administered. All of the patients received prior treatment with migraine therapies. Eighteen of the patients reported to be headache-free by the last dose. Although the article reports on apparently encouraging results in treating migraine attacks with droperidol, no definitive conclusions can be reached from the results reported in that article as the number of patients treated was small, the study was not blinded, all patients received other agents to treat the migraine episode prior to receiving droperidol, and there was no placebo control. Also, there was no attempt to repeat the results with the patients. Further, no attempt was made to prolong therapy beyond the initial treatment to a headache-free state and most patients had continuing symptoms to some degree within 24 hours after the last droperidol treatment.
Additionally, the aforementioned study and article only used intravenous droperidol. Others also have used intramuscular droperidol in uncontrolled studies for treatment of migraine. The use of droperidol by injection raises several issues, not the least of which is inconvenience to the patient, caused by the need to have the droperidol administered by a health care professional.
Accordingly, a need exists for a means to treat patients who suffer from, or are at risk of, a migraine episode, that does not require the use of injections of droperidol.
SUMMARY OF THE INVENTION
In accordance with the present invention, droperidol is supplied in a dosage form that provides better patient tolerance and improved ease of administration. In particular, the present invention relates to the use of oral dosage forms of droperidol.
The dosage forms of the present invention comprise tablets, capsules, powders, syrups and effervescent compositions.
The dosage forms of the present invention may be used to treat migraine episodes, by administration to a patient during a migraine attack, in an amount that is effective to treat symptoms of migraine. The dosage forms of droperidol may be used without pretreatment or in conjunction with other migraine therapies.
The dosage forms of the present invention also may be used to treat patients that are suffering from tension headache, vertigo, or hyperemesis gravidarum. The dosage forms also may be used as antiemetics, to treat nausea and the like, such as that caused by chemotherapy. In each instance the dosage is administered in an amount sufficient to treat the patient's symptoms.
The present invention also provides oral dosage forms of droperidol that comprise from 0.5 to 20 mg of droperidol per unit dosage.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides dosage forms of droperidol containing various amounts of droperidol, such as between about 0.5 and 20 mg droperidol per unit dosage, such as tablets and capsules, that are particularly useful. The present invention also provides liquid solutions of droperidol, such as syrups, having a concentration of droperidol from about 0.5 mg to about 20 mg. Powders, in dry form, will contain from about 0.5 mg to about 20 mg droperidol and effervescent compositions which contain from about 0.5 mg to about 20 mg, by weight.
The droperidol may be present as the lactate, or any other suitable organic salts of droperidol may be used, such as tartrate or acetate.
As indicated, patients that are suffering from a migraine episode, tension headache, vertigo, hyperemesis gravidarum, or nausea may be treated. The patients are administered the droperidol, typically in dosages of 2 mg to 20 mg, until the symptoms subside. The maximum dosage of droperidol administered to a patient at a single session usually will be 10 mg, although it may on occasion be as high as 20 mg.
The patients receiving droperidol to treat migraine may be treated with droperidol as a single therapy. By this it is meant that other agents used to treat an active episode of migraine need not be used prior to or in conjunction with the droperidol treatment. Many patients receive various medications for prophylaxis against active migraine episodes, but such prophylactic therapy is not considered to be pretreatment of an active migraine episode, prior to droperidol treatment. Such therapy is nonspecific in that the goal is to prevent or reduce the number of occurrences of active migraine headache, but not the treatment of a specific migraine episode. The present dosage forms will be useful as a first-line treatment of active migraine headache without the prior use of traditional migraine therapy, or as a rescue medication when other treatment has failed.
Presently, an active migraine episode may be treated with any of a number of therapies, including the following: Simple analgesics, such as aspirin or acetaminophen, combination analgesics as with caffeine, vasoconstrictors, narcotics, and the like.
As indicated, the use of droperidol in accordance with the present invention does not require the prior administration of such other agents for treating migraine.
The migraine patients to whom droperidol should be administered are those that are experiencing a migraine episode or are at risk of such an episode. Such patients may be generally described as those meeting the diagnostic criteria for "migraine with aura" or "migraine without aura" as detailed in: "Classification Committee of the International Headache Society. Classification and Diagnostic Criteria For Headache Disorders, Cranial Neuroalgia and Facial Pain", Cephalgia, 1988, Vol. 8, Supp. 77 at pp. 19-21; or meeting the diagnostic criteria for "status migrainosus", as detailed therein at pp. 26-27.
For some patients it may be beneficial to administer an additional dose of droperidol after the headache has subsided to reduce the probability that the headache will return in a short period of time. Such an additional dose of droperidol may be used to avoid the use of a sedative or other analgesics within the next few hours after the headache symptoms have subsided. Presently it is typical for patients, after they have been rendered headache-free, to resort to such remedies as sedation or use of analgesics shortly after the headache symptoms have subsided to reduce the recurrence of the migraine symptoms after the patient has become headache-free. The present invention may avoid the need for such remedies.
TABLETS
In order to form in tablets, there are used carriers such as vehicles (e.g. lactose, white sugar, sodium chloride, glucose, urea, starches, calcium carbonate, kaolin, crystalline cellulose, silicic acid, etc.), binders (e.g. water, ethanol, propanol, simple syrup, glucose solution, starch solution, gelatin solution, carboxymethyl cellulose, shellac, methyl cellulose, potassium phosphate, polyvinylpyrrolidone, etc.), disintegrators (e.g. dry starch, sodium alginate, agar powder, sodium hydrogen carbonate, calcium carbonate, polyoxyethylene sorbitan fatty acid esters, sodium laurylsulfate, stearic monoglyceride, starches, lactose, etc.), disintegration inhibitors (e.g. white sugar, stearin, cacao butter, hydrogenated oils, etc.), absorption promoters (e.g. quaternary ammonium base, sodium laurylsulfate, etc.), wetting agents (e.g. glycerin, starches, etc.), adsorbents (e.g. starches, lactose, kaolin, bentonite, colloidal silicates, etc.), lubricants (e.g. purified talc, stearates, boric acid powder, polyethylene glycol, etc.), and the like. moreover, the tablets may be in the form of a conventional non-coated tablet, or a sugar-coated tablet, gelatin-coated tablet, enteric coated tablet, film coated tablet, or double or multiple layer tablet.
CAPSULES
The capsules may also contain the following ingredients: a binder such as micro-crystalline cellulose, gum tragacanth or gelatin; an excipient such as starch or lactose, a disintegrating agent such as alginic acid, Primogel, cornstarch and the like; a lubricant such as magnesium stearate or Sterotex; a glidant such as colloidal silicon dioxide; and a sweetening agent such as sucrose or saccharin may be added or a flavoring agent such as peppermint, methyl salicylate, or orange flavoring.
POWDERS
To form a useful powder, the droperidol may be admixed with at least one inert customary excipient (or carrier) such as sodium citrate of dicalcium phosphate or (a) fillers or extenders, as for example, starches, lactose, sucrose, glucose, mannitol and silicic acid, (b) binders, as for example, carboxymethylcellulose, alignates, gelatin, polyvinylpyrrolidone, sucrose and acadia, (c) humectants, as for example, glycerol, (d) disintegrating agents, as for example, agar-agar, calcium carbonate, potato or tapioca starch, alginic acid, certain complex silicates and sodium carbonate, (e) solution retarders, as for example paraffin, (f) absorption accelerators, as for example, quaternary ammonium compounds, (g) wetting agents, as for example, cetyl alcohol and glycerol monostearate, (h) adsorbents, as for example, kaolin and bentonite, and (i) lubricants, as for example, talc, calcium stearate, magnesium stearate, solid polyethylene glycols, sodium lauryl sulfate or mixtures thereof.
EFFERVESCENT POWDER
Effervescent powder may be formulated by the aid of agents such as sodium bicarbonate, citric acid anhydrous, calcium phosphate monobasic, calcium phosphate dibasic, polyvinylpyrrolidone, polyethylene glycol powder, silica gel, L-Leucine, sodium benzoate, simethicone, mineral oil, isopropyl alcohol, water, flavoring agents, sugar, sorbitol, aspartame, saccharin and coloring agents.
SYRUPS AND SOLUTIONS
Droperidol syrups and solutions may be made by adding ingredients such as water, sugar, fructose, sorbitol, aspartame, saccharin, polyethylene glycol, propylene glycol, alcohol, bentonite, tragacanth, alginates, gelatin, carboxymethylcellulose, methylparaben, propylparaben, sodium benzoate, flavoring agents and coloring agents.
The present invention will be described in terms of the following non-limiting examples.
EXAMPLE 1 TABLET FORMULATION
______________________________________ 0.5 20INGREDIENT MG/TABLET MG/TABLET______________________________________Droperidol 0.5 mg 20 mgLactose 50 mg 50 mgCorn Starch 10 mg 10 mgMagnesium Stearate 0.5 mg 1 mg Tablet Weight: 61 mg 81 mg______________________________________
Tablet Process: The ingredients of 1,000 tablets (61 g for 0.5 mg formulation and 81 g for 20 mg 5 formulation)are blended in a suitable mixer and then are compressed into tablets using standard concave punches. Tablets are packaged into bottles or individual blister strips.
The tablets can be further coated using either aqueous film coating in a suitable coating pan and dried. The coated tablets are packaged into bottles or individual blister strips.
The tablets can be further coated using conventional sugar coating procedure in a suitable coating pan and dried. The tablets are packaged into bottles or individual blister strips.
EXAMPLE 2 CAPSULE FORMULATION
______________________________________ 0.5 20INGREDIENT MG/CAPSULE MG/CAPSULE______________________________________Droperidol 0.5 mg 20 mgLactose 50 mg 50 mgPolyvinylpyrrolidone 5 mg 5 mgCorn Starch 25 mg 25 mgMagnesium Stearate 1 mg 2 mg Capsule Weight 81.5 mg 102.0 mg______________________________________
Capsule Process: The ingredients are blended for 1,000 capsules (81.5 g for 0.5 mg formulation and 102 g for 20 mg formulation) in a suitable mixer, then filled into hard shell capsules using conventional procedure. The capsules are cleaned and packaged into bottles or individual blister strips.
EXAMPLE 3 POWER FORMULATION
______________________________________ 0.5 20 MG/BLISTER MG/BLISTERINGREDIENT PACK PACK______________________________________Droperidol 0.5 mg 20 mgSucrose 50 mg 50 mgCarboxymethylcellulose 10 mg 10 mgPeppermint Spray Dried Flavor 2 mg 3 mg Powder Weight: 62.5 mg 83 mg______________________________________
Powder Process: The ingredients of 1,000 powder units (62.5 g for 0.5 mg formulation and 83 g for 20 mg formulation) are blended in a suitable mixer and filled into individual blister packs.
EXAMPLE 4 EFFERVESCENT TABLET AND POWDER
______________________________________ 0.5 20INGREDIENT MG/UNIT MG/UNIT______________________________________Droperidol 0.5 mg 20 mgSodium Bicarbonate 50 mg 80 mgCitric Acid Anhydrous 30 mg 50 mgSaccharin 1 mg 1 mgSilica Gel 5 mg 7 mg UNIT WEIGHT 86.5 mg 158 mg______________________________________
Tablet Process: The ingredients are blended for 1,000 tablets (86.5 g for 0.5 mg formulation and 158 g for 20 mg formulation) in a suitable mixer and compressed into tablets under controlled environmental condition with relative humidity <30%. The tablets are packaged in glass bottles or individually in an aluminum foil pouch to protect from moisture during storage.
Powder Process: The ingredients are blended for 1,000 powder units (86.5 g for 0.5 mg formulation and 158 g for 20 mg formulation) in a suitable mixer in an environmental condition of relative humidity <30%. The individual powder units are packaged in an aluminum foil pouch to protect form moisture during storage.
EXAMPLE 5 SYRUP AND SOLUTION FORMULATION
______________________________________ 0.5 20INGREDIENT MG/ML MG/5 ML______________________________________Droperidol 0.5 mg 20 mgLactic Acid qs to pH 3.5 3.5Sucrose 50 mg 250 mgCitrus Flavor 0.1 mg 0.5 mgMethylparaben 1 mg 5 mgPropylparaben 0.2 mg 1 mgWater, qs.ad 1 ml 5 ml TOTAL WEIGHT 1 ml (1 g) 5 ml (5 g)______________________________________
Syrup and Solution Process: In a suitable vessel, droperidol is dissolved with lactic acid with pH adjusted to about 3.5 in sufficient quantity of water. The remaining ingredients are then added and dissolved. Sufficient water is then added for 1,000 units (1,000 ml for 0.5 mg formulation and 5,000 ml for 20 mg formulation). The solution is filtered and filled into bottles. | Oral dosage form of droperidol are provided and a method for treating migraine using such oral formulations. The dosage forms include tablets, capsules, powders, effervescent formulations and syrups. | 0 |
CLAIM OF PRIORITY
This application claims priority under 35 U.S.C. 119(e)(1) to U.S. Provisional Application No. 60/973,559 filed Sep. 19, 2007 and U.S. Provisional Application No. 61/045,187 filed Apr. 15, 2008.
TECHNICAL FIELD OF THE INVENTION
The technical field of this invention is video data coding.
BACKGROUND OF THE INVENTION
New video conferencing encoding standards such as H.264 employ Context Adaptive Binary Arithmetic Coding (CABAC) for its high compression efficiency. In CABAC data is encoded based upon the probability distributions of the data and the relationship between the most probable next data and other data. The most probable data is encoded in fewer bits than other sequential data. The most probable data is encoded in fewer bits than other data and the probabilities are updated sequentially. Many types of image data can be transmitted in this form. This application discloses an example of encoding of a significance map, but other data types are feasible.
Image data compression often employs a spatial to frequency transform of blocks of image data known as macroblocks. A Discrete Cosine Transform (DCT) is typically used for this spatial to frequency transform. Most images have more information in the low frequency bands than in the high frequency bands. It is typical to arrange and encode such data in frequency order from low frequency to high frequency. Generally such an arrangement of data will produce a highest frequency with significant data that is lower than the highest possible encoded frequency. This permits the data for frequencies higher than the highest frequency with significant data to be coded via an end-of-block code. Such an end-of-block code implies all remaining higher frequency data is insignificant. This technique saves coding the bits that might have been devoted to the higher frequency data. The significance map is one form of encoding described above.
The H.264 video conferencing coding standard uses significance map to perform run-level information encoding after quantization. Every coefficient that is non-significant (zero) is encoded as 0. If a coefficient is significant, that is non-zero, and it is not the last such significant coefficient in the block, then it is encoded as 10. If the coefficient is the last significant coefficient in the block, then it is encoded as 11. If the coefficient is significant and is also the last possible coefficient in the block, then it is encoded as 10. Such a coefficient would be known as the last coefficient in the block by a count of the block coefficients.
A straight forward manner of CABAC decoding such data employs a series of conditional branches. Such conditional branching code is not well matched to a pipelined data processor which experiences a pipeline hit upon each conditional branch. Each taken conditional branch requires that later instructions already partially executed within the pipeline to be aborted and new instructions need be processed within the pipeline. This serves to place a limit on processing speed because data processors tend to be more deeply pipelined at higher operating frequencies. Software loop unrolling may reduce this problem. In any event, conventional CABAC decoding is not well matched to exploiting instruction level parallelism of a very long instruction word (VLIW) data processor such as the Texas Instruments TMS320C6000 series.
SUMMARY OF THE INVENTION
This invention is a method of context adaptive binary arithmetic coding and decoding on multiple binary symbols per cycle. For coding the invention groups a plurality of N binary symbols (bins) which belong to one or more syntax elements. The invention divides a range into 2 N subranges. The initial syntax element divides said range into two subranges according to the probability state of the binary symbol's context. The corresponding probability of the next context corresponding to next syntax elements divides each prior subrange into two parts. This repeats for all N syntax elements. The invention selects an offset found in the subrange determined by the digital states of the N syntax elements according to corresponding contexts. Decoding is similar with the place of the coded offset within the 2 N subranges determining the syntax decoding. When the total number of syntax elements to be coded does not equal an integral multiple of N, the invention codes dummy binary symbols at the end of a grouping of a plurality N binary symbols. This method can be used across syntax element types as a significance map and corresponding coefficient levels can be coded and decoded together. The invention also updates the probability state of the context only after every N binary symbols are coded. It uses a true multiplication rather than a look up table to compute the product of N probabilities for the N binary symbols.
The CABAC engine proposed here is suitable for ASIC implementations and very long instruction word (VLIW) data processor such as the Texas Instruments TMS320C6000 series providing flexibility in the number of parallel units that can be used for processing.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other aspects of this invention are illustrated in the drawings, in which:
FIG. 1 illustrates the organization of a typical digital signal processor to which this invention is applicable (prior art);
FIG. 2 illustrates details of a very long instruction word digital signal processor core suitable for use in FIG. 1 (prior art);
FIG. 3 illustrates the pipeline stages of the very long instruction word digital signal processor core illustrated in FIG. 2 (prior art);
FIG. 4 illustrates the instruction syntax of the very long instruction word digital signal processor core illustrated in FIG. 2 (prior art);
FIG. 5 illustrates an overview of the video encoding process of the prior art;
FIG. 6 illustrates an overview of the video decoding process of the prior art;
FIG. 7 illustrates the difference between the prior art 1-bin CABAC decoding and the 2-bin CABAC decoding of this invention; and
FIG. 8 illustrates an example decision tree determining the possible contexts for 2-bin CABAC decoding of a significance map.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 illustrates the organization of a typical digital signal processor system 100 to which this invention is applicable (prior art). Digital signal processor system 100 includes central processing unit core 110 . Central processing unit core 110 includes the data processing portion of digital signal processor system 100 . Central processing unit core 110 could be constructed as known in the art and would typically includes a register file, an integer arithmetic logic unit, an integer multiplier and program flow control units. An example of an appropriate central processing unit core is described below in conjunction with FIGS. 2 to 4 .
Digital signal processor system 100 includes a number of cache memories. FIG. 1 illustrates a pair of first level caches. Level one instruction cache (L 1 I) 121 stores instructions used by central processing unit core 110 . Central processing unit core 110 first attempts to access any instruction from level one instruction cache 121 . Level one data cache (L 1 D) 123 stores data used by central processing unit core 110 . Central processing unit core 110 first attempts to access any required data from level one data cache 123 . The two level one caches are backed by a level two unified cache (L 2 ) 130 . In the event of a cache miss to level one instruction cache 121 or to level one data cache 123 , the requested instruction or data is sought from level two unified cache 130 . If the requested instruction or data is stored in level two unified cache 130 , then it is supplied to the requesting level one cache for supply to central processing unit core 110 . As is known in the art, the requested instruction or data may be simultaneously supplied to both the requesting cache and central processing unit core 110 to speed use.
Level two unified cache 130 is further coupled to higher level memory systems. Digital signal processor system 100 may be a part of a multiprocessor system. The other processors of the multiprocessor system are coupled to level two unified cache 130 via a transfer request bus 141 and a data transfer bus 143 . A direct memory access unit 150 provides the connection of digital signal processor system 100 to external memory 161 and external peripherals 169 .
FIG. 2 is a block diagram illustrating details of a digital signal processor integrated circuit 200 suitable but not essential for use in this invention (prior art). The digital signal processor integrated circuit 200 includes central processing unit 1 , which is a 32-bit eight-way VLIW pipelined processor. Central processing unit 1 is coupled to level one instruction cache 121 included in digital signal processor integrated circuit 200 . Digital signal processor integrated circuit 200 also includes level one data cache 123 . Digital signal processor integrated circuit 200 also includes peripherals 4 to 9 . These peripherals preferably include an external memory interface (EMIF) 4 and a direct memory access (DMA) controller 5 . External memory interface (EMIF) 4 preferably supports access to supports synchronous and asynchronous SRAM and synchronous DRAM. Direct memory access (DMA) controller 5 preferably provides 2-channel auto-boot loading direct memory access. These peripherals include power-down logic 6 . Power-down logic 6 preferably can halt central processing unit activity, peripheral activity, and phase lock loop (PLL) clock synchronization activity to reduce power consumption. These peripherals also include host ports 7 , serial ports 8 and programmable timers 9 .
Central processing unit 1 has a 32-bit, byte addressable address space. Internal memory on the same integrated circuit is preferably organized in a data space including level one data cache 123 and a program space including level one instruction cache 121 . When off-chip memory is used, preferably these two spaces are unified into a single memory space via the external memory interface (EMIF) 4 .
Level one data cache 123 may be internally accessed by central processing unit 1 via two internal ports 3 a and 3 b . Each internal port 3 a and 3 b preferably has 32 bits of data and a 32-bit byte address reach. Level one instruction cache 121 may be internally accessed by central processing unit 1 via a single port 2 a . Port 2 a of level one instruction cache 121 preferably has an instruction-fetch width of 256 bits and a 30-bit word (four bytes) address, equivalent to a 32-bit byte address.
Central processing unit 1 includes program fetch unit 10 , instruction dispatch unit 11 , instruction decode unit 12 and two data paths 20 and 30 . First data path 20 includes four functional units designated L 1 unit 22 , S 1 unit 23 , M 1 unit 24 and D 1 unit 25 and 16 32-bit A registers forming register file 21 . Second data path 30 likewise includes four functional units designated L 2 unit 32 , S 2 unit 33 , M 2 unit 34 and D 2 unit 35 and 16 32-bit B registers forming register file 31 . The functional units of each data path access the corresponding register file for their operands. There are two cross paths 27 and 37 permitting access to one register in the opposite register file each pipeline stage. Central processing unit 1 includes control registers 13 , control logic 14 , and test logic 15 , emulation logic 16 and interrupt logic 17 .
Program fetch unit 10 , instruction dispatch unit 11 and instruction decode unit 12 recall instructions from level one instruction cache 121 and deliver up to eight 32-bit instructions to the functional units every instruction cycle. Processing occurs simultaneously in each of the two data paths 20 and 30 . As previously described each data path has four corresponding functional units (L, S, M and D) and a corresponding register file containing 16 32-bit registers. Each functional unit is controlled by a 32-bit instruction. The data paths are further described below. A control register file 13 provides the means to configure and control various processor operations.
FIG. 3 illustrates the pipeline stages 300 of digital signal processor core 110 (prior art). These pipeline stages are divided into three groups: fetch group 310 ; decode group 320 ; and execute group 330 . All instructions in the instruction set flow through the fetch, decode, and execute stages of the pipeline. Fetch group 310 has four phases for all instructions, and decode group 320 has two phases for all instructions. Execute group 330 requires a varying number of phases depending on the type of instruction.
The fetch phases of the fetch group 310 are: Program address generate phase 311 (PG); Program address send phase 312 (PS); Program access ready wait stage 313 (PW); and Program fetch packet receive stage 314 (PR). Digital signal processor core 110 uses a fetch packet (FP) of eight instructions. All eight of the instructions proceed through fetch group 310 together. During PG phase 311 , the program address is generated in program fetch unit 10 . During PS phase 312 , this program address is sent to memory. During PW phase 313 , the memory read occurs. Finally during PR phase 314 , the fetch packet is received at CPU 1 .
The decode phases of decode group 320 are: Instruction dispatch (DP) 321 ; and Instruction decode (DC) 322 . During the DP phase 321 , the fetch packets are split into execute packets. Execute packets consist of one or more instructions which are coded to execute in parallel. During DP phase 322 , the instructions in an execute packet are assigned to the appropriate functional units. Also during DC phase 322 , the source registers, destination registers and associated paths are decoded for the execution of the instructions in the respective functional units.
The execute phases of the execute group 330 are: Execute 1 (E1) 331 ; Execute 2 (E2) 332 ; Execute 3 (E3) 333 ; Execute 4 (E4) 334 ; and Execute 5 (E5) 335 . Different types of instructions require different numbers of these phases to complete. These phases of the pipeline play an important role in understanding the device state at CPU cycle boundaries.
During E1 phase 331 , the conditions for the instructions are evaluated and operands are read for all instruction types. For load and store instructions, address generation is performed and address modifications are written to a register file. For branch instructions, branch fetch packet in PG phase 311 is affected. For all single-cycle instructions, the results are written to a register file. All single-cycle instructions complete during the E1 phase 331 .
During the E2 phase 332 , for load instructions, the address is sent to memory. For store instructions, the address and data are sent to memory. Single-cycle instructions that saturate results set the SAT bit in the control status register (CSR) if saturation occurs. For single cycle 16 by 16 multiply instructions, the results are written to a register file. For M unit non-multiply instructions, the results are written to a register file. All ordinary multiply unit instructions complete during E2 phase 322 .
During E3 phase 333 , data memory accesses are performed. Any multiply instruction that saturates results sets the SAT bit in the control status register (CSR) if saturation occurs. Store instructions complete during the E3 phase 333 .
During E4 phase 334 , for load instructions, data is brought to the CPU boundary. For multiply extension instructions, the results are written to a register file. Multiply extension instructions complete during the E4 phase 334 .
During E5 phase 335 , load instructions write data into a register. Load instructions complete during the E5 phase 335 .
FIG. 4 illustrates an example of the instruction coding of instructions used by digital signal processor core 110 (prior art). Each instruction consists of 32 bits and controls the operation of one of the eight functional units. The bit fields are defined as follows. The creg field (bits 29 to 31 ) is the conditional register field. These bits identify whether the instruction is conditional and identify the predicate register. The z bit (bit 28 ) indicates whether the predication is based upon zero or not zero in the predicate register. If z=1, the test is for equality with zero. If z=0, the test is for nonzero. The case of creg=0 and z=0 is treated as always true to allow unconditional instruction execution. The creg field is encoded in the instruction opcode as shown in Table 1.
TABLE 1 Conditional creg z Register 31 30 29 28 Unconditional 0 0 0 0 Reserved 0 0 0 1 B0 0 0 1 z B1 0 1 0 z B2 0 1 1 z A1 1 0 0 z A2 1 0 1 z A0 1 1 0 z Reserved 1 1 1 x
Note that “z” in the z bit column refers to the zero/not zero comparison selection noted above and “x” is a don't care state. This coding can only specify a subset of the 32 registers in each register file as predicate registers. This selection was made to preserve bits in the instruction coding.
The dst field (bits 23 to 27 ) specifies one of the 32 registers in the corresponding register file as the destination of the instruction results.
The scr2 field (bits 18 to 22 ) specifies one of the 32 registers in the corresponding register file as the second source operand.
The scr1/cst field (bits 13 to 17 ) has several meanings depending on the instruction opcode field (bits 3 to 12 ). The first meaning specifies one of the 32 registers of the corresponding register file as the first operand. The second meaning is a 5-bit immediate constant. Depending on the instruction type, this is treated as an unsigned integer and zero extended to 32 bits or is treated as a signed integer and sign extended to 32 bits. Lastly, this field can specify one of the 32 registers in the opposite register file if the instruction invokes one of the register file cross paths 27 or 37 .
The opcode field (bits 3 to 12 ) specifies the type of instruction and designates appropriate instruction options. A detailed explanation of this field is beyond the scope of this invention except for the instruction options detailed below.
The s bit (bit 1 ) designates the data path 20 or 30 . If s=0, then data path 20 is selected. This limits the functional unit to L 1 unit 22 , S 1 unit 23 , M 1 unit 24 and D 1 unit 25 and the corresponding register file A 21 . Similarly, s=1 selects data path 20 limiting the functional unit to L 2 unit 32 , S 2 unit 33 , M 2 unit 34 and D 2 unit 35 and the corresponding register file B 31 .
The p bit (bit 0 ) marks the execute packets. The p-bit determines whether the instruction executes in parallel with the following instruction. The p-bits are scanned from lower to higher address. If p=1 for the current instruction, then the next instruction executes in parallel with the current instruction. If p=0 for the current instruction, then the next instruction executes in the cycle after the current instruction. All instructions executing in parallel constitute an execute packet. An execute packet can contain up to eight instructions. Each instruction in an execute packet must use a different functional unit.
FIG. 5 illustrates the encoding process 500 of video encoding according to the prior art. Many video encoding standards use similar processes such as represented in FIG. 5 . Encoding process 500 begins with the n th (current) frame F n 501 . Frequency transform block 502 transforms a macroblock of the pixel data into the spatial frequency domain. This typically involves a discrete cosine transform (DCT). This frequency domain data is quantized in quantization block 503 . This quantization typically takes into account the range of data values for the current macroblock. Thus differing macroblocks may have differing quantizations. In accordance with the H.264 standard, in the base profile the macroblock data may be arbitrarily reordered via reorder block 504 . As will be explained below, this reordering is reversed upon decoding. Other video encoding standards and the H.264 main profile transmit data for the macroblocks in strict raster scan order. The quantized data is encoded by entropy encoding block 505 . Entropy encoding employs fewer bits to encode more frequently used symbols and more bits to encode less frequency used symbols. This process reduces the amount of encoded that must be transmitted and/or stored. The resulting entropy encoded data is the encoded data stream. This invention concerns content adaptive binary arithmetic coding (CABAC) which will be further described below.
Video encoding standards typically permit two types of predictions. In inter-frame prediction, data is compared with data from the corresponding location of another frame. In intra-frame prediction, data is compared with data from another location in the same frame.
For inter prediction, data from n−1 th (previous) frame F n-1 510 and data from the n th frame F n 501 supply motion estimation block 511 . Motion estimation block 511 determines the positions and motion vectors of moving objects within the picture. This motion data is supplied to motion compensation block 512 along with data from n−1 th frame F n-1 510 . The resulting motion compensated frame data is selected by switch 513 for application to subtraction unit 506 . Subtraction unit 506 subtracts the inter prediction data from switch 513 from the input frame data from n th frame F n 501 . Thus frequency transform block 502 , quantization block 503 , reorder block 504 and entropy encoding block 505 encode the differential data rather than the original frame data. Assuming there is relatively little change from frame to frame, this differential data has a smaller magnitude than the raw frame data. Thus this can be expressed in fewer bits contributing to data compression. This is true even if motion estimation block 511 and motion compensation block 512 find no moving objects to code. If the n th frame F n and the n−1 th frame F n-1 are identical, the subtraction unit 506 will produce a string of zeros for data. This data string can be encoded using few bits.
The second type of prediction is intra prediction. Intra prediction predicts a macroblock of the current frame from another macroblock of the current frame. Inverse quantization block 520 receives the quantized data from quantization block 503 and substantially recovers the original frequency domain data. Inverse frequency transform block 521 transforms the frequency domain data from inverse quantization block 520 back to the spatial domain. This spatial domain data supplies one input of addition unit 522 , whose function will be further described. Encoding process 500 includes choose intra predication unit 514 to determine whether to implement intra prediction. Choose intra prediction unit 514 receives data from n th frame F n 501 and the output of addition unit 522 . Choose intra prediction unit 514 signals intra prediction intra predication unit 515 , which also receives the output of addition unit 522 . Switch 513 selects the intra prediction output for application to the subtraction input of subtraction units 506 and an addition input of addition unit 522 . Intra prediction is based upon the recovered data from inverse quantization block 520 and inverse frequency transform block 521 in order to better match the processing at decoding. If the encoding used the original frame, there might be drift between these processes resulting in growing errors.
Video encoders typically periodically transmit unpredicted frames. In such an event the predicted frame is all 0's. Subtraction unit 506 thus produces data corresponding to the n th frame F n 501 data. Periodic unpredicted or I frames limits any drift between the transmitter coding and the receive decoding. In a video movie a scene change may produce such a large change between adjacent frames that differential coding provides little advantage. Video coding standards typically signal whether a frame is a predicted frame and the type of prediction in the transmitted data stream.
Encoding process 500 includes reconstruction of the frame based upon this recovered data. The output of addition unit 522 supplies deblock filter 523 . Deblock filter 523 smoothes artifacts created by the block and macroblock nature of the encoding process. The result is reconstructed frame F′ n 524 . As shown schematically in FIG. 5 , this reconstructed frame F′ n 524 becomes the next reference frame F n-1 510 .
FIG. 6 illustrates the corresponding decoding process 600 . Entropy decode unit 601 receives the encoded data stream. Entropy decode unit 601 recovers the symbols from the entropy encoding of entropy encoding unit 505 . This invention is applicable to CABAC decoding. Reorder unit 602 assembles the macroblocks in raster scan order reversing the reordering of reorder unit 504 . Inverse quantization block 603 receives the quantized data from reorder unit 602 and substantially recovers the original frequency domain data. Inverse frequency transform block 604 transforms the frequency domain data from inverse quantization block 603 back to the spatial domain. This spatial domain data supplies one input of addition unit 605 . The other input of addition input 605 comes from switch 609 . In inter prediction mode switch 609 selects the output of motion compensation unit 607 . Motion compensation unit 607 receives the reference frame F′ n-1 606 and applies the motion compensation computed by motion compensation unit 512 and transmitted in the encoded data stream.
Switch 609 may also select an intra prediction mode. The intra prediction is signaled in the encoded data stream. If this is selected, intra prediction unit 608 forms the predicted data from the output of adder 605 and then applies the intra prediction computed by intra prediction block 515 of the encoding process 500 . Addition unit 605 recovers the predicted frame. As previously discussed in conjunction with encoding, it is possible to transmit an unpredicted or I frame. If the data stream signals that a received frame is an I frame, then the predicted frame supplied to addition unit 605 is all 0's.
The output of addition unit 605 supplies the input of deblock filter 610 . Deblock filter 610 smoothes artifacts created by the block and macroblock nature of the encoding process. The result is reconstructed frame F′ n 611 . As shown schematically in FIG. 6 , this reconstructed frame F′ n 611 becomes the next reference frame F n-1 606 .
The deblocking filtering of deblock filter 523 and deblock 610 must be the same. This enables the decoding process to accurately reflect the input frame F n 501 without error drift. The H.264 standard has a specific, very detailed decision matrix and corresponding filter operations for this process. The standard deblock filtering is applied to every macroblock in raster scan order. This deblock filtering smoothes artifacts created by the block and macroblock nature of the encoding. The filtered macroblock is used as the reference frame in predicted frames in both encoding and decoding. The encoding and decoding apply the identical processing the reconstructed frame to reduce the residual error after prediction.
Current CABAC implementation for the H.246 standard have limited throughput because its arithmetic coding engine is limited to encoding/decoding a single binary symbol (bin) per cycle. Thus to meet performance requirements of high definition video bit-streams, the CABAC engine needs to run at extremely high frequencies. This either consumes a significant amount of power or is not feasible. Other standards such as SVC, MVC and China AVS have similar issues.
Context-Adaptive Binary Arithmetic Coding (CABAC) is one of two entropy coding techniques used by the video coding standard H.264. This coding compresses the video bit-stream. In the standard H.264 CABAC, the significance map information dominates the total number bins in the average case while the coefficient level information dominates in the worst case (maximum number of bins per macroblock). For a typical 720p resolution video, the significance map bins are 47% of the bins when QP=22 and 39% when QP=27 in the average case. For a typical 720p resolution video, the coefficient level bins are 60% of the total bins when QP=22 and 52% when QP=27 in the worst case. Together these two types of syntax elements make up 69% for QP=22 and 54% for QP=27 in the average case, and 98% of the bins for both QP=22 and QP=27 in the worst case. Accordingly, this description focuses these two syntax elements to demonstrate that this invention increases throughput during the encoding/decoding. Note that this invention can be extended to all the other syntax element types.
Context adaptive binary arithmetic coding (CABAC) employs recursive interval subdivision. The next subinterval size is the product of a current subinterval range and the estimated probability of the least probable symbol (LBS). When encoding the next subinterval is selected based upon whether the current symbol is encoded as a LBS or a most probable symbol (MPS). When decoding the value of the next bin (LPS/MPS) is determined by which subinterval includes the offset. In either encoding or decoding, the current interval range has a limited bit precision requiring renormalization when the range becomes too small.
A set of carefully chosen probabilities are used in bin encoding and decoding. Bins of the same type with the same probability distribution and character are grouped together in contexts. The probabilities used for each context are modeled via a process called source modeling. Bins generally have non-stochastic distributions requiring continual updates by a context modeler. In coding the interval is recursively divided based upon whether the bins encoded are LPS or MPS. The encoding process tracks a current interval range R and a position of the lowest value L. For each bin the corresponding context determines the division between the portion of the range devoted to the LPS and the MPS. The range R and lowest value L are reset following each bin determination as shown in the following pseudo code which assumes the most probable symbol is 0:
If Input = 0 R n+1 = R n *P A (0) L n+1 = L else R n+1 = R n *P A (1) L n+1 = L n + R n *P(0)
where: P A (0) is the probability of 0 taken from the corresponding context A; and P A (1) is the probability of 1 taken from the corresponding context A. After all binary bits are encoded the final L is a binary fraction corresponding to the sequence of bins. Decoding involves a reverse process. A bin is decoded by identifying which subinterval the quantity L is located. The size of the subinterval is determine by the probability state of the context of the bin. The next comparison is based upon the results of all prior decodings. In practice the context may change for each bin in encoding and decoding.
The H.264 coding includes significance maps to mark the locations of zero and non-zero coefficients. The significance map information includes significant_coeff_flag and last_significant_coeff_flag syntax elements. The significance map uses 0 and 1 to mark the location of non-zero coefficients. A 0 in the significant_coeff_flag indicates that the corresponding coefficient is zero. These coefficients are not further coded but only noted in the significance map. A 1 in the significant_coeff_flag indicates the corresponding coefficient is non-zero. A significant_coeff_flag with value 1 is followed by a last_significant_coeff_flag to indicate whether this is the last non-zero coefficient in the transform. The non-zero coefficients levels then are separately encoded. This non-zero coefficient level information consists of the syntax elements coeff_abs_level_minus1 and coeff_sign_flag. Unlike the significance map, binarization is required on coeff_abs_level_minus1 to map the syntax elements to binary symbols.
This invention uses a parallel arithmetic coding scheme that can encode and decode multiple (N) bins at a time. A 2-bin per cycle arithmetic coding engine can be used on the significance map bins as well as coefficient level bins to reduce the required number of cycles. One issue with an N-bin per cycle coding is how to address the case when the number of bins does not equal a multiple of N. For a 2-bin per cycle case his invention inserts a dummy bin for odd runs of significance map elements and coefficient level elements. Simulations indicate that this results in a bin increase of less than 1.5%. Since the dummy bin is always a zero, a highly skewed probability can be used for the encoding/decoding dummy bins resulting in a negligible increase in bits. Thus the compression efficiency remains nearly the same. For the case of a probability pf 0.01, the increase in bits is about 0.03%.
During encoding the values for a sequence of bins to be compressed are known a priori. Thus the contexts to be used for each bin are also known and multiple (N) bins can be encoded in parallel. For example, suppose the next two bins belong to respective contexts A and B. Two bins can be can encoded at the same time using the probabilities shown in Table 2.
TABLE 2
First Bin
Second Bin
Probability
0
0
(1 − P A [1]) * (1 − P B [1])
0
1
(1 − P A [1]) * P B [1]
1
0
P A [1] * (1 − P B [1])
1
1
P A [1] * P B [1]
CABAC uses adaptive contexts to improve its compression efficiency. Each syntax element (and in some cases each bin position within the syntax element) has its own set of contexts which dictate the probabilities that should be used to encode/decode that bin. To properly decode 2-bins at a time, the context of each bin must be know beforehand. In addition, the two bins may have different contexts and different probability distributions.
This becomes problem when performing 2-bin decoding across syntax elements and codewords. Coding across syntax elements means that the two bins may or may not belong to the same element. At the decoder the syntax element and thus context of the two bins are not known a priori. Specifically, the context of the first bin may be known, but syntax element to which the second bin belongs may not be known until the first bin is decoded. This is a problem since both bins are decoded simultaneously. The second bin can be a bin in the current syntax element or the first bin in the next syntax element. Thus the second bin can be one of two different syntax elements, neither of which must to be the same as the first bin. For instance, in coding the significance map bins, the first bin may be known as a significant_coeff_flag, but it is not known whether the second bin is significant_coeff_flag or last_coeff_flag. This depends whether the first bin is a 0 or 1. This is a particularly severe issue for the coefficient level bins where the first bin of the coeff_abs_level_minus1 codewords has a different context than the rest of the bins. Failing to properly identify the transition between codewords immediately and thus assigning the wrong context to this first bin can cause a 5% increase in number of bits.
This invention conditions the probabilities of the second bin based on the first bin and uses these conditional probabilities to build the probabilities for the alphabet table used for 2-bin arithmetic coding engine. For instance, assume that the first bin is in context A with probability A. If the first bin is a zero then the second bin is in context B with probability B; if the first bin is a one then the second bin is in context C with probability C. The probability table can then be built as shown in Table 3.
TABLE 3 First Bin Second Bin Probability 0 0 (1 − P A [1]) * (1 − P B [1]) 0 1 (1 − P A [1]) * P B [1] 1 0 P A [1] * (1 − P C [1]) 1 1 P A [1] * P C [1] FIGS. 7 a and 7 b illustrate the difference between the regular 1-bin decoding versus 2-bin decoding. In general there are no constraints on context B and C. The technique of Table 3 covers where both bins are of the same context, either context B or C is equal to context A. In that case the probabilities state update for the context must be taken into account prior to the encoding/decoding. Thus the probability of B or C could be the updated probability of A. Alternatively, contexts B and C could both be different from context A requiring separate computation.
The context management can be simplified by skipping the probability state update as described above for the second bin when the contexts of both bins are the same. As a result, the probability state of the context is updated every two bins. The probability state of context B and/or C equal non-updated probability state of context A during encoding/decoding, and a full update is performed after the encoding/decoding. While this impacts the probability estimate, simulations show that this has negligible impact on coding efficiency.
Because significance map information is immediately followed by coefficient level information, a 2-bin engine can code both sets of data without flushing in between. This reduces the number of bits that are generated. Accordingly dummy bins are only need inserted after coefficient level bins.
FIGS. 7 a and 7 b illustrate examples of encoding two bins according to the prior art ( FIG. 7 a ) and according to the invention ( FIG. 7 b ). FIG. 7 a illustrates that the two bin encoding according to the prior art requires two cycles. For the first bin the prior art process begins with range R 1 and value L 1 . The updated threshold L 2 and range R 2 for this bin is determined by the probabilities of the corresponding context A, P A [0] and P A [1]. If the first bit to be encoded is 0, then the prior art process branches to branch B for the second bin. Branch B for encoding the second bin has a range R 2B =R 1 *PA[0] and a probability L 2B =L 1 corresponding to the lower bound on the 0 portion of the range R 1 . The next updated range R 3 and threshold L 3 are set by the probability state of the corresponding context B, PB[0] and P B [1]. If the bit to be encoded is 1, then the prior art process branches to branch C for the second bin. Branch C for encoding the second bin has a range R 2C ,=R 1 *P A [1] and L 2C =L 1 +R 1 *P A [0] corresponding to the lower bound of the 1 portion of range R 1 . The nest updated range R 3 and threshold L 3 are set by the probability state of the corresponding context C, P C [0] and P C [1]. This process repeats in the prior art until the number of bins to be encoded are consumed. Decoding proceeds on a similar path. The comparison of a current offset to the current interval L from the corresponding context determines whether the current bit is decoded as a 0 or as a 1. Note this prior art process requires two sequential comparisons: a first comparison with interval L 1 +R 1 *P A [0]; and a second comparison with interval L 2B +R 2 *P B [0] if the first bin is decoded 0 or with interval L 2C +R 2 *P C [0] if the first bin is decoded 1.
FIG. 7 b illustrates a two-bin encoding according to this invention. Two bins to be encoded determine the resulting range and interval. If the two bins to be encoded are 00, then the range is R 3-00 =R 1 *P A [0]*P B [0] and threshold is L 3-00 =L 1 . If the two bins to be encoded are 01, then the range is R 3-01 =R 1 *P A [ ]*P B [1] and the threshold is L 3-01 =L 1 +R 1 *P A [0]*P B [0]. If the two bins to be encoded are 10, then the range is R 3-10 =R 1 *P A [1]*P C [0] and the threshold is L 3-10 =L 1 +R 1 *P A [0]. If the two bins to be encoded are 11, then the range is R 3-11 =R 1 *P A [1]*P C [1] and the threshold is L 3-11 =L 1 +R 1 *(1-P A [1])*P C [1]. In general the context for the second bin may differ from the context of the first bin. Further the context of the second bin may be dependent upon the value of the first bit, thus the context for B and C may differ. However, these contexts are dependent upon the two bins to be encoded and the context for the second bin is known. Therefore the ranges and thresholds are all determinable in advance. Thus two bins may be encoded in a single pass without requiring a conditional branch in software. In general plural bins N may be encoded using 2 N intervals with 2 N −1 thresholds.
Decoding involves an inverse process. The current offset is compared with the four intervals illustrated in FIG. 7 b . The two bins decode to 00 if the current offset Off is less than L 3-01 . The two bins decode to 01 if L 3-01 <Off<L 3-10 . The two bins decode to 10 if L 3-10 <Off<L 3-11 . Finally, the two bins decode to 11 if Off>L 3-11 . Note particularly that thresholds L 3-00 , L 3-01 , L 3-10 and L 3-00 can be computed based upon information available before the first and second bins are decoded. Thus two to N bins can be decoded in a single pass.
As previously noted, this approach can be extended from a 2-bin engine to an N-bin engine that encodes or decodes N bins at a time. This approach can be applied to all sets of syntax elements as previously mentioned, not just the significance maps and coefficient levels of this example. It is possible to use N-bin engine only on certain elements and use a single bin engine for the others. This could be uses with significance map and coefficient levels. If an N-bin engine is used on all syntax elements, dummy bins only need to be inserted at the end of the slice after the last syntax element.
FIG. 8 is an example decision tree used to determine the possible contexts for significance map for decoding N=2 bins per cycle. A similar decision tree can be constructed for any other set of syntax elements. The decision tree 800 of FIG. 8 covers the significance maps significant_coeff_flag and last_significant_coeff_flag. The three possible context types for each bin significant_coeff_flag (sig), last_significant_coeff_flag (last) and dummy. A leaf with end indicates that the significance map has been decoded, while a leaf with next indicates that the next N=2 can begin decoding and we should return to the root of the tree. The first bin (1) of the N=2 binary symbols can either be sig or last. Depending on the coding of the first bin (1), branches for the second bin (2) and the next first bin (next) can be constructed. The variable i keeps track of the number of current nonzero coefficients and ensures that it does not exceed i1 which is the total number of coefficient positions coeff_ctr. Once i equals i1, the process is completed and the significance map designated by end. If i equals i1 at the first bin (1), then the second bin (2) will be a dummy.
Starting at node 801 , bin (1) may be decoded as a significance bin (sig) 810 or as a last bin (last) 830 . If bin (1) is a significance bin 810 , then the context of the following bin depends upon the coding of this bin. A decoded 1 at node 810 means that bin (2) is a last bin (node 811 ). The variable i is incremented at node 811 . A further 1 coding means that the following bin is an end at node 812 . A further 0 coding goes to test of node 813 . If i≧i1, then the current position is at the maximum position and thus the end at node 814 . If i<i1, then the following bin is sig(next) at node 815 . The next set of N=2 binary symbols can be decoded with the first bin being a sig by returning to node 810 . A 0 coding at node 810 causes variable i to increment. At test node 816 if i≧i1, then the followings bins are dummy(2) followed by end of the significance map at node 817 . At test node 816 if i<i1, then the following bin is sig( 2 ) at node 818 . For a further 1 coding the following bin is last(next) at node 819 and the next set of N=2 binary symbols can be decoded with the first bin being a last by returning to node 830 . For a further 0 coding variable i increments. At test node 820 if i≧i1, then the end of the significance map is reached at node 821 . At test node 820 if i<i1, then the next bin is sig(next) 822 and the next set of N=2 binary symbols can be decoded with the first bin being a sig by returning to node 810 .
Following node 830 , variable i increments. Upon a 1 coding the following bins are dummy( 2 ) and end(next) at node 831 . Upon a 0 coding the sequence advances to test node 832 . At test node 832 if i≧i1, then the following bins are dummy( 2 ) and the end of the significance map at node 833 . At test node 832 if i<i1, then the following bin is sig( 2 ) 834 . For a further 1 coding the following bin is last(next) at node 835 and the next set of N=2 binary symbols can be decoded with the first bin being a last by returning to node 830 . For a further 0 coding the sequence advances to test node 836 . At test node 836 if i≧i1, then the following bin is the end of the significance map at node 837 . At test node 836 if i<i1, then the following bin is sig(next) 838 and the next set of N=2 binary symbols can be decoded with first bin being a sig by returning to node 810 .
The preferred embodiment described in this application addresses the CABAC engine in the video standard H.264. However, one skilled in the art would realize that this technique can be applied to other standard such as SVC, MVC, China AVS, etc.
The prior art H.264 CABAC uses a single bin per cycle engine for arithmetic encoding done in H.264. For our high performance CABAC, this invention uses multi-bit per cycle engine, such as a 2-bin per cycle engine, for the significance map and the coefficient levels to increase the overall throughput. Applying a 2-bin/cycle coding on both the significance map bins and coefficient levels, the overall CABAC throughput and performance can potentially be improved by 1.5 to 2 times for the average 720p bit-stream (QP=22). With N-bin per cycle coding, this throughput can be further increased. This reduces the operating frequency requirements and power consumption. | A method of context adaptive binary arithmetic coding and decoding groups a plurality N binary symbols in corresponding syntax elements and divides a range into 2 N subranges based upon corresponding contexts. The invention encodes data by selecting an offset determined by the probability states of the context of the N binary symbols. Decoding is similar with the place of the coded offset within the 2 N subranges determining the syntax decoding. When the total number of binary symbols to be coded does not equal an integral multiple of N, the invention codes dummy binary symbols at the end of a grouping of a plurality N binary symbols. Probability state updates occur only following every N binary symbols. | 7 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application is related to application Ser. No. 428,340 filed Sep. 29, 1982 entitled "INTEGRAL DEVICE FOR GARAGE DOOR OPENER" in which the inventor is Kiyoshi Iha and which is assigned to the assignee of the present invention and it is also related to application Ser. No. 428,328 filed Sep. 29, 1982 entitled "COLLAPSIBLE GARAGE DOOR" now U.S. Pat. No. 4,460,030 which issued on July 17, 1984 in which the inventors are Kazuo Tsunemura, Kiyoshi Iha and Anthony T. Janiszewski which is assigned to the assignee of the present application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to garage door openers and in particular to a novel garage door opener which can be shipped in units and easily and simply assembled and installed.
2. Description of the Prior Art
The present garage door openers are sold as units which are to be connected to garage or other doors which are separately manufactured and installed. Such garage doors are very heavy which makes them difficult to open and are very expensive. Certain of the doors are too light and have poor insulation and security. The garage doors are mounted with steel hardware on rails and are difficult to assemble and are noisy to install. The garage doors require substantial space in the ceiling above the door when in the opened position.
Present day garage doors and openers require frequent maintenance, painting, spring adjustment and lubrication. Also, the present garage door openers are unsafe as, for example, when a spring fails which causes the door to fall and also the emergency release may be inaccessible which could result in injury to personnel. Present day garage door openers are normally installed after the door has been installed and, thus, a two step installation is required where first the garage door is mounted and then subsequently the garage door opener is connected to the garage door to actuate it. Such installations require additional wiring of the receiver and switches and each installation is different and, thus, the obstruction reversing forces, the limit switches at the top and bottom and the other parameters for the door and the opener are different for each installation.
This results in dangerous situations in that the installation may be improperly connected and also the various adJustments may be improperly made resulting in injury and even death to personnel. For example, in garage door openers of the prior art, since each door has different weight and requires different pull-down and pull-up force it is necessary to have a motor which is larger than would be required for other doors and garage door openers. This leads to excessive speeds and forces which can be applied to the garage door which can result in injury. Also, since the weight of each door varies, the obstruction detecting force is made adJustable by either the installer or the home owner and if such adjustment is made to be too tight, the door may not reverse if it encounters a child, for example, and this has resulted in the death of children.
SUMMARY OF THE INVENTION
The present invention comprises a fully integrated automatic garage door wherein the door with its guide rails and the door operator and controls are constructed at the factory and shipped in modular units such that it can be easily installed by the home owner or installers and which does not have any adjustments which are to be made by the home owner or the installer. Such adjustments can be made at the factory and, thus, each installation will be properly adjusted substantially improving the safety of such units.
The garage door opener is shipped to the installation site with two side frame units and a spreader frame unit with a drive shaft which can be detachably connected to the side unit at the location where the door is to be installed. The door comprises thermal core panels which are light weight have improved insulation and provide improved security.
The installation is simple and quick. The unit results in improved appearance over prior art doors and operators and there are no external units which are attached to the structure.
A compact folding stacking door is provided so that the minimum space is utilized and the unit is maintenance free and has long life.
The garage door and operator is designed to have maximum safety in that the preset forces are set at the factory and cannot be adjusted by the home owner or installer so as to render the unit dangerous. Failure of the spring will not cause the door to fall and there is an easily accessible emergency release if it is desired to disconnect the door from the opener unit.
The unit is convenient and compact in that the garage door opener is integrally formed with the garage door and its mechanism.
The various electrical wiring for the accessories and built-in features such as the lights are pre-wired and no extra wiring is required for the unit. The efficiency of the operator is optimized and the units are completely self-contained.
Other objects, features and advantages of the invention will be readily apparent from the following description of certain preferred embodiments thereof taken in conjunction with the accompanying drawings, although variations and modifications may be effected without departing from the spirit and scope of the novel concepts of the disclosure and in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the garage door and operator installed;
FIG. 2 is a partial top sectional view illustrating the invention;
FIG. 3 is a perspective view illustrating the method of assembling the garage door and opener;
FIG. 4 is another perspective view illustrating the door and operator being assembled;
FIG. 5 illustrates the door and opener mechanism assembled before attaching it to the door opening;
FIG. 6 is a perspective view illustrating the door and opener attached to the door opening;
FIG. 7 is a sectional view illustrating the drive shaft and the cables for the left side of the door;
FIG. 8 is a top view illustrating the mechanism;
FIG. 9 is a perspective exploded view illustrating the invention;
FIG. 10 is a partially cut-away end view of the invention;
FIG. 10A illustrates the clutch
FIG. 11 illustrates the door in the upper stored position;
FIG. 12 llustrates the cable mechanism;
FIG. 13 illustrates the cable mechanism with the door in the opened position; and
FIG. 14 is a sectional view through the door panels.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates the garage door and opener of the invention installed to cover the opening of a garage. Side headers 36 and 38 are mounted vertically on the sides of the door opening and a top header 37 is mounted to the structure at the top of the door opening. The garage door and opener 10 is connected to the headers 36, 37 and 38.
A pair of side cable drive frame assemblies 12 and 13 are connected by a spreader frame unit 14 which includes a drive shaft 16 and the members 12, 13 and 14 are shipped unassembled and can be conveniently and uniformly packaged for shipping. When the door and opener is to be assembled, the cable drive frame assemblies 12 and 13 are laid out on the floor as illustrated in FIG. 3 and the spreader frame unit 14 is connected to the cable drive frame assemblies 12 and 13 as shown, for example, in FIG. 7. The drive shaft 16 is rotatably supported at either end by bearings such as 21 and 22 illustrated in FIG. 7 which are supported by a bracket 18 connected to an angle iron 17 that extends the width of the spreader frame unit 14. The cable drive assembly frame unit 13 has a side wall 25 that supports a bearing 31 which carries a shaft 24 upon which cable reels 101 and 102 are supported. The reel 101 carries a cable 71 and the reel 102 carries a cable 73. The external end 28 of shaft 24 is splined and is received in a splined female opening 20 on the end of shaft 16 with a slide fit so that the frame units can be coupled together so that shaft 16 will turn the reels 101 and 102 when they are assembled. Bolts 26 connect the angle iron 17 to the cable drive frame assembly 13. As illustrated in FIGS. 8 and 9, the cable drive frame assembly 12 also has a splined shaft 29 which carries reels 103 and 104 and which is received in a splined end of shaft 16 within bracket 19 which is supported from the angle iron 17 as illustrated in FIG. 9. Bolts also attach angle iron 17 to the cable drive frame assembly 12. A motor 104a is mounted in cable drive frame assembly 12 as shown in FIGS. 10, 12 and 13 and drives shaft 29 through a worm 107 mounted on the output shaft of the motor which engages a gear 108 mounted on shaft 29. An emergency release clutch 109 is illustrated in FIG. 10 and is mounted between the gear 107 and the shaft 29 and a lever 111 is connected to the clutch 109. A linkage such as a table 110 extends from the clutch lever 111 to an emergency release handle 112 mounted on the side of the cable drive frame assembly 12 as illustrated in FIG. 10 so that the motor can be disconnected from drive shafts 29 and 16 at any time either to stop the motor drive or alternatively to allow manual opening and closing of the door 90. FIG. 10a illustrates the clutch in greater detail.
FIG. 4 illustrates the cable drive frame assemblies 12 and 13 after they have been attached to the spreader drive frame shaft unit 14 and a front valance panel 201 and a bottom valance panel 202 have been connected to the cable drive frame assemblies 12 and 13 so as to cover the drive shaft 14 and the angle iron 17 of the spreader frame unit 13.
The garage door 90 is formed of a plurality of door panels 80 through 84a and 86 through 89. As illustrated in FIG. 4, the door panels come pre-assembled in pairs and may be of the form of the panels illustrated in application Ser. No. 428,328 wherein each of the pairs are hinged to each other so as to fold in a first direction. Each of the cable drive assembly frame members 12 and 13 are formed with rails as, for example, the rail 56 illustrated in FIG. 2 for the cable drive assembly frame unit 13 into which rollers 62 mounted on shaft 61 can be received and which are attached to the panels 80 through 89. Other pins 50 extend from the panels 80 through 89 and ride on the outer surface of the rail 56 as illustrated in FIG. 2. The roller 62 can be received in the end of the rail 56 and proJections 57 and 58 which prevent the rollers 62 from pulling out of the rail 56.
A first pair of panels 80 and 81 are inserted into the frame members 12 and 13 with the roller 62 in rail 56, then the next pair of panels 82 and 83 are inserted with the rollers 62 into the rail 56 and the panels 81 and 82 are connected together at hinges 206 and 207 by inserting pins 208. Then the next pair of panels 84 and 85 are inserted into the frame units 12 and 13 and are connected by the hinges on the panel 83 until the entire door is assembled as illustrated in FIG. 5. After the door has been assembled, it is tilted upwardly to the vertical position illustrated in FIG. 6 and bolts 51 are utilized to connect the units 12, 13 and 14 to the headers 36, 37 and 38. For example, FIG. 2 illustrates a bolt 51 which passes through a flange 52 which is an extension of the planar member 53 of the cable drive assembly 13.
As shown in FIGS. 1 and 2, the lower panel 89 has an extension shaft 66 which is received within the confines of the cable drive assembly 13 which has side wall 54 and which carries a bracket 67 that can be clamped by bolts 68 and 69 to the drive cable 71. The drive cable 71 passes up to the drive pulley 101 as illustrated in FIG. 7. The drive cable 73 passes down through the confines of the cable drive frame assembly 13 and around the pulley 72 which is mounted by brackets 70 to the lower end of cable drive frame assembly 13. The cable 73 also attaches to the bracket 67. A counter balance spring 127 has one end attached to frame member 13 by bracket 131 as illustrated in FIG. 1 and in FIGS. 12 and 13. The upper end of spring 127 is connected to a pulley 128 and a cable 129 has one end connected to a bracket 134 connected to the frame member 12 as illustrated in FIGS. 12 and 13. A pulley 133 is also rotatably supported adjacent the top of member 12 and cable 129 passes over the pulleys 128 and 133 and is attached to the lower panel 89 of the door 90 with a suitable bracket 135. It is to be realized that both of the frame units 12 and 13 include cable drives and counter balance springs 127 and the left counter balance spring is illustrated in FIG. 1 and the right counter balance spring structure is illustrated in FIGS. 12 and 13. As shown in FIGS. 12 and 13 the cable 122 passes from pulley 103 around pulley 123 which is rotatablty supported by bracket 124 which is attached to the floor. Bracket 120 is attached to door panel 89 and to cable 122. Cable 121 passes from pulley 104 to bracket 120.
The upper ends of cable drive assembly frame members 12 and 13 have enlarged portions 41 and 43 respectively, and light covers 42 and 44 are attached to the enlarged portions 41 and 43 and lights 240 are mounted therein.
FIG. 11 is similar to FIG. 5 in application Ser. No. 428,328 which description is incorporated by reference and illustrates how the panels 80 through 89 fold up accordian-wise in the upper portions of 41 and 43 of the cable drive assembly frame units 12 and 13. FIG. 14 is a sectional view through panels 89, 88 and 87 after they have been assembled together. FIG. 14 is the same as FIG. 2 in U.S. application Ser. No. 428,328 now U.S. Pat. No. 4,460,030 the description from this application is hereby incorporated by reference.
FIG. 11 shows the door 90 in the folded or up position. Guides 401 and 402 and the rail 56 engage the rollers 62 and pins 50 to cause the panels to store as shown in FIG. 5 of Ser. No. 428,328. The hinges 206 and 207 are connected by pins 208. Hinges 305 join the panels also as shown.
FIG. 14 is a sectional view through three panels such as 87, 88 and 89. The panels are made of aluminum walls 400 which are received in extrusions 401 and 402 and are filled with styrofoam 403.
FIG. 10 illustrates a control unit 302 which is mounted in portion 41 of frame member 12 and a door actuating switch 301 is connected to the control 302 to energize the garage door opener. When this occurs the motor 104a is energized to either open or close the door in a conventional manner by driving shaft 16 to drive the reels 101, 102, 103, 104. The control unit 302 also includes a radio receiver which is connected to energize the motor 104a when energized by a remote transmitter not shown. This allows the garage door opener to be actuated remotely as, for example, by the driver of an automobile who desires to open or close the garage door. A light switch 303 is connected to the control 302 so as to allow the lights 240 within the light cover panels 42 and 44 to be energized manually. It is to be realized that the lights also turn on automatically when the garage door opener is energized to either open or close the door but the switch 303 also allows the lights to be turned on manually when desired.
The emergency release pull handle 112 actuates the clutch 109 by moving the lever 111 which disconnects the motor 104a from the shafts 29 and 16 thus allowing the door to be manually moved upwardly or downwardly under emergency conditions as when power is not available due to power failure or for other reasons. The clutch 109 disconnects the shaft 29 from shaft 16 when the lever 111 is pulled down by the handle 112 and cord 110. A similar clutch arrangement is shown in U.S. Pat. No. 4,472,910.
A power cord 306 has a plug 307 which can be connected to a suitable power outlet and merely inserting the plug 307 in the power outlet completes the wiring required for installation of the garage door and the garage door opener.
The setting of the tensions on the obstruction detecting is in a unit 321 of the control 302 and this is not readily available to the home owner or the installer since it is within the sealed control unit 302 and this adjustment is made at the factory. This can be done since the weight of the door 90 is known at the factory and this can be set to points wherein an installer or the home owner cannot make this adjustment such that it is too tight which would render the garage door opener dangerous. In other words, this is a factory setting and once set cannot be changed by the installer or home owner and, thus, the obstruction detecting mechanism will not be adjusted to a dangerous setting as can occur with prior art devices.
It is seen that this invention provides a new and novel garage door opener and although it has been described with respect to preferred embodiments, it is not to be so limited as changes and modifications can be made therein which are within the full intended scope as defined by the appended claims. | A garage door and opener which can be manufactured as separate units and shipped in pre-assembled units and which can be easily and quickly assembled and installed by one or more persons. The door and the operator are self-contained in the units and all of the wiring and apparatus including the door and rails are self-contained in the units. | 4 |
FIELD OF THE INVENTION
The present invention relates to a powdered wax particularly suited for use as a tablet polishing wax which (wax) is to carry print, to tablets polished with such wax, and to a method for preparing such powdered wax.
BACKGROUND OF THE INVENTION
It is standard practice in the pharmaceutical industry to coat or polish printed sugar tablets with waxes applied in a chlorinated or flammable hydrocarbon solvent to achieve a shiny gloss and protection for the print. Thus, typically, a print base solution containing ethanol, water, ethyl cellulose and shellac is applied to the tablets, the tablets are dried and then the dried tablets are printed. During the printing operation, talc is applied to enable the tablets to feed properly in the printing machine. After printing, the tablets are loaded into a polishing pan and a wax solution formed of various conventional waxes in a chlorinated or hydrocarbon solvent is applied over the print.
Although the above procedure has achieved some commercial success, it has been found to be lacking in several respects. The use of chlorinated solvents in the wax emulsion has been found to create a potential health problem while the use of talc in connection with the printing machines has been found to create a sanitary problem. Moreover, it unfortunately has been found that the wax coating is quite soft and does not readily protect the print. Further, if the wax coating is first applied and the tablet printed over the wax coating, the print is easily rubbed off.
It is also known to polish tablets with powdered carnauba wax. However, the shine is too hard to serve as a substrate for printing.
Accordingly, it is seen that a need exists in the tablet polishing and printing art for a wax coating and polish for tablets which will not only provide a durable shiny coating but also a substrate for printing which will retain print for extended periods.
DESCRIPTION OF THE INVENTION
In accordance with the present invention, a wax is provided which is in a fine powdered state having an average particle size of less than about 100 microns and preferably less than about 90 microns. The powdered wax of the invention is preferably comprised of beeswax (also referred to as white wax), or mixtures of beeswax and carnauba wax, although one or more other waxes may be employed in combination with the beeswax and/or carnauba wax or by themselves. Examples of such other waxes suitable for use herein include, but are not limited to, paraffin wax, polyethylene glycol waxes, other hard waxes such as candelilla wax, ozokerite, oricury, microcrystalline wax and the like.
The powdered wax of the invention may be applied as a polish to tablets to produce a durable shiny protective coating. Furthermore, the wax coating may be printed over with the print being retained for extended periods of time. In fact, the overall appearance and durability of both the print and shine is superior to that of conventionally wax-coated and printed tablets.
In addition, in accordance with the present invention, a method is provided for preparing the powdered wax described above, which method includes the steps of providing a desired wax formulation, melting the wax formulation to form a homogeneous mass, allowing the wax formulation to harden, breaking the hardened wax formulation into small pieces, milling the small pieces of wax with dry ice employing a weight ratio of wax to dry ice of within the range of from about 0.5:1 to about 5:1, preferably from about 0:5.1 to about 2:1, and then allowing the dry ice to evaporate from the milled wax formulation while maintaining the wax at a temperature of below about 5° C., thereby leaving the wax in a fine powdered state free of clumps.
In carrying out the above method, the homogeneous melted wax formulation is preferably frozen before it is broken up into small chunks prior to milling. The size of the small chunks of wax to be milled is not critical. However, for convenience, it is preferred that the wax be broken up into pieces of from about 1 to 5 microns up to about 1 to 10 centimeters in size to facilitate milling.
The milling of the frozen pieces of wax with dry ice is carried out employing conventional high speed milling apparatus such as a Fitzpatrick mill employing hammers forward through a small herring bone screen. However, other conventional milling equipment may be employed as will be apparent to those skilled in the art.
The milling procedure may be carried out as a one step procedure. However, it is preferred that the milling step be carried out stepwise so that a first portion of the dry ice will first be milled, thereafter a second larger portion of dry ice together with milled dry ice will be mixed with the wax chunks and the mix milled, and finally the remainder of the dry ice will be milled with the wax-dry ice mixture.
After the wax is milled with dry ice, a snow of dry ice and wax is formed which is kept in a cooled state as the dry ice is allowed to evaporate. The snow may be placed in conventional refrigeration apparatus to maintain the snow at a temperature of within the range of from about -5° to about 5° C. If during the dry ice evaporation period, the wax is allowed to reach temperatures of greater than about 10° C., the wax will form clumps as opposed to the desired fine powder.
The powdered wax produced by the method of the present invention is particularly suited as a polishing agent and print substrate for tablets. In fact, heretofore, where it has been attempted to powder wax, the result has been melted globs or a semi-powder-like wax product replete with clumps and therefore unsatisfactory as a polishing agent for tablets.
The following Examples represent preferred embodiments of the present invention. All temperatures are expressed in °C.
EXAMPLE 1
A fine powdered wax containing equal parts of carnauba wax and white wax particularly suitable for use as a polishing agent for sugar-coated tablets was prepared as described below.
Carnauba wax (10 kg) and white wax (10 kg) were placed in a suitably sized container and melted at 100°. The melted homogeneous wax mix was then placed in a freezer maintained at -10° C. for four hours. The resulting frozen block of wax was removed from the freezer, placed in a cloth and then broken into small chunks of average size of less than 2 inches. The wax chunks were immediately milled with dry ice in a Fitzpatrick impact mill with hammers forward high speed through a 0.15" by 17/32" long herring-bone or finer herring-bone screen, as follows. 1 Kg of milled dry ice was milled with 13 kg of dry ice chunks together with all 20 kg of the wax mix. Thereafter, the milled dry ice-wax mix was milled with another 1 kg portion of dry ice. A dry ice/wax snow was thereby formed which was spread on a tray. The tray was placed in a refrigerator maintained at about 4° C., for 12 hours, thereby allowing the dry ice to evaporate and leaving fluffy powdered wax having a fineness of 100% through #60 mesh screen and over 25% through #400 mesh screen on an Alpine sieve.
The so-formed powdered wax was placed in an air-tight container and refrigerated until used.
The 50-50 carnauba wax-white wax powder was applied as a polishing agent for sugar coated tablets to produce a durable quality shiny coating without the need for use of chlorinated hydrocarbon solvents or flammable hydrocarbon solvents. The so-polished tablets were printed over to form a durable print which was not easily rubbed off.
EXAMPLE 2
A fine powdered pure white (beeswax) wax was formed employing the procedure as described in Example 1 except that all carnauba wax was replaced with white wax.
The resulting powdered white wax was found to be of the same fineness as the Example 1 wax. | A novel powdered wax is provided which is especially adapted for use as a polishing agent for tablets and as a substrate for print carried by such tablets. A method for forming such powdered wax is also provided which includes the steps of milling pieces of wax with dry ice and then allowing the dry ice to evaporate while maintaining the milled wax at cool temperatures to prevent clumping. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This non-provisional patent application is a continuation-in-part of and claims priority from U.S. Non-Provisional patent application Ser. No. 13/965,097 filed Aug. 12, 2013, which claims priority to U.S. Provisional Patent Application No. 61/681,689 filed Aug. 10, 2012, each of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present disclosure relates to medical devices, and more particularly to medical crutches. Medical crutches are used in the medical field, often through the orthopedics department of a treatment facility. Medical crutches are often sold in the category of durable medical equipment (DME). Medical crutches can be used to support all or part of a patient's body weight. Medical crutches can be made of wood, metal, or other structural material. Medical crutches are typically configured to reach from a patient's underarm to a walking surface. Other configurations extend from the forearm, wrist area, hand, and the like.
[0003] Referring to FIG. 1 , crutches 400 are usually configured to have a fixed-length frame 402 having an arm support 404 for placement under the arm, a handle 406 that extends horizontally between two support legs 408 a , 408 b to support the weight of a patient, and a surface contact heel 410 configured to contact the ground. The legs 408 a , 408 b have a plurality of holes 412 for adjusting the position of the handle 406 , which is secured by wing nuts 414 .
[0004] Shock absorbing devices, including springs, have been used with crutches 400 to lessen the impact to a patient as the body weight is transferred to the walking surface. Traditionally, these devices have been located in the upper portion of the crutches. Further, various adjustment mechanisms have been used to modify the length of medical crutches. These adjustment mechanisms are typically difficult to operate or do not provide the ability to fine tune overall crutch length to a specific desired length.
SUMMARY
[0005] While various configurations have been attempted, there remains a need for an adjustable medical crutch having a shock absorbing device located on the lower portion of the crutch. There is also a need for a medical crutch that allows a user to easily adjust the overall length of the crutch to a specific desired length. The subject technology is equally applicable to other devices such as canes, walkers, forearm crutches, and walking sticks. The present disclosure preserves the advantages of existing medical crutches while providing new advantages not found in currently available medical crutches and overcoming many disadvantages of currently available medical crutches.
[0006] In one embodiment, the subject technology is directed to an elongated medical crutch. The crutch includes an upper portion with an arm support coupled to a handle, a lower portion with a shock absorbing system coupled to a surface contact heel, and an adjustable system. The adjustable system couples the upper portion and lower portion. The adjustable system includes a threaded rod extending from the upper portion along a longitudinal axis, a pushbutton assembly surrounding the threaded rod, and a tubular shaft capturing the pushbutton assembly and connecting the threaded rod and the lower portion. For fine adjustment of the overall length of the crutch, the threaded rod can be rotated with respect to the tubular shaft. For coarse adjustment of the overall length of the crutch, the pushbutton assembly can be actuated to disengage the pushbutton assembly from the threaded rod for sliding the tubular shaft linearly along the threaded rod. In one embodiment, the tubular shaft can define a tunnel along the longitudinal axis. Further, in one embodiment, the pushbutton assembly can include a main body having an axial bore and a transverse bore, a pushbutton extending through the transverse bore, and a spring, oriented between the pushbutton and main body to apply a force along the transverse axis.
[0007] Another aspect of the subject disclosure is directed to an elongated walking assistance device. The device includes an upper portion with a handle, a lower portion including with a shock absorbing system coupled to a surface contact heel, and an adjustable system. The adjustable system couples the upper portion and lower portion. The adjustable system includes a threaded rod extending from the upper portion along a longitudinal axis, a pushbutton assembly surrounding the threaded rod, and a tubular shaft capturing the pushbutton assembly. For fine adjustment of the overall length of the device, the threaded rod can be rotated with respect to the tubular shaft. For coarse adjustment of the overall length of the device, the pushbutton assembly can be actuated to disengage the pushbutton assembly from the threaded rod for sliding the tubular shaft linearly along the threaded rod. The elongated walking assistance device can be a cane, a walker, a forearm crutch, a walking stick, or any other walking assistance device. The pushbutton assembly can include a threaded push button. The tubular shaft of the device may define a tunnel along the longitudinal axis. The pushbutton assembly can also include a main body having an axial bore and a transverse bore, a pushbutton extending through the transverse bore, and a spring, oriented between the pushbutton and main body to apply a force along the transverse axis. The pushbutton can also have an axial bore with inner threads.
[0008] It should be appreciated that the subject technology can be implemented and utilized in numerous ways, including without limitation as a process, an apparatus, a system, a device, a method for applications now known and later developed. These and other unique features of the system disclosed herein will become more readily apparent from the following description and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The novel features which are characteristic of the crutches are set forth in the appended claims. However, the crutch, together with further embodiments and attendant advantages, will be best understood by reference to the following detailed description taken in connection with the accompanying drawing Figures.
[0010] FIG. 1 is a side view of a prior art medical crutch.
[0011] FIG. 2 is a side view of a medical crutch in accordance with the subject technology.
[0012] FIG. 3 is a side view of another embodiment of a medical crutch in accordance with the subject technology.
[0013] FIG. 4A is a perspective view of a shock absorbing system in accordance with the subject technology.
[0014] FIG. 4B is a perspective view of a shock shaft, as in the shock absorbing system of FIG. 3 in accordance with the subject technology.
[0015] FIG. 4C is a perspective view of a connector, as in the shock absorbing system of FIG. 3 in accordance with the subject technology.
[0016] FIG. 5 is a perspective view of a shock absorbing system in accordance with the subject technology.
[0017] FIG. 6 is a side view of an adjustable system in accordance with the subject technology, shown disassembled for illustrative purposes.
[0018] FIG. 7 is a side view of an adjustable system in accordance with the subject technology.
[0019] FIG. 8A is a side view of a medical crutch with a pushbutton assembly in accordance with the subject technology.
[0020] FIG. 8B is an enlarged view of a portion of the adjustable system of FIG. 8A coupled to a threaded rod in accordance with the subject technology.
[0021] FIG. 9 is a perspective view of a pushbutton assembly of in accordance with the subject technology.
[0022] FIG. 10 is an exploded view of a pushbutton assembly in accordance with the subject technology
[0023] FIG. 11 is an exploded view of a tubular shaft and a pushbutton assembly in accordance with the subject technology.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] The subject technology overcomes many of the prior art problems associated with crutch shock absorber systems while providing the user with the ability to effectively adjust the length of the crutch. The advantages, and other features of the system disclosed herein, will become more readily apparent to those having skill in the art from the following detailed description of certain preferred embodiments taken in conjunction with the drawings which set forth representative embodiments of the present invention and wherein like reference numerals identify similar structural elements. It is understood that references to the figures such as up, down, upward, downward, left, and right are with respect to the figures and not meant in a limiting sense.
[0025] Referring now to FIG. 2 , a side view of a medical crutch in accordance with the subject technology is shown generally by reference numeral 100 . The crutch 100 includes an upper portion 102 having an arm support 104 for placement under the shoulder of a user or patient. A handle 106 extends horizontally between two support legs 108 A, 108 B for the patient to hold onto. The legs 108 A, 108 B have a plurality of holes 110 which allow the handle 106 to be secured to the legs 108 A, 108 B via wing nuts 112 at various locations. The upper portion 102 is coupled to an adjustable system 114 which allows the user to adjust the crutch length along the longitudinal axis “a” to achieve their desired length. The adjustable system 114 includes an adjustable shaft 116 which runs along the axis “a” and connects to a lower portion 101 inside an absorber coupler 120 .
[0026] The lower portion 101 includes a shock absorbing system 118 which provides cushioning as a user shifts their weight onto the crutch 100 , as well as a surface contact heel 128 which provides friction between the lower portion 101 and a ground surface. The shock absorbing system 118 includes a shock 122 , housed within the absorber coupler 120 . The resistance of the shock 122 can be adjusted by turning the shock adjuster 124 . A shock shaft 126 extends from the lower end of the absorber coupler 122 . The surface contact heel 128 is secured to the lower end of the shock shaft 126 . In one embodiment, the arm support 104 and handle 106 are made of a soft material, such as rubber or a foam rubber coated material, while the other pieces are made of structural material such as anodized aluminum. One skilled in the art would recognize that alternatively, other materials which provide sufficient structural strength may be used. The medical crutch may also have additional components or features that are known in the prior art or a used with standard crutches.
[0027] Referring to FIG. 3 , a side view of another embodiment of a medical crutch in accordance with the subject technology is shown generally by reference numeral 200 . The primary difference between the crutch shown in FIG. 2 and the crutch shown in FIG. 3 is the type of adjustable system shown. In FIG. 3 , the crutch has an adjustable system of the type shown in FIG. 6 , coupled to a shock absorbing system of the type shown in FIG. 4A .
[0028] Still referring to FIG. 3 , the crutch 200 has support legs 208 A, 208 B which are affixed, at their lower end, to a frame coupler 230 . The crutch has an adjustable system 214 which includes a top plate 232 that reaches between the support legs 208 A, 208 B. A threaded rod 234 is affixed, at its top end, to the top plate 232 by a nut 236 . In other embodiments, the threaded rod 234 could be affixed to the top plate 232 by a set screw, spring pin, or the like. The threaded rod 234 extends along the longitudinal axis “a”, passing through the top plate 232 and a lower plate 238 . The frame coupler 230 and lower plate 238 include a coupler tunnel 240 and lower plate tunnel 242 , respectively, as depicted more clearly in FIG. 6 , which allow the adjustable shaft 216 to move along the longitudinal axis “a”. The adjustable shaft 216 includes a threaded top end 246 which can engage the threaded rod 234 . Thus, counter-clockwise rotation of the adjustable shaft 216 about the axis “a” forces the adjustable shaft 216 to move upward along the axis “a” with respect to the threaded rod 234 . In this way, rotation of the adjustable shaft 216 around the longitudinal axis “a” results in an adjustment in the total length of the crutch 200 . The user may adjust the length of the crutch 200 in this way to achieve a desired length based on their height and personal preferences. When the user has adjusted the crutch 200 length to reach a minimum length, the top 245 of the adjustable shaft 216 will come in contact with the bottom 247 of the top plate 232 . Clockwise rotation of the shaft 216 moves the shaft 216 downward along the axis “a.” For stability, at a maximum overall length, the top 245 is still within the lower plate 238 .
[0029] Referring now to FIG. 4A-4C , a shock absorbing system is shown generally at 218 . The shock absorbing system 218 is configured for removable attachment to the adjustable shaft 216 via a connector 250 . The connector 250 is configured for insertion into the absorber coupler 220 , where it connects with a shock 222 housed within. The connector 250 includes an axial bore 252 for receiving the adjustable shaft 216 . The connector 250 also includes an upper transverse bore 254 and a lower transverse bore 256 . When the adjustable shaft 216 is inserted into the axial bore 252 , a pin, threaded bolt, or the like may be inserted through the upper transverse bore 254 to affix the adjustable shaft 216 to the connector 250 . The connector 250 also defines a lower gap 258 . The lower gap 258 allows the connector 250 to slide over the top of a shock 222 such that a pin, threaded bolt, or the like may be inserted through the lower transverse bore 256 to affix the shock 222 to the connector 250 . The shock shaft 226 includes a hook 260 to allow for fixation to the shock 222 within the absorber coupler 220 .
[0030] Referring now to FIG. 5 , a perspective view of a shock absorbing system 218 is shown. A shock 222 is shown extending from the absorber coupler 220 . The shock 222 is affixed to the connector 250 by a lower pin 258 , which runs through the lower transverse bore 256 . The connector 250 is affixed to the adjustable shaft 216 by an upper pin 260 which runs through the upper transverse bore 254 . Within the absorber coupler 220 , the shock shaft 226 is affixed to the shock 222 via the hook 260 , shown in FIG. 4B .
[0031] The shock 222 provides a dampening means when the crutch is used. The shock 222 may be any of a variety of typical shock absorbers, such as a pneumatic shock absorber, an air over oil shock absorber, or the like. In one embodiment, a pneumatic shock is used which has an adjustable rebound control to modify the time it takes a plunger to return to the starting position. This adjustment may be made using the adjustment knob 224 . In this way, the rebound control can be adjusted depending on the user's step speed. In one embodiment, the shock 222 also has an adjustable compression force, which is a dampening force based on the air pressure delivered into the shock 222 as a result of the user's weight. This adjustment can be accomplished by the adjustment knob 224 , or any other similar adjustment mechanism. Thus, the user can easily adjust the compression distance and stiffness of the shock 222 depending on their step speed, body weight, and preferences. Alternatively, in another embodiment, the shock absorbing system 218 may include an air over oil shock which may operate at specific air pressure and includes an oil orifice inside that helps to maintain smooth movement of a piston inside of the shock.
[0032] Referring now to FIG. 6 , a side view of the adjustable system 214 is shown disassembled for illustrative purposes. The threaded rod 234 is affixed, at its top end 235 , to the top plate 232 by a nut 236 . In other embodiments, the threaded rod 234 could be affixed to the top plate 232 by a set screw, spring pin, or the like. In the embodiment shown, the threaded rod 234 extends along longitudinal axis “a”, through the lower plate 238 and the frame coupler 230 . The threaded rod 234 need not extend all the way through the frame coupler 230 , and in other embodiments the threaded rod 234 extends to a location between the bottom of the lower plate 238 and frame coupler 230 , for example. For illustrative purposes, the adjustable shaft 216 is shown separated from the threaded rod 234 . The frame coupler 230 and the lower plate 238 include a coupler tunnel 240 and a lower plate tunnel 242 , respectively, which allow the adjustable shaft 216 to move along the axis “a”. The adjustable shaft 216 includes a threaded top end 246 which can engage the threaded rod 234 .
[0033] Referring now to FIG. 7 , a side view of the adjustable system 214 is shown, adjusted to a position which would place the medical crutch very near a maximal overall length. The threaded top end 246 of the adjustable shaft 216 is shown engaging with the threaded rod 234 . The adjustable shaft 216 has been rotated in the clockwise direction around the longitudinal axis “a”, causing the adjustable shaft 216 to move downward along the axis “a”. As the adjustable shaft 216 moves further downward along the axis “a”, the total length of the crutch is increased. In the position shown, the adjustable shaft 216 is shown barely penetrating the lower plate tunnel 242 . Increasing the crutch length further, such that the adjustable shaft 216 no longer extends through the lower plate tunnel 242 runs the risk of potential instability.
[0034] Referring to FIG. 8A , a side view of a medical crutch with an adjustable system in accordance with the subject technology is shown generally by numeral 300 . Similar elements to those described in connection with the above-described embodiments are indicated with like reference numbers. Many elements are essentially the same as those of the foregoing embodiments and, thus, are not further described herein. The primary difference is that in this embodiment the adjustable system 314 includes a pushbutton assembly 327 that allows for quick and easy large adjustments as well as fine adjustments. The adjustable system 314 also includes a tubular shaft 335 which defines an axial tunnel 337 and retains the pushbutton assembly 327 . The threaded rod 334 is affixed to the upper portion 302 of the crutch 300 by a support plate 321 which extends between the legs 308 A, 308 B.
[0035] Referring now to FIG. 8B , an enlarged view of a portion of the adjustable system of FIG. 8A is shown. The pushbutton assembly 327 has a main body 329 which includes an axial bore 343 for receiving the threaded rod 334 . The main body 329 has an upper surface 339 flush with the top end 341 of the tubular shaft 335 . The pushbutton assembly 327 also includes a pushbutton 333 which can be depressed to disengage the threaded rod 334 , as depicted in FIGS. 9-10 , allowing for large adjustments in the length of the crutch 300 . The pushbutton assembly 327 is secured to the tubular shaft 335 with the pushbutton 333 locked into a transverse bore 359 in the tubular shaft 335 .
[0036] Referring now to FIGS. 9-10 , the pushbutton assembly 327 is shown. The pushbutton assembly 327 includes a main body 329 which has an axial bore 343 for receiving the threaded rod 334 and a transverse bore 345 for receiving the pushbutton 333 . The transverse bore 345 couples to the outer surface 360 of the pushbutton 333 . The pushbutton 333 is biased such that the proximal end 362 of the pushbutton 333 protrudes from the transverse bore 345 of the main body 329 . A spring 349 is located between the distal end 351 of the pushbutton 333 and the main body 329 . The spring 349 applies force along the transverse axis “b”, resisting actuation of the pushbutton 333 . The pushbutton 333 has an axial bore 353 of an inner diameter large enough to receive the threaded rod 334 . The axial bore 353 may be formed by drilling an oval bore, two overlapping bores, or one bore of a larger diameter than the threaded rod 334 . When assembled, the axial bore 353 of the pushbutton 333 generally aligns with the axial bore 343 of the main body 329 , and the threaded rod 334 extends through both axial bores 343 , 353 along the longitudinal axis “a.” The axial bore 353 of the pushbutton 333 has inner threads 347 on the side nearest the distal end 351 which, when assembly, mesh with the threaded rod 334 to resist movement along the longitudinal axis “a.” Additionally, a set screw 355 passes through the main body 329 on the side opposite the transverse bore 345 . When the set screw 355 is tightened, it applies force to the distal end 351 of the pushbutton 333 . Thus, when a threaded rod 334 is inserted through the axial bores 343 , 353 , tightening the set screw 355 causes the inner threads 347 of the pushbutton 333 to mesh tightly with the threaded rod 334 . In this way, when the set screw 355 is tight, the inner threads 347 will prevent the threaded rod 334 from moving, with respect to the pushbutton assembly 327 , along the longitudinal axis “a.” On the other hand, when the set screw 355 is loose, the proximal end 362 of the pushbutton 333 may be pressed in along the transverse axis “b” to allow the threaded rod 334 to slide freely along the longitudinal axis “a.”
[0037] Referring now to FIG. 11 , an exploded view of the tubular shaft 335 and the pushbutton assembly 327 in accordance with the subject technology are shown. The tubular shaft 335 defines an axial tunnel 337 which runs along the longitudinal axis “a.” The pushbutton assembly 327 has a main body 329 with an outer surface 366 . The outer surface 366 has a diameter which allows the main body 329 to slide into the axial tunnel 337 . When assembled, the main body 329 is housed within the axial tunnel 327 and the pushbutton 333 protrudes from the transverse bore 359 , as depicted in FIG. 8B .
[0038] Referring now to FIGS. 8A-8B , the pushbutton assembly 327 allows the user to make both fine and coarse adjustments. The pushbutton assembly 327 is retained within the axial tunnel 337 of the tubular shaft 335 . The user may depress the proximal end 362 of the pushbutton 333 to disengage the threaded rod 334 , allowing the tubular shaft 335 and pushbutton assembly 327 to slide along the longitudinal axis “a.” In this way, the user may depress the pushbutton 333 to carry out large adjustments in the overall length of the crutch 300 . When the user has reached their desired position, the user can release the pushbutton 333 and the inner threads 347 of the pushbutton 333 will then engage with the threads of the threaded rod 334 . After large adjustments are made in this fashion, the user may twist the tubular shaft 335 around the threaded rod 334 , with respect to the longitudinal axis “a”, to make fine adjustments in the overall length of the crutch 300 . When a desired length is obtained, the set screw 355 is then tightened on the opposite side of the pushbutton 333 , as shown in FIG. 12 , to apply pressure on the pushbutton 333 and maintain a tight locking fit of the pushbutton assembly 327 to the threaded rod 334 . The user can then operate the crutch 300 .
[0039] It would be appreciated by those skilled in the art that various changes and modifications can be made to the illustrated embodiments without departing from the spirit of the present disclosure. All such modifications and changes are covered by the appended claims. | An elongated walking assistance device includes an upper portion, a lower portion, and an adjustable system which couples the upper and lower portions. The lower portion includes a shock absorbing system attached to a surface contact heel. The adjustable system includes a threaded rod which extends from the upper portion along a longitudinal axis, a pushbutton assembly surrounding the threaded rod, and a tubular shaft capturing the pushbutton assembly. For fine adjustments, the user may rotate the threaded rod with respect to the tubular shaft to adjust the overall length of the device. For coarse adjustments, the user may disengage the pushbutton and slide the tubular shaft along the longitudinal axis. | 0 |
RELATED APPLICATION
This application is a continuation-in-part application of commonly owned, co-pending U.S. Ser. No. 07,274,557 filed Nov. 22, 1988 entitled "Minimizing Deactivation of Ether Synthesis Catalyst", the disclosure of which is hereby incorporated in its entirety by reference thereto.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to methods of conducting catalytic chemical reactions under conditions so as to minimize or substantially avoid deactivation of the catalyst material due to a reaction of polar components, i.e. nitrogenous substances, which may be present in the hydrocarbon feedstream with the catalyst material.
More particularly, the present invention relates to the preparation of alkyl tertiary alkyl ether by catalytic reaction of hydrocarbon streams containing mixtures of isoolefins and alcohols under conditions which minimize or substantially avoid reaction of the catalytic material in the catalytic reaction zone with any nitrogenous components which may be present in the stream.
Specifically, the present invention is directed to a catalytic reaction for producing alkyl tertiary alkyl ether which involves removing nitrogenous components from the hydrocarbon stream prior to introduction of the stream into the catalytic reaction zone to inhibit reaction of the nitrogenous components which may be present in the stream with the catalyst material.
2. Discussion of Background and Material Information
As a general matter, processes are known whereby specific hydrocarbon fractions may be purified using solid adsorbents. In these prior art processes a bed of a solid adsorbent material is contacted with a hydrocarbon stream in either liquid or vapor phase under conditions favorable to adsorption. During contacting, a minor portion of the hydrocarbon stream, including contaminants, is adsorbed into pores in the solid adsorbent, while the major portion, which may be termed the effluent or raffinate, passes through for subsequent processing.
Depending on the process and the product involved, the adsorbent may be used either to adsorb the desired product, which is then desorbed and recovered, or to adsorb the undesired contaminants, to result in an effluent which is the purified product, as is the intended goal of the present invention.
The efficiency of the adsorption is determined by several factors, including the precise adsorbent selected, the contaminants to be adsorbed, temperature, pressure, flow rate of the hydrocarbon stream, and concentrations of feedstream components.
The prior art in this area demonstrates the complexity and the high degree of specificity involved in matching a given feedstock, containing given contaminants, from which a certain product is desired, with a suitable adsorbent under appropriate conditions to arrive at a commercially acceptable process.
U.S. Pat. No. 4,831,206, ZARCHY, is directed to a process for removing deleterious components, for example, nitrogen-containing substances, from a fluid stream wherein the feedstream containing the deleterious components is contacted with a sorbent while in the vapor phase which is capable of selectively removing the deleterious component as compared to the remaining components contained within the feedstream and then, while still maintaining the feedstream in the vapor phase, subjecting the feedstream effluent, now having a reduced concentration of the deleterious component, to the step of the processing operation which is sensitive to the deleterious component, which step is carried out in the vapor phase at conditions suitable for such step. The ZARCHY patent emphasizes that for purposes of his invention, the hydrocarbon feed which may contain sulfide and/or ammonia is maintained in the vapor phase as it is passed through the adsorption zone at temperatures which are well above the dew point of the feedstream, generally in the range of about 250° F. to about 600° F.
U.S. Pat. No. 4,831,207, O'KEEFE et al., is directed to a process similar to the one disclosed by ZARCHY, which utilizes two adsorption zones to provide for continuity of the adsorption step which are switched or cycled in service at intervals that would preclude breakthrough of the adsorbed deleterious component. A disclosed advantage is that the fluid feedstream containing one or more of the deleterious components, such as nitrogen-containing substances, can continuously flow through an adsorption zone, the effluent from which can flow continuously to at least the sensitive step of the process, and at least a portion thereof can be passed continuously to a desorption zone. At an appropriate point in time, i.e., when the adsorption zone is substantially laden with the deleterious component and before there is any breakthrough, the adsorption zone is switched to become a desorption zone, and the desorption zone is then switched to become an adsorption zone in conjunction with the proper switching of the feedstream flow path.
Notwithstanding attempts to improve the production of isobutene and MTBE, a problem associated with conventional processes for the production of MTBE is that the catalyst material used in the catalyst reaction processes has a tendency to deactivate in an unacceptably short period of time.
SUMMARY OF THE INVENTION
The present invention is based on the discovery that nitrogenous components in a feedstream, such as nitrogen containing materials, e.g., nitriles, i.e., acetonitrile (CH 3 CN); amines, including alkylamines (CH 3 NH 2 ), diethanolamine (DEA), monoethanolamine (MEA); amides, such as dimethylformamide (DMF); pyrrolidines, e.g., methylpyrrolidine (NMP); and ammonia (NH 3 ), if present in hydrocarbon streams, react with acidic sites on catalyst material so as to result in the neutralization of these sites with the concomitant loss of catalyst activity.
An object of the present invention, therefore, is the provision of methods for conducting catalytic reaction processes wherein the components of the hydrocarbon stream are catalytically reacted under conditions which favor forming resultant products, i.e., ethers, such as alkyl tertiary alkyl ethers having a normal boiling point in the range of 130° F.-200° F., and particularly MTBE, while inhibiting the reaction of nitrogenous components, such as nitrogen containing materials, e.g., nitriles, i.e., acetonitrile; amines, including alkylamines, diethanolamine, monoethanolamine; amides, such as dimethylformamide; pyrrolidines, e.g., methylpyrrolidine; and ammonia which may be present in the hydrocarbon stream, with the catalyst material whereby the deactivation of the catalyst material due to the reaction of such nitrogenous components with the catalytic material is substantially reduced or avoided. Although some of these nitrogenous substances may be naturally present in hydrocarbon streams, the hydrocarbon stream typically becomes contaminated with such nitrogenous substances as a result of being subjected to upstream extraction processes using such nitrogenous substances, for example, as solvents which become entrained in the hydrocarbon stream leading to the downstream catalytic reactors.
In general, the present invention is directed to any catalytic reaction process, but preferably to catalytic distillation reaction processes, performed in a manner which minimizes or substantially avoids the reaction of nitrogenous components of a hydrocarbon feedstream, containing saturated and/or unsaturated hydrocarbons, and particularly C 4 hydrocarbons, and particularly unsaturated C 4 hydrocarbons, such as olefins, and the catalytic material, which has been discovered to be responsible for deactivation of acidic catalysts used in the catalytic distillation reaction zone.
In accordance with the present invention, the nitrogenous substances present in the hydrocarbon stream may be removed by subjecting the streams to an adsorption treatment before introducing the stream into the catalytic reaction zone. Preferably the adsorption of the nitrogenous components is performed in a cyclic operation involving the use of two adsorption columns.
The present invention relates to a process for purifying a hydrocarbon feedstock which contains at least one nitrogenous contaminant selected from the group consisting of nitrogen-containing compounds, wherein the nitrogen-containing compounds are selected from the group consisting of nitriles, i.e., acetonitrile (CH 3 CN); amines, including alkylamines (CH 3 NH 2 ), diethanolamine (DEA), monoethanolamine (MEA); amides, such as dimethylformamide (DMF); pyrrolidines, e.g., methylpyrrolidine (NMP); ammonia (NH 3 ) and mixtures thereof.
The process involves the steps of contacting feedstreams of the hydrocarbon feedstock, and preferably C 4 unsaturated hydrocarbon streams, containing such nitrogenous contaminants with an adsorbent selected from the group consisting of zeolites, aluminas, clays under conditions suitable for the adsorption of at least one contaminant by the zeolite to produce a contaminant-loaded zeolite.
Although zeolites are the most preferred adsorbents for purposes of the present invention, other adsorbent materials which are no more acidic than zeolite may also be used. The preferred zeolites, however, are selected from the group consisting of zeolite X, and zeolite Y (which also may be referred to as faujasites when naturally occurring), zeolite L, zeolite beta and mordenite.
The zeolite preferably has a pore size of between about 5 to about 11 Angstroms, and may be substantially in the form of crushed or beaded particles.
In a particularly preferred embodiment, a cation type X zeolite is more preferred, with NaX zeolite being most preferred.
In the process according to the present invention, the feedstream, preferably in the liquid state, may be contacted with the zeolite at a weight hourly space velocity of from about 0.5 to about 10, with a weight hourly space velocity of from about 1 to about 8 being preferred, about 1 to about 3 being more preferred, and about 1 to about 2 being most preferred.
The operating temperature used for conducting the process according to the present invention may range from about 0° C. to about 200° C., preferably within the range of about ambient to about 100° C., with a range of from about 20° C. to about 40° C. being more preferred, and a range of from about 25° C. to about 35° C. being most preferred. In general, however, temperatures and pressures sufficient to maintain the feedstock in the liquid state are preferred for use in accordance with the present invention.
While it is to be understood that the process according to the present invention is suitable for practice on a variety of hydrocarbon feedstocks, which will contain an extremely varied and diverse assortment of contaminants, the adsorption process of the present invention has been discovered to be a particularly preferred removal technique where the hydrocarbon feedstream contains nitrogenous contaminants which may be present in the feedstream in an amount up to about 2000 ppm, but typically within the range of about 1-300 ppm, more typically at a concentration within the range of about 1 ppm to about 100 ppm, and most typically at a concentration of from 5 ppm-50 ppm.
In the preferred embodiment of the present invention which is directed generally to the treatment of C 4 unsaturated hydrocarbon streams, for purposes of producing methyl tertiary butyl ether (MTBE), the preferred components of the hydrocarbon feed comprise isobutylene and methanol, and preferably comprise isobutylene, butenes, C 4 saturated hydrocarbons, C 3 hydrocarbons and C 5 hydrocarbons. The hydrocarbon streams suitable for purposes of the present invention have a boiling point within the range of about 10° F. -47° F. The hydrocarbon streams may also comprise water and sulfur contaminants, such as dialkyl sulfides, e.g., dimethyl sulfide (DMS). The hydrocarbon stream most preferred in the preparation of methyl-t-butylether (MTBE) comprises about 25% of a mixture of isobutylene and butene- 1, about 20% butene-2, about 50% C 4 saturated hydrocarbons, and about 5%-10% C 3 hydrocarbons and C 5 hydrocarbons.
The adsorption of the present invention has been discovered to be the preferred removal process for treating hydrocarbon streams, which are to be subjected to a catalytic reaction processes, which contain sulfur contaminants and specifically dialkyl sulfides, i.e., dimethyl sulfide, wherein the nitrogenous contaminants, such as nitriles, and most preferably acetonitriles, are present in amounts less than about 2000 ppm, and more preferably less than about 300 ppm, but most preferably where acetonitrile is present within the range of about 1 ppm to about 100 ppm, and more preferably within the range of about 5 ppm to about 50 ppm.
BRIEF DESCRIPTION OF THE DRAWING
The Figures annexed hereto are flow diagrams showing catalytic distillation processes in accordance with the present invention.
FIG. 1 is a flow diagram of a catalytic distillation process, wherein an adsorption column is installed prior to the mixing point of the hydrocarbon stream feed and the methanol streams.
FIG. 2 is a flow diagram of a conventional catalytic distillation process which is not equipped with an adsorption column in accordance with the present invention.
DETAILED DESCRIPTION
The present invention is based on the discovery that typical hydrocarbon streams which are subjected to catalytic reaction processes, e.g., in the producing of ethers, such as streams containing C 4 hydrocarbons, i.e., unsaturated hydrocarbons, which are used in the production of alkyl tertiary alkyl ethers, and particularly such ethers having a normal boiling point within the range of 130° F.-200° F., and most notably MTBE, contain sulfur contaminants, and specifically dialkyl sulfides, i.e., dimethyl sulfide, in addition to nitrogenous contaminants, such as nitrogen-containing substances or materials which react in the presence of the acidic sites on the catalyst material so as to result in the neutralization of these sites with the concomitant loss of catalyst activity. This has been found to be particularly the case for the production of MTBE by catalytic distillation reaction processes.
Thus, the present invention relates to performing catalytic reactions in a manner which minimizes or substantially avoids reaction of nitrogenous contaminants, and particularly nitrogen-containing materials which may be present in the hydrocarbon stream when fed or introduced into the catalytic reaction zone, i.e., the lead synthesis reactor and the catalytic distillation column, even though the hydrocarbon stream may have previously been subjected to procedures in an attempt to remove contaminants, such as sulfur and nitrogen contaminants, therefrom. Accordingly, the present invention is directed to any catalytic reaction process, but preferably to catalytic distillation reaction processes, which are performed in a manner which minimizes or substantially avoids the reaction of nitrogenous contaminants, as well as dialkyl sulfides such as dimethyl sulfide, in the presence of the catalytic material which has been discovered to contribute to deactivation of acidic catalysts used in the catalytic distillation reaction zone.
In general, therefore, the present invention is directed to any process whereby a reaction of dimethyl sulfide, nitrogenous contaminants, and catalyst material, is minimized or substantially avoided.
One embodiment of the present invention relates to catalytic reaction processes of hydrocarbon streams and particularly catalytic reactions of C 4 hydrocarbon streams, e.g., isoolefins, such as isobutene, containing dimethyl sulfide and nitrogen-containing materials, over an acid catalyst, such as an acid resin catalyst. In this embodiment, the deactivation of the catalyst material used in such catalytic reaction processes is minimized or substantially eliminated by removing, and preferably substantially alcohols, C 5 alcohols and ethanol in addition to methanol.
A critical parameter in catalytic reactions, such as the manufacture of MTBE, is the maintenance of high catalytic activity. In the synthesis of MTBE, as practiced in the art, however, catalyst deactivation has been shown to occur by different mechanisms in different areas of the process. For example, as disclosed in commonly-owned application U.S. application Ser. No. 07,274,557, it is recognized that, in the fixed bed or tubular reactor wherein an acidic resin such as Amberlyst 15 (trademark) is employed to catalyze the formation of MTBE from isobutene and methanol, deactivation of the catalyst occurs over time if the catalyst is exposed to cationic or strongly basic material, such as metals, nitrogen compounds and the like. In order to drive the reaction of methanol and isobutene to MTBE to completion, therefore, it has been proposed to use the same acidic resin catalyst downstream of a first stage reactor, thereby permitting more complete utilization of the isobutene in the feed.
The solution to avoid catalyst deactivation proposed in U.S. application Ser. No. 07,274,557, was based on the discovery that catalyst deactivation results from the reaction of low levels, i.e., as low as 10 ppm or lower, of dimethyl sulfide with highly acidic catalyst sites which are present primarily due to the relatively low levels of methanol, i.e., about 0.6-2 wt.%, and MTBE in the reaction zone. One alternative solution disclosed in U.S. application Ser. No. 07,274,557 is that increasing the levels of oxygenates, i.e., methanol or other alcohols as well as ethers, attenuates the acidity of the catalyst so that reaction between dimethyl sulfide and catalyst is substantially reduced without adversely affecting the reaction of choice, i.e., the reaction of alcohol and isobutene to MTBE.
Another alternative to minimize the adverse effect of dimethyl sulfide disclosed in U.S. application Ser. No. 07,274,557, is to install an adsorption column prior to the mixing point of the feed and methanol streams in a catalytic distillation procedure for the expressed purpose of removing such sulfide contaminants therefrom before exposing the catalyst to the feed.
The present invention, as disclosed and claimed herein, however, is specifically directed to removal of nitrogenous contaminants, i.e., as nitrogen-containing compounds, e.g., nitriles, such as acetonitrile, and the like as otherwise identified herein, in addition to dialkyl sulfides, such as dimethyl sulfide, from the hydrocarbon feedstream to minimize deactivation of the catalyst caused thereby.
The nitrogenous contaminants of the feedstream which are a primary concern for purposes of the present invention include members of a group consisting of ammonia, alkylamines, diakyl amine, such as diethyl amines, diethanolamine, monoethanolamine, acetonitrile, dimethylformamide and methyl-pyrrolidine, although any nitrogenous substance present in the feedstream which poses a problem for the catalyst in the downstream catalytic reactions would also be subject to treatment in accordance with the present invention. The previously mentioned nitrogenous contaminants with which the present invention is primarily concerned, however, are normally those which may contaminate the feedstream as a result of upstream processing, for example, in upstream extraction units which may leak nitrogenous solvents which contaminate the feedstream.
As disclosed in U.S. application Ser. No. 07,274,557, unless special steps are taken to remove dialkyl sulfides, such as dimethyl sulfide, from such feedstreams, the feedstream must also be treated to remove or otherwise minimize the deleterious effects of the dimethyl sulfide which are present in the feedstream so as to prevent deactivation of the catalyst used in the downstream catalytic reaction zones. Although nitrogenous contaminants may not always be present in the feedstream which is to ultimately be subjected to such catalytic reactions, depending upon the upstream processing to which the hydrocarbon feedstream has been subjected or the source of the hydrocarbon feedstream, it has been observed that the hydrocarbon feedstream will substantially always include an amount of dimethyl sulfide which must be removed prior to catalytic reaction in order to minimize the deactivation of the catalyst used in the downstream catalytic reactions.
Thus, the present invention is based on the discovery of an adsorbent material which effectively removes dimethyl sulfide present in the feedstream as well as nitrogenous substances which may also be present in the feedstream.
Adsorbent materials which have been discovered to be suitable for this purpose are adsorbent materials which are substantially devoid of protons as a cation, i.e., which have relatively low acidity, such as zeolite, which preferably are selected from the group consisting of zeolite X and zeolite Y (which may also be referred to as faujasites) zeolite beta and mordenite. The zeolite used for purposes of the present invention preferably has a pore size of between about 5 to about 11 Angstrom units and may be substantially in the form of crushed or beaded particles. A more preferred zeolite includes a cation X zeolite, with NaX zeolite being most preferred.
The acidity of the adsorbent material used for purposes of the present invention is critical inasmuch as hydrocarbon feedstreams which may be processed in accordance with the present invention include saturated as well as unsaturated hydrocarbons. This being the case, the acidity of the adsorbent is of a concern because it has been discovered that if an adsorbent material having too high acidity is used, the acidity of the adsorbent could promote undesirable reactions of the unsaturated hydrocarbons, for example, polymerization, isomerization, and the like. In particular, for purposes of the preferred embodiment wherein the present invention finds particularly utility, there is a concern for minimizing the reaction of isobutylene prior to its reaction with alcohol in the preparation of MTBE. Thus, it has been discovered that zeolites are preferred catalysts for purposes of the present invention with this consideration in mind.
Another critical aspect of the adsorbent material used for purposes of the present invention is that the adsorbent material must not only be effective for purposes of adsorbing the nitrogenous substances, which are of primary concern for purposes of the present invention, but also an adsorbent material which is also effective for removing sulfides, and particularly dialkyl sulfides, such as dimethyl sulfide, from the feedstream. As previously indicated, although the feedstream may not always contain nitrogenous contaminants, depending on how the feedstream was previously treated in upstream processing, unless special steps are taken to remove dimethyl sulfide from the feedstream, as disclosed in U.S. application Ser. No. 07,274,557, the dimethyl sulfide which is present in the feedstream must also be removed, or the feedstream must be otherwise treated in order to prevent deactivation of the catalyst used in the downstream catalytic reaction zones, i.e., the lead synthesis reactor and the catalytic distillation column.
Therefore, the present invention is directed to the removal of contaminants, i.e., nitrogenous substances as well as dimethyl sulfide, which would be harmful to the downstream catalytic reaction zones, but not to the detriment of the removal of dimethyl sulfide which is substantially always present in the feedstream to be subjected to such reactions.
Related to this, it has been unexpectedly discovered that NaX zeolite is a most preferred adsorbent material for this purpose. In this regard, NaX zeolite has a specified capacity for the adsorption of sulfides, for example, of about 3%. A common concern, therefore, is the effect that the presence of other contaminants, for example, nitrogenous containing contaminants, such as nitriles, may have if present in the feedstream undergoing the adsorption treatment. In accordance with the present invention, therefore, it has been discovered that NaX zeolite also has an adsorption capacity of about 15% for nitriles; thus, there is a similar concern as to whether the capacity of the adsorbent material for nitriles, such as acetonitriles, would be adversely affected by the presence of sulfur components, i.e., dialkyl sulfides such as dimethyl sulfide, which, as indicated above, is substantially always present.
As previously indicated, the concern for an adsorbent material which effectively removes nitrogenous contaminants, as well as dimethyl sulfide, is of a primary concern for purposes of the present invention inasmuch as the dimethyl sulfide has been discovered to substantially always be present in the feedstream unless extraordinary steps are taken to effect their removal; and that this is true regardless of whether the feedstream has been subjected to conventional sulfur-removal techniques.
In this regard, the feedstreams to be subjected to subsequent catalytic reactions normally contain dimethyl sulfide in a concentration of up to about 50 ppm. When the nitrogenous contaminants are present in such a feedstream, the nitrogenous contaminants may be present at a concentration up to about 1000 ppm, but more often within the range of up to about 300 ppm, and most often within the range of about 5 ppm-50 ppm. In such amounts, for example, where the amounts of acetonitrile and dimethyl sulfide are substantially equal, NaX zeolite has been found to be most preferred for purposes of effectively removing both the nitrogenous contaminants, as well as the dimethyl sulfide, from the feedstream. As indicated above, however, normally the nitrogenous contaminants are present in the feedstream in an amount greater than the dimethyl sulfide. Although if the level of nitrogenous contaminants is substantially greater than the level of dimethyl sulfide in the feedstream, i.e., in amounts greater than about 300 ppm-1000 ppm, the presence of such high amounts of nitrogenous contaminants may adversely affect the performance of the adsorbent material. Accordingly, it has been discovered that for purposes of the present invention the ratio of nitrogenous substances to dimethyl sulfide may be present within the range of 1:1 to about 20:1 before the performance of, for example, NaX zeolite, may be observed to be adversely effected.
The present invention is, therefore, based on the discovery of the fact that the presence of nitrogenous contaminants within these prescribed ranges does not adversely affect the adsorption of dimethyl sulfide by zeolite adsorbent material, such as NaX zeolite. As previously indicated, this is a particularly important discovery inasmuch as the zeolites used in accordance with the present invention, and particularly NaX zeolite, have been discovered to have a high capacity for adsorbing acetonitriles. Such zeolite have also been discovered to adsorb acetonitrile to substantially complete capacity for acetonitriles without having its capacity for adsorbing dimethyl sulfide, which is substantially always present in the feedstream and must also be removed, adversely affected, i.e., this acetonitrile capacity does not affect the zeolite capacity for adsorbing dimethyl sulfide.
Therefore, the present invention is based on the new and unobvious discovery that zeolites, and preferably NaX zeolite, are not only an effective adsorbent material for nitrogen-containing substances, but also effectively adsorb dimethyl sulfide, which has been discovered to be a particularly difficult sulfur contaminant to remove from hydrocarbon streams and which is not always removed by conventional sulfur removing techniques that, for example, would be effective to remove other sulfur contaminants, such as mercaptans.
EXAMPLES
The following examples are given to illustrate the advantages of the present invention.
EXAMPLE I
Laboratory static tests were carried out to determine the ability of NaX to adsorb nitrogenous compounds. The results showed that a feed containing dimethylformamide (DMF) at the 290 ppm level can be lowered to 13 ppm. With monoethannamine a feed level of 70 ppm changed to 9 ppm.
A dynamic test was carried out using a 5 cc charge of NaX at 35° C. The feed contained 10% isobutylene, 90% n-heptane and 195 ppm each of dimethylsulfide/acetonitrile. The sieve capacity for sulfur at DMS breakthrough was 2.96%. At that point the acetonitrile had not broken through and was at a capacity of 6.2%.
TABLE I______________________________________ NaX Initial FinalStatic Equilibrium Test Concentration Concentration______________________________________dimethylformamide (DMS) 290 ppm 13 ppmmonoethanolamine 70 ppm 9 ppm______________________________________
Dynamic Tests
The feed contained 10% isobutylene, 90% n-heptane, and 195 each of dimethylsulfide and acetonitrile. The capacity of NaX for acetonitrile is 16%.
When both acetonitrile and dimethyl sulfide are present, the DMS breaks through first. The DMS capacity at 1PPM breakthrough is about 2.5 to about 2.96% at which time no CH 3 CN had broken through although present at a level of about 6.2%.
EXAMPLE II
Another laboratory static test was carried out to determine the ability of NaX to adsorb nitrogenous compounds. The results showed that a feed containing dimethylformamide (DMF) at the 288 ppm level can be lowered to 14 ppm; with diethanolamine, a feed level of 352 ppm changed to 56 ppm; and with ethanolamine at a feed level of 474 ppm changed to 43 ppm.
TABLE II______________________________________ NaX Initial FinalStatic Equilibrium Concentration Concentration______________________________________Diethanolamine 352 PPM 56 PPMethanolamine 474 PPM 43 PPMdimethylformamide 288 PPM 14 PPM______________________________________
Dynamic Tests
Another dynamic test was carried out using a 5cc charge of NaX at 35° C. The feed contained 10% isobutylene, 90% n-heptane and 198 ppm of dimethylsulfide and 145 ppm of acetonitrile. The sieve capacity for sulfur at DMS breakthrough was 2.5-2.96%. At that point the acetonitrile had not broken through. Capacity of NaX for acetonitrile is 16%.
EXAMPLE III
The following example shows that NaX zeolite adsorbs various nitrogen-containing compounds, preferably other than nitriles, as well as examples which show the effectiveness of NaX zeolite as an adsorbent for nitrogen-compounds alone and in combination with dimethyl sulfide in a feedstream.
TABLE IIIA______________________________________NaX 10 × 14 MESH CRUSHED TO 40 × 60 MESHDRIED AT 170° C./48 HOURS DMSFeed Rate DMS CH.sub.3 CN Temp. CAPACITYRun ml/min ppm ppm °C. % %______________________________________1 0.446 203.4 200 35 2.472 0.416 178.3 200 35 2.033 0.391 183 200 35 3.044 0.45 181.6 193.8 35 3.625 0.417 181 3621 35 --6 .407 186 1800 35 1.28______________________________________
If acetonitrile concentration is increased to 0.18% (1800 ppm) while DMS concentration is kept at 190 ppm then the DMS capacity drops to 1.3% at breakthrough.
TABLE IIIB__________________________________________________________________________CRUSHED TO 40 × 60 MESH NaXDRIED AT 170° C./48 HOURS CH.sub.3 CN Fd DMS Fd Feed Rate Temp. CH.sub.3 CN DMSRun ppm ppm ml/min °C. Capacity % Capacity %__________________________________________________________________________1 198 194.6 0.41 35 6.22* 2.962 211/193 -- .42/.65 35 14.05 --3 193.3 -- 0.80 35 16.06 --__________________________________________________________________________ *at DMS breakthrough
When both acetonitrile (198 ppm) and dimethyl (145 ppm) sulfide are present the DMS breaks through first. The DMS capacity at IPPM breakthrough is 2.5-2.96%. At this time no CH 3 CN has broken through.
For purposes of the present invention, the catalyst material used in the downstream reaction zone may be any material appropriate for the downstream reaction, but is preferably an acid catalyst, such as catalytic metals and their oxides or halides suitable for a multitude of catalytic reactions and particularly heterogeneous with the reaction or other fluids in the system. The term "catalyst" or "catalytic material", therefore, as used herein includes any solid material which is recognized for the reaction under consideration as performing as a catalyst.
For example, where the present invention is practiced in a catalytic distillation process, the catalytic material may be in a form which permits its incorporation into a distillation tower, such as a fixed bed, but may also be in a form which serves as a distillation packing, for example, rings, saddles, balls, irregular pieces, sheets, tubes, spirals, packed in bags, plated on grills or screens, and reticulated polymer foams.
Catalysts which have been found to be suitable for use in such catalytic reactions include cation exchange resins. Preferred catalysts for this purpose, however, are acid catalysts, such as acidic resin catalysts. A more preferred catalyst for this purpose is a macroreticular sulfonic acid cation exchange resin, selected from the group consisting of Amberlyst 15 (trademark), Lewatit SPC 18 BG, Dowex M-31 and Dowex DR-2040, with Dowex DR-2040 being most preferred.
Referring now the Figures, a schematic system is shown, which can be used to produce MTBE.
In FIG. 1, a hydrocarbon stream containing a stoichiometric amount of methanol based on isobutylene is introduced together with an isobutylene containing stream to a lead synthesis, or guard bed, reactor 14. For purposes of the present invention, however, the nitrogenous contaminants in the feedstream 4 may be removed by installing an adsorption column 6 prior to the mixing point of the hydrocarbon feed 10 and methanol 7 streams. The removal of nitrogenous contaminants has been discovered to be most effective for a methanol-free feedstream. Although not shown, in practice, the removal is preferably accomplished with a cyclic operation involving the use of two adsorption columns so that while one column is adsorbing the sulfides or the nitrogenous substances, the other column is being regenerated to recover the capacity. The preferred process according to the present invention, therefore, comprises two fixed beds of solid adsorbent being operated in cyclic fashion, so that one bed is undergoing adsorption while the other bed is being desorbed. Before the process is initiated, the beds are preferably blanketed with hot nitrogen to create a dry oxygen-free environment. This prevents oxygen from being introduced into the hydrocarbon stream; otherwise, oxidative degradation of the feed hydrocarbon components could occur, resulting in formation of undesirable side products.
When the bed undergoing adsorption reaches the end of its cycle, as measured by a breakthrough value for the contaminant, i.e., nitrile or sulfide in the adsorption effluent, the beds are switched. The switching may be accomplished using a programmable controller and remote-operated valves. A typical adsorption cycle will last from about 4 hours to about 75 hours, but can vary considerably depending on variables such as feed rate, the concentration of contaminants, i.e., nitriles or sulfides in the feed, the age of the solid adsorbent and the amount of adsorbent used. The lead synthesis reactor or guard bed reactor 14 is provided with an acidic resin catalyst, such as Amberlyst-15 (trademark), Dowex DR-2040, Lewatit SPC 18 BG, or Dowex M-31, and is heated to an appropriate temperature. The effluent or product stream 16 leaving the reactor is composed of MTBE, unreacted hydrocarbons, and methanol (MeOH). The resultant product stream is the feedstream 18 which is then fed to a distillation column 20. The vaporized overhead 22 is composed of raffinate depleted in olefins branched at the point of unsaturation (sometimes referred to as tertiary olefins) which is passed through methanol removal and final clean-up procedures.
Consistent with the process disclosed in U.S. application Ser. No. 07,274,557, a stream 12 of methanol may be introduced into the catalytic distillation reaction zone. The catalyst in the catalytic distillation reaction zone may also be Amberlyst 15 or equivalent, but is preferably Dowex DR-2040. The effluent is then passed to a product topping tower 26, wherein C 5 hydrocarbons are removed for separate processing. The resultant effluent stream 30 is then passed to product tailing tower wherein MTBE is removed as overhead product. The effluent 36 from tailing tower contains various components including oxygenates, such as TAME, which are recycled through conduit 38 to supply oxygenate to catalyst reaction zone.
Notwithstanding the foregoing to preferred embodiment, catalytic reaction processes which are suitable to being practiced in accordance with the present invention may be a catalytic distillation process performed in a conventional manner, such as that which is disclosed by any of the previously discussed U.S. patents in the name of SMITH, Jr.; the disclosures of which are hereby specifically incorporated by reference thereto.
Referring to FIG. 2, a feedstream 10 containing 13 wt.% isobutylene, 30 wt.% isobutane, 14 wt.% butene-1, 13 wt.% n-butane, 18% 2-butenes, 0.5 wt.% butadiene, 6% isopentane, approximately 5 wt.% other C 5 hydrocarbons (including paraffins, olefins, and diolefins), 200 wt. ppm methyl and ethyl thiol and 10 wt. ppm dimethyl sulfide are combined with a methanol stream 7 in the weight ratio of methanol in stream 7 to isobutylene in stream 10 of 0.75:1.0. This combined stream is heated to 130° F. to 170° F. and introduced to a lead synthesis reactor which contains acidic ion exchange resin catalyst such as Amberlyst 15 (trademark) in a quantity which provides for a weight space velocity of 3.5 W/H/W to 4.0 W/H/W.
In passing through the lead synthesis reactor 14, approximately 85 wt.% of the isobutylene in the feedstream is converted to MTBE. In contrast to the present invention described above wherein the hydrocarbon stream is exposed to an adsorption treatment before being subjected to catalytic reaction to remove nitrogenous contaminants, in this reactor, strongly basic compounds and metallic compounds contained in the hydrocarbon or methanol feed react with acidic catalyst. Although this may remove the contaminants from the feed, so as to minimize their adverse effect on the catalyst in the downstream catalytic distillation tower 20, in so reacting with the catalyst, however, these basic compounds reduce the number of acidic sites on the catalyst, and over time result in its deactivation.
The hydrocarbon stream 16, which exits reactor 14, contains 17 wt.% MTBE, about 2 wt.% isobutylene and all the remainder of unreacted hydrocarbon and methanol. This stream is fed to a catalytic distillation tower 20. The overhead from this column containing only 0.5 wt.% isobutylene in hydrocarbons is passed through methanol removal and sent to other processing.
In accordance with the present invention, therefore, a procedure has been developed to minimize or substantially eliminate the deleterious effects which would otherwise be caused by the presence of nitrogenous contaminants in the catalytic reaction zone. This is accomplished by adsorbing the nitrogenous contaminants, and particularly nitrogen-containing materials and compounds, such as nitriles and amines, from the hydrocarbon feedstream before the feedstream contacts the catalyst in either the lead synthesis reactor 14 or the catalytic distillation tower 20.
EXAMPLE IV
The following test was conducted to evidence that the previously identified adsorbents are effective to remove nitrogen-containing materials from an ether synthesis hydrocarbon stream.
The experiments were carried out with a laboratory-scale, continuous-flow tubular reactor. A 5 cc charge of sodium-X zeolite was placed in a stainless steel column and held in place by porous metal plugs. The tube was kept at ambient temperature. The single liquid feed was introduced by an HPLC pump controlling the liquid flow to yield a Liquid Hourly Space Velocity of 3.6. The temperature was maintained at 22° C. and back pressure at the exit of the tube was kept at 200 psig. The feed was a synthetic blend of 10% isobutylene, 90% n-heptane and 200 ppm acetonitrile. The acetonitrile concentration in the column effluent was less than the GC detectable limit of 5 ppm before the acetonitrile loading on the NaX zeolite reached a level of 12.8 wt.%.
Notwithstanding the foregoing detailed discussion of preferred embodiments, in general it can be said that the present invention may be used in connection with any reaction of a hydrocarbon stream over an acid catalyst, such as Amberlyst 15 or Dowex DR-2040. Included among the catalytic reactions to which the discoveries of the present invention are believed to be suitable are catalytic isomerization, esterification, dimerization, cracking and distillation processes, although all other types of reactions are contemplated within the scope of the invention process, for example, chlorination, hydration, dehydro-halogenation, alkylation, polymerization and the like.
It is also believed that in general isomerization reactions over acidic ion exchange resin catalysts can be improved and deactivation of the catalyst minimized by removing such nitrogenous contaminants from the hydrocarbon stream. Accordingly, the principles of the present invention may be applied to the isomerization of numerous hydrocarbon feed compositions, such as feedstreams containing a mixture of saturated hydrocarbons, other straight chain and branched olefins, and small amounts of certain diolefins. One example of such a feed is the naphtha fraction from a refinery catalytic cracking unit.
Although in the past it has been suggested to include alcohols and water at this stage of catalytic isomerization reactor to provide the necessary environment to render the catalyst operable, it has been found that alcohols tend to react with the isoolefins to form ethers, thereby resulting in a product loss. Moreover, the presence of water causes solubility problems and also tends to react with the isoolefins to form alcohol; thus, water is not a particularly desirable solvent. Water also tends to deactivate the catalyst. It has been proposed to include ether with isoolefins to provide the necessary environment for resin catalyst operability, with tertiary amyl methyl ether (TAME) and methyl tertiary butyl ether (MTBE) being preferred, and TAME being most preferred for this purpose.
Although the invention has been described with reference to particular means, materials and embodiments, from the foregoing description, one skilled in the art can easily ascertain the essential characteristics of the present invention; and various changes and modifications may be made to various usages and conditions, without departing from the spirit and scope of the invention as described in the claims that follow. | A catalytic reaction process which involves exposing a hydrocarbon feed including nitrogenous contaminants as well as dialkyl sulfides to a material capable of adsorbing the nitrogenous contaminants as well as dialkyl sulfides from the feed before introducing the stream substantially devoid of nitrogenous contaminants and dimethyl sulfide into a feed zone of a reactor; contacting the hydrocarbon stream with a catalyst material in the reaction zone; and catalytically reacting the hydrocarbon stream under conditions which favor forming a reaction product and inhibiting reaction of nitrogenous contaminants and dimethyl sulfide with the catalyst material. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is claims priority to provisional application Ser. No. 60/927,614, entitled “Aerodynamic trailer with sliding rear door” filed May 4, 2007 and provisional application Ser. Nos. 61/070,669 and 61/070,670 filed Mar. 25, 2008 entitled “Rounded Cargo Doors for Trailers and Trucks” and “Drag Reduction Arrangement for Cargo Trucks and Trailers” to Mark Roush, the contents of which are all incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates to a trailer design. More specifically, it relates to a cargo container with improved aerodynamic efficiency, sliding or slatted rear doors, and a crash attenuating rear skirt.
BACKGROUND OF THE INVENTION
[0003] There are many types of cargo containers. There are cargo containers designed to be loaded onto ocean going ships. There are cargo containers specially shaped to fit into the curved hulls of airplanes. There are cargo containers that are transported by train. Cargo containers are often transported as trailers by trucks.
[0004] There are several problems associated with cargo containers. One problem is that the rectangular shape of the container creates drag that hinders the transport of the container. It is desirable to have an aerodynamic cargo container that reduces drag.
[0005] A drag force acts on an object which moves in a fluid environment such as air or water. This drag force includes several specific drag forces wherein the main one is known as a pressure drag force. The pressure drag force is caused by a net pressure force acting on the object. The rear end contribution to the pressure drag is called “base drag”. Flow separation at the base of the moving object creates a vortex system and reduces base pressure thus increasing drag. This problem exists for truncated objects, which have blunt bases, such as a box, a cylinder and the like. Drag forces on the trailer reduce the fuel efficiency of the truck pulling the trailer, and increase the cost of transporting the cargo container. It is desirable to reduce the cost in transporting a cargo container.
[0006] Another problem is that automobiles often crash into the rear of trailers causing injury to the automobile and passengers. It is desirable to have a trailer that is designed to reduce the damage caused to automobiles and passengers that crash into the rear of a trailer.
[0007] Another problem is that cargo containers pulled by trucks must often be moved into close proximity to a loading dock so that the cargo can be loaded or unloaded. The hinged doors of a cargo container can limit how close a cargo container can be positioned to a loading dock. It is desirable to have a cargo container that can be opened while in close proximity to a loading dock.
[0008] There have been attempts to solve some of these problems. For example, U.S. Pat. No. 6,286,894 that issued to Kingham teaches a transportable hauling container, such as a trailer of a tractor-trailer combination, has a rear portion that is configured in or convertible to a wedge shape. Movable portions are located at the rear sides of the trailer that can pivot inward toward a longitudinal centerline. Movable flaps also are located at the rear top of the trailer, which can pivot downward in alignment with the movable portions. The movable portions and flaps can be secured relative to each other in various combinations, thereby providing a more aerodynamic configuration of the trailer rear end. The container or trailer can be configured in such an arrangement, or be convertible from a standard configuration which also includes doors at the rear of the trailer, to a more aerodynamic configuration. A method is also disclosed, which includes operations for converting such a convertible trailer between the standard and aerodynamic configurations.
[0009] For example, U.S. Pat. No. 4,924,780 that issued to Hart teaches a rail car enclosure having a bottom deck, sidewalls and a curved roof defined by at least one slope on each side connecting a flat top of the roof with the sidewalls and the deck connecting the opposite end of each sidewall to form an open end of the rail car. At least one intermediate deck extending between and connecting the sidewalls. An upper track mounted on the uppermost intermediate deck and a bottom track mounted on the bottom deck such that the upper track and bottom track curve around the sidewalls of the rail car. A plurality of panels hinged together at the marginal edges thereof to form a left and right door to slide on the upper and bottom curved tracks between a closed and stowed position. The doors parallel to the exterior of the sidewalls in the stowed position and standing substantially in one plane to fill the open end of the rail car in the closed position.
[0010] U.S. Pat. No. 4,236,745 that issued to Davis teaches a truck body streamlining device, and more specifically to a collapsible, pivoted rear door attachment which when deployed in its operative position forms a reduced air drag surface on the rear of the truck body to minimize the wind resistance of the vortex which normally forms at the rear of a square backed truck.
[0011] U.S. Pat. No. 4,077,330 that issued to Peisner teaches an end closure for a rail car which comprises a pair of sliding doors mounted for movement between open and closed positions. One of the doors has a recess to clear a brake lever when the door is open. A panel is provided to close the recess when the door is closed. The panel is automatically moved to a position opening the recess when the door is opened and automatically moved to a position closing the recess when the door is closed.
[0012] U.S. Pat. No. 3,995,563 that issued to Blunden teaches an end closure for a rail car which comprises a pair of sliding doors. Locking mechanisms provided for securing the doors in closed position extending across the end of the rail car as well as in open and in intermediate positions. Each door moves from closed to open position through an opening in the side wall of the rail car to an open space on the outer side of the side wall within the allowed rail car clearance.
[0013] Thus, it is desirable to provide a cargo container with an improved aerodynamic design, doors that can be operated while the container is in close proximity to a loading dock, and a rear skirt that attenuates the damage caused to automobiles that crash into the rear of the container.
SUMMARY OF THE INVENTION
[0014] In accordance with preferred embodiments of the present invention, some of the problems associated with cargo containers are overcome. A cargo trailer with improved aerodynamic efficiency, sliding rear doors, and a crash attenuating rear skirt is presented.
[0015] The cargo container includes an aerodynamic rear design that reduces the base drag on the container when it is transported. The cargo container may further include a crash attenuating skirt that contains angled sections that deflects vehicles away from the truck. The cargo container may further include rear sliding doors.
[0016] The cargo container may have a pair of cargo doors at the rear of the container which themselves define the rear curvature of the container structure. These doors may each have pivoted segmented sections that assume the curved contour of an edge when the doors are moved to a closed position. When opened, the doors each can be fully flattened out against the sides of the trailer to minimize side clearance needed and allow parking closely spaced from adjacent trailers in normal fashion at loading docks
[0017] The foregoing and other features and advantages of preferred embodiments of the present invention will be more readily apparent from the following detailed description. The detailed description proceeds with references to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Preferred embodiments of the present invention are described with reference to the following drawings, wherein:
[0019] FIG. 1 is a perspective view of a trailer with 5 sided rear section.
[0020] FIG. 2 is a view of a trailer with a 5 sided rear section with a rear bumper that follows the contour of the trailer.
[0021] FIG. 3 is a side view of rear section of the trailer.
[0022] FIG. 4 is a top view of the rear section of the trailer
[0023] FIG. 5 shows the interior of the rear section of the trailer
[0024] FIG. 6 is a view of the rear section of the trailer
[0025] FIG. 7 is a back view of the trailer
[0026] FIG. 8 is a back view of the trailer showing door handles for opening the rear doors, a locking device on the rear doors, and a sealing means between the two rear doors.
[0027] FIG. 9 is a back perspective view of the trailer highlighting the rear bumper following the contour of the trailer.
[0028] FIG. 10 is a view of a trailer with an 18 sided rear section, and a rear bumper that follows the contour of trailer.
[0029] FIG. 11 is a view of a trailer with an 18 sided rear section, and a rear bumper that follows the contour of trailer. The rear doors of the trailer are open.
[0030] FIG. 12 is a view of a trailer with an 18 sided rear section, and a rear bumper that follows the contour of trailer. The rear doors of the trailer are open. The rear doors move along a track when the doors are operated.
[0031] FIG. 13 is a view of a trailer with an 18 sided rear section, and a rear bumper that follows the contour of trailer. The trailer shown does not have a flat roof.
[0032] FIG. 14 is a view of a trailer with an 18 sided rear section. The rear bumper has a similar contour to the rear of the trailer, but is not directly below the trailer.
[0033] FIG. 15 is a view of a trailer with an 18 sided rear section. The rear bumper has a vertical angle.
[0034] FIG. 16 is a side view of a trailer with an 18 sided rear section. The rear bumper has a vertical angle.
[0035] FIG. 17 is a side view of a trailer with an 18 sided rear section.
[0036] FIG. 18 is a perspective view of a trailer with slatted rear doors.
[0037] FIG. 19 is another perspective view of a trailer with slatted rear doors.
[0038] FIG. 20 is an upward view of a trailer with slatted rear doors.
[0039] FIG. 21 is a pictorial downward view of a trailer section from the top with the roof covering removed to show the overhang structure.
[0040] FIG. 22 is a rear view of a trailer rear section.
[0041] FIG. 23 is a side elevational view of a trailer rear section.
[0042] FIG. 24 is a top view of a trailer rear section showing the doors in various positions being opened.
[0043] FIG. 24A is a cross section of a rear door with pivoted segments in a closed position.
[0044] FIGS. 25-30 are various views showing frame edges at the top and bottom which the doors.
DETAILED DESCRIPTION OF THE INVENTION
[0045] Referring to the figures, exemplary embodiments of the invention will now be described. The exemplary embodiments are provided to illustrate aspects of the invention and should not be construed as limiting the scope of the invention. The exemplary embodiments are primarily described with reference to the figures.
[0046] FIG. 1 illustrates and exemplary embodiment of the aerodynamic cargo container with a rear sliding door 5 and a crash attenuating skirt/underride guard 10 . In this embodiment, the cargo container is in the form of a truck trailer. The container has a roof 15 with a front roof edge 20 , first and second side edges ( 25 and 30 ), first and second fore edges ( 35 and 40 ), first and second aft edges ( 45 and 50 ) and a rear edge 55 . The container also has a floor 60 with edges similar to and parallel to those of the roof. Eight flat sections connect the roof and the floor. The eights flat sides are a front flat section, a first and second side flat section, and five flat rear sections. The five rear sections are two fore angled rear sections, two aft angled rear sections, and a back flat section. To each side flat section is connected a fore angled rear section, and to each fore angled rear section is a connected to an aft rear angled section. The back flat section is connected to both aft rear angled sections.
[0047] The rear doors of the trailer shown in FIG. 1 comprise the five flat rear sections of the trailer. The back flat section shown in FIG. 1 comprises two door handles for operating the rear doors, and two door panels that can be separated. When the rear doors of the trailer are operated, the fore and aft angled rear sections and the two door panels of the back rear section slide towards side flat section to which they are closest. The fore and aft angled rear sections and the two door panels slide along a path generally defined by the perimeter of the roof and floor.
[0048] FIG. 1 illustrates a crash attenuating skirt below the five flat rear sections of the cargo container. The crash attenuating skirt is connected to the floor of the trailer by at least one skirt connector. The crash attenuating skirt has segments which are angled towards the side sections of the trailer. An automobile crashing into the angled segments crash attenuating skirt would be diverted away from the trailer thereby reducing damage to the automobile and trailer.
[0049] FIG. 2 is a side view of the trailer showing the landing gear 65 and the wheel assembly 70 , a kingpin for connecting the trailer to a tractor is located near the landing gear. The angled segments of the crash attenuating skirt are highlighted.
[0050] FIG. 3 is a side partial view of the trailer. The connections between the roof and the floor of the trailer are highlighted.
[0051] FIG. 4 is a top partial view of the trailer. The five flat rear sections, and part of the two side flat sections are shown.
[0052] FIG. 5 is a partial perspective view of the interior of the trailer. In this exemplary embodiment, the floor and roof of the trailer have integral grooves 75 along which the rear doors travel.
[0053] FIG. 6 is a partial perspective view of the rear of the trailer and the crash attenuating skirt. A bar of the underride guard (skirt) oriented parallel to the rear edge of the floor 80 is shown. Also shown are portions of the guard oriented substantially parallel to the aft, fore, and side edges ( 85 , 90 , and 95 respectively). The posts 100 connecting the bar to the floor of the trailer are also illustrated.
[0054] FIGS. 7 and 8 are back view of the rear of the trailer. In the embodiment illustrated in FIG. 8 , the each door panel of the back flat section has a handle for operating the doors. Each door panel has a sealing means, such as rubber, plastic, or vinyl. When the sealing means of one door panel presses against the sealing means of the other door panel, a water-tight seal with improved insulation characteristics is formed. One of the door panels shown in FIG. 8 also comprises a locking means to prevent the operation of the door.
[0055] FIG. 9 is a back perspective partial view of the trailer.
[0056] FIG. 10 is a back perspective partial view of the trailer showing an embodiment of the trailer where there are eighteen rear flat sections. The crash attenuating skirt shown in FIG. 10 has more angled segments than the crash attenuating skirt shown in FIG. 9 .
[0057] FIG. 11 illustrates a back perspective partial view of the trailer showing an embodiment of the trailer where there are eighteen rear flat sections. The rear doors shown in FIG. 11 are partially rolled away. Partially opening the doors of the trailer is desirable to reduce loss of refrigeration or heating. FIG. 11 further shows a rear roof section 105 with a horizontal surface that is bounded by a half circle 110 with a diameter 115 equal to the width of the trailer body. Although the diameter 115 of the half circle is shown, the rear roof section may also be also be a circular section where with a chord that is substantially equal to the width of the trailer. The chord of a curve is a geometric line segment whose endpoints line on a curve.
[0058] FIG. 12 a back perspective partial view of the trailer showing an embodiment of the trailer where there are eighteen rear flat sections. In the embodiment of the invention shown, there is a track, attached to the floor of the trailer on which the rear doors slide. The rear doors can also hang from, or be guided by a track attached to the roof of the trailer.
[0059] FIG. 13 a back perspective partial view of the trailer showing an embodiment of the trailer where there are eighteen rear flat sections. In this embodiment of the invention, the roof of the trailer is angled to further reduce base drag.
[0060] FIG. 14 a back perspective partial view of the trailer showing an embodiment of the trailer where there are eighteen rear flat sections. In this embodiment of the invention, the crash attenuating skirt is not directly below the floor of the trailer.
[0061] FIG. 15 is a partial perspective view of the trailer illustrating an embodiment of the crash attenuating skirt that has segments angled towards the floor of the trailer.
[0062] FIG. 16 is a partial side view of the trailer illustrating an embodiment of the crash attenuating skirt that has segments angled towards the floor of the trailer. The angled side bar 120 connects to both the floor of the trailer and other portions of the rear underride guard.
[0063] FIG. 17 is a partial side view of the trailer illustrating an embodiment of the crash attenuating skirt that has does not have segments angled towards the floor of the trailer.
[0064] FIG. 18 shows a perspective view a trailer with flexible rear door made from interconnected pivoted slats 120 having a plurality of pivoted slats. In the door illustrated, there are both wide slats 125 and thin slats 130 , but in other embodiments the slats may have a homogenous width. The flexible door is secured to another flexible door through a latching mechanism 135 . The flexible door may also be secured to the roof and floor of the trailer with locks 140 connected to the door. The door is further secured to trailer sidewall with a hinge mechanism 145 that the door may rotate around.
[0065] FIG. 19 shows another perspective view of the flexible door. The top of the flexible door is secured to a rounded overhang 150 that may or may not be an integral part of the trailer roof. The trailer shown has floor with squared corners 155 that facilitates rolling of cargo pallets onto the trailer.
[0066] FIG. 20 shows a trailer where the roof has rounded rear corners 160 to reduce the base drag of the trailer. In another embodiment of the invention, the roof corners are squared to match the corners of the floor. Alternatively, the floor corners may be rounded to further decrease the base drag of the trailer.
[0067] FIG. 21 shows a view of the perspective view of the trailer where the internal structure of the rounded overhang is revealed. FIGS. 22 and 23 show side and back views of the flexible trailer door in a closed state.
[0068] FIG. 24 shows a top view of the rear of the trailer with flexible doors secured together in a fully closed state 160 . The doors are also shown in a fully open state 165 , where slats of the door cooperate to form a substantially flat surface located near the sidewalls of the trailer. Also shown are a plurality of partially open states 170 . The flexible doors do not have to be opened to the fully open state to remove cargo from the trailer; however the fully open state of the doors minimizes the total width of the trailer. FIG. 24A shows a cross section of a flexible door in a fully closed state where a plurality of pivoted slots are cooperating to form a highly curved surface.
[0069] The flexible nature of the doors also allows the doors to be fully or partially opened when there is a minimal amount of space available, such as when multiple trailers are docked at a loading bay.
[0070] FIG. 25 shows a cross section of a trailer with pivoted slat 120 in contact with a rounded overhang 150 and a trailer floor. FIG. 26 is a close view of the interconnection of the slat and the overhang. In the closed position, the slat abuts against an upper edge 175 of the rounded overhang. The connection between the upper edge and the slat may include waterproofing features to seal the connection. FIG. 27 is a zoomed view of the interconnection between the slat and the trailer floor of FIG. 25 . The slat 120 abuts against a lower edge 180 in the closed position. Similar to the upper edge, the lower edge may have features to waterproof and seal the connection with the pivoted slats.
[0071] FIG. 28 shows a partial perspective view of the rear of a trailer showing the curvature of both the upper edge 175 and the lower edge 180 . When the flexible door is in the fully closed state the pivoted slats abut against both the upper and lower curved edges. The edges substantially shape the orientation of the pivoted slats of the flexible door when the door is in a fully closed state. Brake lights are shown behind the raised curved edge. The surface between the raised curved edge and the brake lights is substantially flat to allow the slatted doors to be opened. FIGS. 29 and 30 are side and back views of the trailer of FIG. 28 where the upper edge 175 and the lower edge 180 are shown.
[0072] It should be understood that the programs, processes, methods and system described herein are not related or limited to any particular type components unless indicated otherwise. Various combinations of general purpose, specialized or equivalent components may be used with or perform operations in accordance with the teachings described herein.
[0073] In view of the wide variety of embodiments to which the principles of the present invention can be applied, it should be understood that the illustrated embodiments are exemplary only, and should not be taken as limiting the scope of the present invention. The inventors contemplate several alterations and improvements to the disclosed invention. Other alterations, variations, and combinations are possible that fall within the scope of the present invention. Although various embodiments of the present invention have been described, those skilled in the art will recognize more modifications that may be made that would nonetheless fall within the scope of the present invention. Therefore, the present invention should not be limited to the apparatus described. Instead, the scope of the present invention should be consistent with the invention claimed below. | An aerodynamic cargo container with rounded rear doors is disclosed. The aerodynamic cargo container includes an angled rear area that reduces base drag when the container is transported. The rear sliding door allows for partial opening of the door and allows for operation of the door when the rear of the container is in close proximity to another object. The crash attenuating skirt deflects vehicles away from the cargo container. A pair of cargo doors may define the curved contour of the trailer rear section. These doors may have a plurality of pivoted and segmented sections that assume the curved contour of a stationary edge when the doors are moved to a closed position. | 1 |
The purpose of this invention is to bring forth a small, portable, low cost, battery operated radio-controlled decoy that simulates the sound of small arms fire. This would distract and confuse defending forces when attacked by advancing or infiltrating forces, such as Special Forces, Scouts Units and others. The decoy system can also be used to divert enemy soldiers that are in pursuit of units that have infiltrated their territory.
A simple scenario will indicate the tactical application: assume that a Scout Unit or a Special Forces unit has entered enemy territory, and suddenly they are discovered and are pursued by the enemy forces. As they retreat, they activate their radio transmitter decoys, which they have placed around the enemy camp earlier. The decoys are set up to transmit sounds that simulate an M16 or a machine gun. Now the enemy, hearing the sounds of many guns firing from many directions, believes that they are being attacked by a large force and returns fire in the directions of the decoys. The Scouts or Special Forces then have enough time to retreat.
The decoy operates by means of digitized sound signals which are stored in a computer memory such as an EPROM (erasable programmable read only memory) or EEPROM (electrically erasable programmable read only memory). The sounds corresponds to sounds made by standard military issue weapons such as the M16 rifle or the SAW or M60 machine gun. Since the sounds from a rifle or machine gun contain mostly high frequencies they can be simulated effectively by small, transducer, i.e. low cost horns or dome tweeters that are commercially available.
The sound simulator is installed in a small box, which also incorporates a radio-controlled link. The radio control is coded to prevent unauthorized activation and to enable individual activation of a number of different sound simulator units each responsive to a unique code. Such a remote control radio link is available in the military arsenal, and is known as the Remote Activated Munitions System (RAMS). Remote control will enable friendly forces to deploy the decoy, move some distance away, and then activate the decoys as needed to confuse the enemy in pursuit. The decoy will be able to project sounds simulating rifles and machine guns for at least several hundred feet.
DESCRIPTION OF DRAWINGS
FIG. 1 shows a schematic of an embodiment of the invention;
FIG. 2 shows a tactical scenario in which a decoy, hidden in the brush, attracts the enemy in pursuit, and allows friendly forces to escape;
FIG. 3 is an illustration of a physical configuration of the decoy, showing some of the internal components;
FIG. 4 shows a drawing of the Remote Activation Munition System (RAMS);
FIG. 5 shows a schematic of a control module;
FIG. 6 shows a graph of the pulses that were selected for the 7.62 mm machine gun;
FIG. 7 shows a graph of the pulses shown in FIG. 6 after electronic processing to remove noise;
FIG. 8 shows a schematic of an OSV Russian troop carrier;
FIG. 9 shows that the low frequency output of a low frequency amplifier is conducted to the woofers through the slip rings in the turret;
FIG. 10 shows vehicle batteries suitable for powering an embodiment of the present invention.
DETAILED DESCRIPTION
With reference to FIG. 1, remote control sound simulator 10 includes high frequency horns ( 100 ) which emit a high frequency sound from a audio amplifier ( 110 ). The signal being amplified emanates from a signal source or EPROM ( 120 ), which is activated by a radio receiver ( 130 ) when it is stimulated by a transmitter (not shown).
Note that in FIG. 1, a battery 140 is used to power all system components at all times. When the radio receiver is activated by a transmitter (not shown) it turns on an electrical switch 142 (transistor board) which in turn activates the signal source 120 , the high frequency amplifier 110 and the high frequency horns 110 .
Example of Initializing System for Decoy
An example of a small, portable, battery operated radio transmitter and receiver suitable for use with the gun sound simulator and readily available in the military arsenal is shown in FIG. 4 . The receiver 410 provides an electrical output to initiate the decoy upon receipt of a signal from the transmitter 420 . The system in FIG. 4 is known as the Remote Activation Munition System (RAMS).
The Transmitter.
In a preferred embodiment, this control unit is capable of generating user-set special coded signals and radio transmitting them to any RAMS (or similar) receivers, which have been set by users to respond to these signals. With line of sight transmission, the transmitter, powered by its internal batteries, can actuate a matched receiver at a range of 1.2 miles. A RAMS antenna, (or a field expedient 10-foot piece of wire) must be attached to the transmitter's antenna post to properly facilitate transmission. The RAMS transmitter is powered by four user-installed standard 9-volt (transistor radio type) batteries.
The Receiver.
Preferably, the receiver will be like a RAMS receiver, i.e., a small, rectangular, handheld device which will function when it receives a specifically coded radio signal. The receiver may be set to respond to any of three common code signals, which can be transmitted by any RAM transmitter. Receivers can also be programmed by a specific transmitter to respond to one of four unique coded signals that can be generated only by that specific transmitter. Each Receiver is capable of functioning multiple decoys through up to 100 feet of WD-1/TT or other common type two-conductor signal wire. A suitable external antenna, such as a 10-foot piece of wire, must be attached and rigged as an antenna since the unit has no internal antenna and the best range is gained by the use of a well matched antenna. The receiver is turned on and its operational mode is set with its function selector switch. The function selector switch can be set to allow the receiver to be programmed to respond to common coded signals or a specific transmitter, perform an internal self-test, or perform an operational test. An arming tab on the side of the receiver starts a five-minute arming delay timer that does not allow the receiver to actually function until the five-minute arming delay has elapsed.
The receiver is reusable, and is equipped with a status indicator light and a sealable compartment for the single 9-volt battery used to power it. A lithium battery will allow the receiver to remain on duty, fully capable of performing for 15 days. The receiver will actuate the electrical output circuit when it receives the proper coded signal from the RAMS transmitter.
Decoy Circuit
The decoy box contains a control module as shown in FIG. 5, which consists of an input section 150 , a memory 180 , a sequence controller 160 , and an output section 170 .
The Input Section
The input section 150 contains several terminals that are optically isolated from the interior circuitry and can receive signals from remote stations, i.e. it can have an on-off switch activated directly by the RAMS transmitter or an electrical switch activated by the RAMS receiver. The decoy box could also be activated by a simple timer. The remote control signal is coded and carries information to select a weapon, and its firing mode (single-fire, low-rate-of fire, and high-rate-of-fire). For instance, it can select the sound of an M16 or that of an M60 machine gun and it can set the speed of fire; it can alternatively switch between the two weapons to further confuse the pursuing forces.
The Memory Section
The memory section 180 contains the digitized sound pulse information for the weapons that the decoy simulates. A sequencer section receives 160 instructions from the input section 150 , activates the selected weapon and rate of fire, and directs the digitized gun sounds to the digital-to-analog (D/A) converter 172 , the filter network 174 , the amplifier section 176 , crossover network 178 and finally to the sound transducers which may include both low and high frequency transducers. The digitized sound pulse information which is programmed into the EPROM is obtained from field recordings of the weapons to be simulated via either analog high-speed tape or digital recorder. In the laboratory the recording is played through a D/A converter, which digitizes the signal and outputs it to computer memory or floppy disk. By using a sound card and software such as Turtle Beach WAVE® for Windows, the sound may be processed by modifying it and playing it back through the amplifier and speaker system for aural evaluation.
Two types of modifications are done. In the first one, the portion of the sound pulse to be stored in the decoy memory is selected. The digitized recorded sound contains many sound pulses, some having less noise than others. The best pulse, that is the pulse that provides the most realistic sound when played back through the amplifiers and speaker system, is chosen. The precise start and stop time of the pulse also are selected when playing back repeatedly through the system. The pulses that were selected for the 7.62 mm machine gun are shown in FIG. 6 .
In the second modification, the sound pulse is cleaned to remove noise and further enhance the audio playback sound. The recording system is more susceptible to noise than the human ear, so it records noise along with the signal. The noise worsens the sound when it is played back through the system. Therefore, the pulse must be cleaned up electronically to remove the noise. The modified signal is shown for the 7.62 mm machine gun in FIG. 7 . The same procedure is used for simulating the sound of an M16 rifle or any other weapon used for decoy.
The modified pulse shown in FIG. 7 is stored permanently on an EPROM. The EPROM can be small and inexpensive since it will store only one pulse of each type of weapon used. The stored pulses can be played back at any desired repetition rate through the decoy speakers.
Simulator for Vehicle Gun Sound
The concept, which has been described for the filed deployable decoy, can be extended to simulate other weapons, which can be used during forces-on-forces training. In training areas such as the U.S. Army's National Training Center, Fort Irwin, CA (NTC), training vehicles currently in use lack systems that can simulate the sound of real guns. A sound system that simulates that of a cannon for the OSV troop carrier would add reality to the battlefield training experience. The OSV is a Russian troop carrier used extensively by the opposing forces at NTC. A schematic of the OSV vehicle is shown in FIG. 8 . The vehicle is furnished with a machine gun similar to the 7.62 mm gun and a cannon similar to the 15 mm cannon. The cannon can be fired in the single-shot mode, at a low-rate of fire of 100 rounds per minute, or at a high rate of fire of 200 rounds per minute. The machine gun has a single rate of fire of 700 rounds per minute.
The gun simulator is mounted on the vehicle 500 of FIG. 8 transducers such as. Acoustic horns 502 are mounted on the turret 508 , and are powered by an audio amplifier 506 mounted inside the turret 508 . Two woofers 504 are installed in the VISMOD compartment 510 and are connected to amplifier 506 in the turret 508 . Woofers i.e., low frequency sound transducers 504 can be mounted on the hull of VISMOD 510 because the low frequency gun sounds are non directional. Control of all equipment takes place from the turret 508 .
FIG. 9 is a schematic of the components of the vehicle gun sound simulation system. The operator selects a weapon and firing rate and pushes the trigger button on the firing circuit 520 . The signal source 522 then reproduces the corresponding audio signal. The signal then passes to a crossover network 524 that separates the sound signal into a high frequency band and a low frequency band. The high frequency band signal is directed to the input of a single-channel high frequency amplifier 506 . The output of the amplifier goes to four horns 502 mounted outside the turret 508 . Horns 502 broadcast the higher frequency portions of the signal. The low frequency band signal is directed to the input of single channel low frequency amplifier 507 mounted in the turret 508 . The output goes to two woofer speakers 502 that are mounted in the VISMOD 510 and broadcast the lower frequency portions of the signal.
FIG. 9 shows that the low frequency output of a low frequency amplifier is conducted to the woofers through the slip ring 512 in the turret.
The system is powered by the batteries shown in FIG. 10 . Battery 526 is mounted in the turret to power the amplifiers 506 and 507 and other equipment in the turret 508 . The systems are turned on and off through a control panel 528 . The control circuit for the system is the same as that used by the decoy and was described in FIG. 5 .
The invention described in this application can be used to simulate the sound of virtually any type of gun or cannon. One can also simulate the sound of multiple guns firing at the same time (tandem mode) or firing randomly. The technology to accomplish all of the above is the same as that described by the decoys application.
Having thus shown and described what are at present considered to be preferred embodiments of the present invention, it should be noted that the same have been made by way of illustration and not limitation. Accordingly, all modifications, alterations and changes coming within the spirit and scope of the present invention are herein meant to be included. | A small, portable, low cost, battery operated, radio-controlled decoy simulates the sound of small arms fire. The units may be deployed remotely in the field to distract and confuse defending forces when attacked by advancing or infiltrating forces. | 5 |
CLAIM OF PRIORITY
The present application claims priority from Japanese Patent Application JP 2012-220114 filed on Oct. 2, 2012, the content of which is hereby incorporated by reference into this application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a display device and it particularly relates to a liquid crystal display device that ensures the reliability of seal in spite of a narrow frame.
2. Description of the Related Art
A conventional liquid crystal display device includes a TFT substrate having a pixel electrode, thin film transistors (TFT), etc. formed in a matrix; a counter substrate disposed in facing relation to the TFT substrate and having a color filter, etc. formed at portions corresponding to the pixel electrodes of the TFT substrate; and liquid crystals put between the TFT substrate and the counter substrate. Images are formed by controlling the transmittance of light for every pixel by liquid crystal molecules.
Since the liquid crystal display devices are flat and light in weight, their application use has been extended in various fields. Small-sized liquid crystal display devices have been used generally for mobile phones, DSCs (Digital Still Cameras), etc. For the small-sized liquid crystal display devices, there is a strong demand for decreasing the outer dimension while ensuring a predetermined display region. Then, a distance between the end of the display region and the end of the outer contour, that is, a so-called, frame is narrowed. In this case, the area of a seal portion for sealing liquid crystals is decreased, resulting in a problem in ensuring the reliability of the seal portion.
It is inefficient to manufacture liquid crystal display panels on a one by one basis. Thus a method has been adopted of forming a plurality of liquid crystal display panels on a mother substrate, and then separating individual liquid crystal display panels from the mother substrate by scribing, etc. Further, as a method of sealing liquid crystals, a method of injecting liquid crystals through a sealing port has been used so far, but in this case it takes much time for injection of the liquid crystals. To cope with this, a so-called one drop fill (ODF) method has been adopted, in which a sealant is first formed to a TFT substrate or a counter substrate, and the liquid crystals are then sealed inside of the liquid crystal display panel while accurately controlling the amount of the liquid crystals in the inside of the sealant.
With the ODF method, the sealant is formed as a closed loop. While the sealant is coated by a dispenser or the like, portions of the sealant will overlap at the starting point and the end point of sealant coating, resulting in an increase in thickness of the sealant at the overlap portion. This may cause gap failure between the TFT substrate and the counter substrate or protrusion of the sealant toward the display region.
As a countermeasure for the problem with the sealant overlapping, JP-A-2010-145897 describes a configuration in which a recess is formed to an overcoat film formed to a counter substrate at portions corresponding to a starting point and an end point of the coated sealant, thereby absorbing an excessive sealant to the portion.
SUMMARY OF THE INVENTION
JP-A-2010-145897 describes a method in which a coated sealant forms a closed loop in one liquid crystal display panel and the overlap portion of the sealant is present at the side of the liquid crystal display panel.
In the configuration of JP-A-2010-145897, a recess is formed to the overcoat film of the counter substrate only at a portion corresponding to the overlap portion of the sealant.
JP-A-2010-145897 does not describe clear effects obtained when the overlap portion of the sealant is formed at the corner of the counter substrate. In particular, when the sealant is coated on a plurality of TFT substrates on a mother TFT substrate in which a plurality of TFT substrates are formed as illustrated in FIG. 5 of the present application, a cross portion of the sealants is formed at two positions on the liquid crystal display panel, but it is not certain whether the configuration described in JP-A-2010-145897 is applicable to such a configuration. Further, in the configuration of JP-A-2010-145897, it is necessary to partially cut out the periphery of an overcoat film. While general overcoat films can be formed by merely coating and curing, the overcoat film provided in JP-A-2010-145897 has to be formed with recessed portion by applying photolithography to the overcoat film resulting in increase the cost.
FIG. 5 illustrates an example of a coating configuration of a sealant 10 to a TFT substrate 100 on a mother TFT substrate to which the invention is applied. In FIG. 5 , a dotted line indicates a boundary for a portion where a counter substrate is disposed when a liquid crystal display panel is in a completed state. A portion below the dotted line is a portion where one sheet of the TFT substrate is present, serving as a terminal portion 150 . The sealant 10 is formed at the periphery where a TFT substrate and a counter substrate overlap each other.
The configuration of the sealant in FIG. 5 has such a shape that the sealant 10 can be coated continuously by a dispenser or the like to a plurality of TFT substrates on a mother TFT substrate. For example, one sealant is coated in a U-shaped configuration along a cut line 50 of the TFT substrate from the right and then another sealant 10 is coated in an inverted U-shape configuration from the left. At portions C in FIG. 5 , two sealants 10 are formed in an overlapping manner. With such a coating method, the sealant can be coated efficiently to a mother TFT substrate having many TFT substrates formed therein or to a mother counter substrate having many counter substrates formed therein.
In this case, the width of the sealant 10 increases in the overlap portion of the counter substrate and the TFT substrate. In FIG. 5 , two sealants 10 are formed on both sides of the cut line 50 along the longer side. After coated on the TFT substrate, the sealants 10 are pressed to bond the TFT substrate and the counter substrate each other so as to define a predetermined gap and thus the sealants 10 are extended. As a result, the sealants 10 are formed over the cut line 50 .
A display region 30 is formed inside of the coated sealant 10 . A distance from the end of the display region 30 to the cut line 50 of the TFT substrate, that is, the width of a so-called frame is, for example, D 1 =0.8 mm at the longer side, D 3 =2.3 mm at the shorter side on the side of the terminal, and D 2 =1.0 mm at the shorter side opposite to the terminal. In a conventional manner for coating the sealant as above, a sealing failure has occurred as follows. The sealant 10 protrudes to the display region 30 from the overlap portion of the sealants 10 in the corner portion.
FIG. 6 is a plan view near the cut line 50 at the corners of each TFT substrates on a mother TFT substrate. An organic passivation film 109 is formed as far as the outside of the display region 30 . A peripheral circuit 40 such as a scanning line driving circuit is formed below the organic passivation film 109 at the outside of the display region 30 . In FIG. 6 , hatched portions show removed portions 20 of the organic passivation film.
The organic passivation film removed portions 20 are formed as three grooves at the periphery of the display region 30 . Further, the organic passivation film removed portions 20 are formed each at a predetermined width with the cut line 50 of the individual TFT substrate being put therebetween. In FIG. 6 , a portion indicated by a dotted line is a portion in which the sealant 10 is to be formed. As shown in FIG. 6 , two sealants 10 overlap each other at the corners of the TFT substrates.
FIG. 7 is a cross sectional view along line B-B in FIG. 6 . While FIG. 7 is a simplified cross sectional view, a detailed cross sectional view is to be described specifically in FIG. 1 . In FIG. 7 , an organic passivation film 109 is formed over a TFT substrate 100 . Layers below the organic passivation film 109 are not illustrated. Organic passivation film removed portions 20 are formed to the organic passivation film 109 and each portion is formed as a groove. The end of the TFT substrate is formed as an organic passivation film removed portion 20 . An inorganic insulation film 111 made of SiN, etc. is formed to cover the organic passivation film 20 .
The TFT substrate 100 and the counter substrate 200 are bonded by a sealant 10 , and liquid crystals 300 are sealed inside the sealant 10 . In FIG. 7 , the TFT substrate 100 and the counter substrate 200 are superposed with a predetermined gap formed between them in which the sealant 10 is in a pressed state. If the width of the sealant 10 increases a predetermined dimension or more when the sealant 10 is pressed, this may cause a failure that the sealant 10 protrudes to the display region.
In the TFT substrate 100 and the counter substrate 200 , formed at the surface in contact with liquid crystals 300 is an alignment film which is not illustrated. When the alignment film is present between the sealant 10 and an inorganic insulation film 111 , bonding strength of the sealant 10 is lowered. To deal with the deterioration of the sealant 10 mentioned above, as shown in FIG. 7 , an organic passivation film removed portions 20 are formed in a groove shape and serve as dams for preventing the alignment film from flowing out to the outside. A portion A in FIG. 7 shows that such three dams are formed.
In FIG. 7 , since neither the alignment film nor the organic passivation film 109 is formed in a portion B, bonding strength between the sealant 10 and the TFT substrate 100 is great and the reliability of the seal can be ensured at the portion. As shown in FIG. 6 and FIG. 7 , the width of the groove-like organic passivation film removed portion 20 has a width which is identical between the side and the corner. This is because the main purpose of the groove-like organic passivation film removed portions 20 is to provide a dam to the alignment film.
FIG. 8 is a plan view illustrating the state in which the width of the sealant 10 is enlarged at an overlap portion of the sealants 10 , and the sealant 10 protrudes as far as the display region 30 as indicated by C in FIG. 5 . FIG. 8 illustrates the presence of a sealant protrusion portion 31 in which a portion of the sealant 10 protrudes to the display region 30 . Such a liquid crystal display panel is defective.
The subject of the present invention is to prevent the sealant from protruding to the display region while ensuring the reliability of the seal in a liquid crystal display panel having a narrowed frame.
The present invention intends to overcome the problems described above and specifically comprises the following configurations. That is, the present invention provides a liquid crystal display device comprising a TFT substrate including a region for display and having an organic passivation film formed thereover, a counter substrate disposed with a sealant formed in a seal portion between the TFT substrate and the counter substrate, and liquid crystals put between the TFT substrate and the counter substrate, in which, the organic passivation film is formed as far as the outside of a display region of the TFT substrate, the organic passivation film having a groove-like organic passivation film removed portion surrounding the display region in the seal portion, the width of the groove-like organic passivation film removed portion being larger at the corner than at the side, a peripheral circuit is formed in the seal portion of the TFT substrate, and a gap between the TFT substrate and the counter substrate in the seal portion is defined by a pillar spacer formed on the counter substrate and a pedestal of the organic passivation film formed over the TFT substrate.
According to the present invention, when sealant is formed to each of the TFT substrates in the mother TFT substrate, since the width of the groove-like organic passivation film removed portion also that serves as a dam for the alignment film is enlarged at the corner than at the side, even if the sealants are formed overlapping each other in the portion, the sealants do not protrude to the display region.
Further, when a peripheral driving circuit is formed in a layer below the organic passivation film removed portion, since the gap between the TFT substrate and the counter substrate at the seal portion is controlled by using a pillar spacer formed on the side of the counter substrates with the organic passivation film at a portion other than the organic passivation film removed portion being as a pedestal, the peripheral driving circuit is not injured.
Further, in the present invention, since no additional photolithographic step is necessary for preventing protrusion of the sealant at the corner, the cost does not increase when the invention is applied.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a liquid crystal display device having a common electrode top structure to which the present invention is applied;
FIG. 2 is a plan view illustrating a relation between a pixel electrode and a common electrode;
FIG. 3 is a plan view for the corner of a TFT substrate in the invention;
FIG. 4 is a cross-sectional view along line A-A in FIG. 3 ;
FIG. 5 illustrates a configuration of coating a sealant in the liquid crystal display device to which the invention is applied;
FIG. 6 is a plan view of a corner in a TFT substrate in a conventional embodiment;
FIG. 7 is a cross sectional view along line B-B in FIG. 6 ; and
FIG. 8 is a plan view illustrating a state in which a sealant protrudes to a display region.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is to be described specifically by way of preferred embodiments.
First Embodiment
FIG. 1 is a cross sectional view of an IPS pixel region of a common electrode top structure to which the invention is applied. TFT in FIG. 1 is a so-called top gate TFT. As a semiconductor, LTPS (Low Temperature Poly-Si) is used. In addition to the common electrode top structure, IPS of a pixel electrode top structure is also present, to which the invention is also applicable.
On the other hand, when an a-Si semiconductor is used, a so-called bottom gate TFT is often used. In the subsequent description, while the top gate TFT is to be described as an example, the invention is applicable also to a case of using the bottom gate TFT. Also in a case of using the bottom gate TFT, the invention is applicable to any of a common electrode top type or a pixel electrode top type.
In FIG. 1 , a first underlayer film 101 made of SiN and a second underlayer film 102 made of SiO 2 are formed over a glass substrate 100 by CVD (Chemical Vapor Deposition). The first underlayer film 101 and the second underlayer film 102 serve to prevent impurities in the glass substrate 100 from contaminating a semiconductor layer 103 .
The semiconductor layer 103 is formed over the second underlayer film 102 . The semiconductor layer 103 is provided by forming an a-Si film over a second underlayer film 102 by CVD and converting the a-Si film into a poly-Si film by laser annealing. The poly-Si film is patterned by photolithography.
A gate insulating film 104 is formed over the semiconductor film 103 . The gate insulation film 104 is an SiO 2 film formed from TEOS (tetraethoxy silane). The film is also formed by CVD. A gate electrode 105 is formed over the insulation film 104 . The gate electrode 105 is formed in the same layer and at the same time as a scanning signal line. The gate electrode 105 is formed, for example, of an MoW film. An Al alloy is used when it is necessary to lower the resistance of the gate interconnect 105 .
The gate electrode 105 is patterned by photolithography and, during patterning, impurities such as phosphorus or boron are doped in the poly-Si layer to form a source S or a drain D in the poly-Si layer by ion implantation. Further, a LDD (Lightly Doped Drain) layer is formed between the channel layer of the poly-Si layer and the source S or the drain D by utilizing a photoresist upon patterning the gate electrode 105 .
Then, a first interlayer insulation film 106 is formed by SiO 2 covering the gate electrode 105 or a gate interconnect. The first layer insulation film 106 is formed for insulating the gate interconnect 105 and a source electrode 107 . A through hole 120 is formed in the first interlayer insulation film 106 and the gate insulation film 104 for connecting the source S of the semiconductor layer 103 and the source electrode 107 . Photolithography for forming the through hole 120 in the first interlayer insulation film 106 and the gate insulation film 104 is performed simultaneously.
The source electrode 107 is formed over the first insulation film 106 . The source electrode 107 is connected to a pixel electrode 112 by way of the through hole 130 . In FIG. 1 , the source electrode 107 is formed in a wide area so as to cover the TFT. On the other hand, the drain D of the TFT is connected to a drain electrode in a not illustrated portion.
The source electrode 107 , the drain electrode, and a video signal line are formed in the same layer and at the same time. For example, an AlSi alloy is used for the source electrode 107 , the drain electrode, and the video signal line (hereinafter typically represented by the source electrode 107 ) in order to lower the resistance. Since the AlSi alloy generates hillock or Al diffuses into other layers, a structure of sandwiching AlSi with a not illustrated barrier layer and a cap layer made of MoW is adopted.
An inorganic passivation film (insulation film) 108 is formed to cover the source electrode 107 to protect the entire TFT. The inorganic passivation film 108 is formed by CVD in the same manner as the first underlayer film 101 . An organic passivation film 109 is formed to cover the inorganic passivation film 108 . The organic passivation film 109 is formed of a photosensitive acrylic resin. The organic passivation film 109 can be formed, for example, of silicone resin, epoxy resin, polyimide resin, etc. in addition to the acrylic resin. Since the organic passivation film 109 serves as a planarization film, the film 109 is formed to have a large thickness. The thickness of the organic passivation film 109 is 1 to 4 μm and is about 2 μm in most cases.
For establishing electric conduction between the pixel electrode 110 and the source electrode 107 , a through hole 130 is formed in the inorganic passivation film 108 and the organic passivation film 109 . A photosensitive resin is used for the organic passivation film 109 . After coating of a photosensitive resin, when the resin is exposed, only the portion exposed to light is dissolved in a predetermined developer. That is, formation of a photoresist can be saved by using the photosensitive resin. After the through hole 130 is formed in the organic passivation film 109 , the organic passivation film is baked at about 230° C. to complete the organic passivation film 109 .
In the invention, the organic passivation film extends as far as the seal portion of the liquid crystal display panel and the organic passivation film removed portion is formed in a groove-like shape at the seal portion so that the film serves as a dam that prevents the alignment film from flowing to the outside. Further, in the invention, the width of the groove of the organic passivation film removed portion is made larger at the corner than at the side thereby preventing the sealants from protruding to the display region when the sealant are coated being overlapped each other.
A through hole is formed in the inorganic passivation film 108 by etching using the organic passivation film 109 as a resist. Thus, a through hole 130 for electric conduction between the source electrode 107 and the pixel electrode 110 is formed. Since the inorganic passivation film 108 is etched using the patterned organic passivation film 109 as a resist, it is not necessary to use an additional mask and the photolithographic step can be performed by one step. Since the organic passivation film 109 has a large thickness, the dimension of the hole is different between the upper part and the lower part of the through hole 130 .
In FIG. 1 , the upper surface of the thus formed organic passivation film 109 is planar. Amorphous ITO (Indium Tin Oxide) is deposited by sputtering over the organic passivation film 109 , patterned by using a photoresist, and then etched with oxalic acid to pattern a pixel electrode 112 . The pixel electrode 112 is formed also covering the through hole 130 . The pixel electrode 112 is formed of ITO as a transparent electrode and has a thickness, for example, of 50 to 70 nm.
Then, a second interlayer insulation film 111 is deposited covering the pixel electrode 112 by CVD. The CVD is performed under the condition of temperature at about 200° C., so this CVD is referred to as low temperature CVD. The low temperature CVD is used for preventing denaturation of the already formed organic passivation film 109 .
The second interlayer insulation film 111 is patterned by a photolithographic step in which the patterning is performed for a terminal portion and patterning for the through hole region is not necessary.
Amorphous ITO is sputtered over the second interlayer insulation film ill, and a comb-shaped common electrode 110 is formed by a photolithographic step. The thickness of the common electrode 110 is, for example, about 30 nm. The common electrode 110 is formed thinly so as to prevent alignment failure by rubbing shadow when the alignment film 113 formed over the common electrode 110 is applied with rubbing.
FIG. 2 is a plan view illustrating a relation between the comb-shaped common electrode 110 and the pixel electrode 112 coated in a solid form. In FIG. 2 , the common electrode 110 is disposed above the pixel electrode 112 with a not illustrated second interlayer insulation film being put therebetween. As illustrated in FIG. 1 , lines of electric force extend from the upper surface of the common electrode 110 through slits 115 in the comb-shaped common electrode 110 to the pixel electrode 112 and liquid crystal molecules are rotated by the lines of electric force.
In FIG. 1 , both the pixel electrode 112 and the common electrode 110 are formed in the region of the through hole 130 . Accordingly, a light transmitting region can be formed also to the upper end of the through hole 130 or the inner wall of the through hole 130 when the liquid crystal molecules 301 can be aligned properly. Accordingly, compared with a pixel electrode top structure, the pixel region can be used more efficiently for forming images.
In FIG. 1 , a counter substrate 200 is provided with the liquid crystal layer 300 being sandwiched between the substrates. A color filter 201 is formed to the inner side of the counter substrate 200 . As the color filter 201 , color filters of red, green, and blue are formed on every pixels to form color images. A black matrix 202 is formed between adjacent color filters 201 to improve the contrast of images. The black matrix 202 also serves as a light shielding film for the TFT to prevent photocurrent from flowing to the TFT.
An overcoat 203 is formed to cover the color filter 201 and the black matrix 202 . Specifically, since each of the color filter 201 and the black matrix 202 has an uneven surface, the overcoat film 203 is adapted to have a flat surface. An alignment film 113 is formed over the overcoat film 203 for determining initial alignment of liquid crystals. Since FIG. 2 illustrates an IPS system, the common electrode is formed on the side of the TFT substrate 100 and not formed on the side of the counter substrate 200 .
As illustrated in FIG. 1 , a conduction film is not formed to the inner side of the counter substrate 200 in IPS. Then, the potential of the counter substrate 200 becomes instable. Further, external electromagnetic noises intrude to the liquid crystal layer 300 to give an undesired effect on images. For overcoming such a problem, an external conductive film 210 is formed to the outside of the counter substrate 200 . The external conductive film 210 is formed by sputtering ITO, which is a transparent conductive film.
FIG. 3 is a plan view near cut lines 50 at corners of individual TFT substrates on a mother TFT substrate in the invention. The organic passivation film 109 is formed as far as the outside of the display region 30 . A peripheral circuit 40 such as a scanning line driving circuit is formed below the organic passivation film 109 at the outside of the display region 30 . In FIG. 3 , hatched portions are the organic passivation film removed portions 20 .
The organic passivation film removed portions 20 are formed as two grooves at the periphery of the display region 30 . In FIG. 3 , the width of the grooves of the inner organic passivation film removed portions 20 is larger at corner than at side. In FIG. 3 , the groove-like organic passivation film removed portions 20 are indicated only to portions of the TFT substrate, but the portions are actually formed surrounding the entire display region 30 .
In FIG. 3 , portions indicated by dotted lines are portions where the sealants 10 are formed. As illustrated in FIG. 3 , two sealants 10 overlap each other at the corners of the TFT substrates. While the width of the sealant 10 is larger in the overlap portion of the two sealants 10 , since the width of the grooves of the organic passivation film removed portions 20 are larger at the corners, protrusion of the sealant 10 to the display region 30 can be prevented also in the overlap portion of the sealants 10 . Also in the invention, the groove-like organic passivation film removed portions 20 also serve as dams for preventing the alignment film from flowing to the outside.
FIG. 4 is a cross-sectional view along line A-A in FIG. 3 . In FIG. 4 , an organic passivation film 109 is formed over a TFT substrate 100 . While layers as illustrated in FIG. 1 are formed below the organic passivation film 109 , such layers are not illustrated in FIG. 4 .
An organic passivation film removed portions 20 are formed in the organic passivation film 109 and the portions form grooves. The groove-like organic passivation film removed portions 20 are formed by the number of two and the portions serve as dams for preventing the alignment film from flowing to the outside. In this embodiment, the width of the inner groove on the of the two grooves is made larger at the corner so that protrusion of the sealant 10 does not reach the display region 30 even when the sealants 10 are formed being overlapped each other.
The end of the TFT substrate 100 forms the organic passivation film removed portion 20 . An inorganic passivation film 111 formed of SiN or the like is formed to cover the organic passivation film 109 . The region A shown by a dotted line in FIG. 4 is a portion where groove-like passivation film removed portions 20 are formed which serve, in the invention, as dams for preventing the alignment film from flowing to the outside and preventing the sealant 10 from protruding into the display region 30 at a portion where the sealants 10 are coated overlap each other.
A dotted region B in FIG. 4 is an organic passivation film removed portion 20 and, since only the inorganic insulation film 111 is present, bonding strength between the sealant 10 and the TFT substrate 100 is strong to improve the reliability of the seal portion.
A pillar spacer 60 is formed from the counter substrate 200 for defining the gap between the TFT substrate 100 and the counter substrate 200 at the seal portion. While a black matrix, a color filter, an overcoat film, etc. are formed below the pillar spacer 60 in the counter substrate 200 , they are not illustrated in FIG. 4 . The gap between the TFT substrate 100 and the counter substrate 200 at the seal portion has been defined so far by glass fibers. However, in this embodiment, the peripheral circuit 40 is formed at the seal portion on the side of the TFT substrate 100 . When the groove-like organic passivation film removed portion 20 is formed with a large width at the corner, the peripheral circuit 40 may possibly be damaged by glass fibers or beads at the portion.
In the invention, as illustrated in FIG. 4 , since the gap between the TFT substrate 100 and the counter substrate 200 at the seal portion 10 is defined not by using the glass fibers, beads, etc. but by the pillar spacer 60 on the organic passivation film 109 being as a pedestal, a not illustrated peripheral circuit 40 formed below the organic passivation film 109 undergoes no damages.
Further, in the present invention, since the groove of the organic passivation film removed portion 20 for preventing the alignment film from flowing to the outside is used also as a concave portion for preventing the sealant 10 from protruding to the display region 30 in the overlap portion thereof, there is no requirement for additional step for practicing the configuration of the invention. It may suffice to merely change the mask for forming the groove-like organic passivation film removed portion 20 compared with the conventional case.
In FIGS. 3 and 4 , while two groove-like organic passivation film removed portions 20 are used, they may be one or three or more. Importance is attached in that the width of the groove-like organic passivation film removed portions 20 are made larger near the corner where the coated sealants 10 overlap each other than that at the side. The width of the grooves of the organic passivation film removed portion 20 is preferably three times or more larger at the corner than at the side.
In FIG. 3 , also a trigonal organic passivation film 109 is present at the corners of each of the TFT substrates partitioned by cut lines 50 , that is, the organic passivation film 109 is present at the outermost portion in FIG. 4 can also be removed in accordance with the protrusion amount of the sealant 10 .
In FIG. 5 , since the sealants 10 cross at the upper left corner and at the lower right corner of the TFT substrate, the width of the organic passivation film removed portion 20 is made larger than that at the side. However, since the sealants 10 do not cross at the upper right corner and the lower right corner, the width of the organic passivation film removed portions 20 at the upper right corner and the lower right corner may be made identical with the width at the side. In this case, the peripheral circuit 40 can be protected more widely by the organic passivation film 109 than in the upper left corner and the lower right corner where the sealants 10 cross each other.
In the foregoing description, it has been described that the organic passivation film is removed completely with the organic passivation film removed portions 20 , but the organic passivation film 109 can be left thinly by using a half tone exposure technique to the organic passivation film removed portions 20 . In this case, the peripheral circuit 40 can be protected by the thin organic overcoat film that remains in the removed portion while suppressing protrusion of the sealant 10 . | At a corner of a TFT substrate in which sealants are coated overlapping each other, a phenomenon that the width of the sealants is increased and protrude to the display region is prevented. An organic passivation film is formed as far as the outside of the display region. A groove-like organic passivation film removed portion is formed surrounding the display region. Since the sealants are coated overlapping each other at the corner, when a TFT substrate and a counter substrate are superposed at a predetermined gap, the width of the groove-like organic passivation film removed portion is made larger at the corner than the side in order to prevent the sealant from extending. Since an excessive sealant is absorbed in the groove-like organic passivation film removing portion of a larger width at the corner, the sealant can be prevented from protruding to the inside of the display region. | 6 |
This application claims priority to Chinese Patent Application No.: 200510063260.4 filed Apr. 7, 2005 and Chinese Patent Application No.: 200510124185.8 filed Nov. 21, 2005.
TECHNICAL FIELD OF THE INVENTION
This invention relates to a slow and controlled-release polymeric fertilizer with multiple nutrients, in particular relates to an environment-protection slow and controlled-release fertilizer with multiple nutrients. This invention also relates to the preparing process for the fertilizer and the use method of the fertilizer in agriculture.
BACKGROUND OF THE INVENTION
In the prior art, complex-mixing methods are used to obtain the fertilizers with all three elements of nitrogen, phosphorus and potassium, for example, combination of carbamide with potassium dihydrogen phosphate, or mixture of carbamide, calcium phosphate and potassium sulfate. In order to reduce the pollution of fertilizer runoff to the environment, especially to water bodies, slow (controlled)-release fertilizer has become the focus of researches and applications. But the currently available slow-release and controlled-release fertilizers generally adopt coating methods, for example, coating carbamide with a layer of urea-formaldehyde resin film, the coating film is damaged gradually as urea-formaldehyde resin degrading so as to slowly release the fertilizer. WO2003/082005 discloses a preparing method for highly dispersed urea-formaldehyde polymer fertilizer slow-release agent. This polymer achieves slow release of nitrogen fertilizer and the mixture of calcium carbonate, plaster, metallic silicate, talcum powder, sulfur, active carbon, chelated iron, zinc and manganese is added into granulating process. But the material cannot supply phosphorus and potassium needed for crop growth after the material degrades. U.S. Pat. No. 19,810,288,456 discloses a preparing method for solid urea-formaldehyde polymer slow-release fertilizer comprising preparing a liquid mixture of carbamide, formaldehyde and ammonia, heating and acidifing the mixture to start the polymerization of methylene urea, and heating to finish the polymerization of methylene urea, then drying the obtained product which cannot provide phosphorus and potassium needed for crop growth after it degrades in soil. In JP10259083, fertilizer is added into pipes which are biologically degradable polymer, then holes are drilled on the pipes with a certain intervals so that the fertilizer can be released slowly in soil. When the product of JP10259083 is used, the nutrients that the soil can get depend upon the fertilizer ingredients filled into the pipes.
SUMMARY OF THE INVENTION
Different from the prior arts, the present invention surpasses the field of physical mixing and chemically combines three key elements of nitrogen, phosphorus and potassium to form a single polymer and the proportion of each of these three elements can be adjusted in a certain range so as to meet the demands of different crops and soils, therefore, the fertilizer's effective availability is enhanced dramatically. Besides, this invention surpasses the field of coating slow release and makes use of the polymer's gradual biological degradation and hydrolization in soil to release the nutrients that can be absorbed by plants. Therefore, the mechanism of slow and controlled release of the fertilizer of the invention is completely different from that of the ordinary slow-release fertilizers: the slow and controlled-release fertilizer of the present invention depends on degradation and hydrolization of the polymeric fertilizer per se for slow and controlled releasing the nutrients, while the ordinary slow (or controlled)-release fertilizers achieve slow release effect with the help of polymeric coating film.
Generally, one aspect of the invention is to provide a slow and controlled-release polymeric fertilizer. Said slow and controlled-release polymeric fertilizer is a compound with the following general formula:
wherein n is in the range of from 50 to 200, m is in the range of from 0 to 5, and for each repeating unit, M is same or different and is independently selected from the group consisting of K, NH 4 , NHCONH 2 and the like, preferably M is further selected from the group consisting of microelements of Fe, Cu, Zn, Mn and Mg and the like, or of some other microelements needed by crops.
In a preferable embodiment of the slow and controlled-release polymeric fertilizer of the present invention, based on the total mass of the slow and controlled-release polymeric fertilizer, it comprises:
27.9% K 2 O, 42% P 2 O 5 and 16.6% N when m is 0 and all M is K; 12% K 2 O, 18.2% P 2 O 5 and 28.7% N when m is 3 and all M is K; and 8.2% K 2 O, 12.5% P 2 O 5 and 29.4% N when m is 5 and all M is K, wherein the amounts of K, P and N are calculated as that of K 2 O, P 2 O 5 and N respectively.
In addition, the slow and controlled-release polymeric fertilizer of the present invention, based on the total mass of the slow and controlled-release polymeric fertilizer, comprises:
48.4% P 2 O 5 and 28.6% N when m is 0 and all M is NH 4 ; and 19.5% P 2 O 5 and 34.5% N when m is 3 and all M is NH 4 , wherein the amounts of K, P and N are calculated as that of K 2 O, P 2 O 5 and N respectively.
In the slow and controlled-release polymeric fertilizer with multiple nutrients of the invention, the content of nitrogen, phosphorus and potassium can be regulated according to the demand of crops and soils. The adjustable range of the nutrients is 16˜35% by mass of N, 13%˜48% by mass of P 2 O 5 , 6%˜27% by mass of K 2 O and 0.1%˜1% by mass of each microelement, wherein the contents of K, P and N are calculated as that of K 2 O, P 2 O 5 and N respectively.
Another aspect of the invention is to provide a preparing process for the polymeric fertilizer having general formula (I), which comprises:
(1) adding reactants and phosphoric acid into a reactor, heating to generate dihydric phosphate, wherein said reactants are potassium chloride, potassium carbonate or potassium hydroxide and the like. The reactants can also be selected from the group consisting of oxides or hydroxides of Fe, Cu, Zn, Mn, Mg or other metal elements which needed.
(2) adding carbamide and formaldehyde into another reactor, adjusting the pH value to generate methylene urea oligomer at a suitable temperature.
(3) in another reactor, adding the dihydric phosphate obtained in step (1) and product of step (2) or carbamide sufficient to provide needed amount of nitrogen, heating to start the reaction polycondensation, then making the reaction polycondensation continue under the action of the reaction heat; and
(4) granulating the melted polycondensation product.
Another aspect of the invention still relates to the use method of the slow and controlled-release polymeric fertilizer having general formula (I) in crops, wherein said fertilizer is applied independently or in combination with farmyard manure. Preferably the crops are fruit crops, and more preferably the crops are maize and potato. Also the slow and controlled-release polymeric fertilizer with multiple nutrients of the invention can be used as special fertilizer containing microelements.
The slow and controlled-release fertilizer of the invention is a polymeric compound integrating three key elements of nitrogen, phosphorus and potassium into a single polymer. After fertilizing, under the action of water and microorganism in soil, the fertilizer gradually degrades and hydrolyzes to produce nutrients which can be absorbed by plants. The degrading and hydrolyzing process are accelerated gradually, so the fertilizer releases nutrients slowly in early phase, fastly in middle phase and again slowly in anaphase, which is exactly coincides with the nutrients demanded cycles by the plants, therefore, the fertilizer's availability is high. Furthermore, the rest comprising elements of the slow and controlled-release fertilizer of the invention are carbon, hydrogen and oxygen besides three key elements of nitrogen, phosphorus and potassium. The fertilizer does not have any elements harmful to soil, its water solution is neutral, innocuous, flavourless, non-corrosive, so it's environment-friendly and will not pollute the environments and leads to no acidulation or alkalization of the soil, thus is environmental-protective fertilizer.
Comparing with the prior arts, this invention has remarkable advantages, for example:
(1) It integrates the nutrients of nitrogen, phosphorus, potassium, iron, copper, zinc, and manganese etc. into a single polymer, so the fertilizer is more convenient for use.
(2) The total nutrients content (N %+P 2 O 5 %+K 2 O %) of the fertilizer is from 50% to 86% by mass, therefore, the applying amount of this fertilizer is only ⅓˜½ of that of the currently available fertilizers for the same production increasement.
(3) The durative period of the fertilizer can be adjusted according to demand.
(4) The pH value of the water solution of the fertilizer is from 6.5 to 7.5, which is harmless to soils and plants.
(5) After degradating and hydrolyzing, all the nutrients released by the fertilizer can be absorbed completely by the plants with no residues, thus it is an environment-friendly slow and controlled-release fertilizer.
(6) As one of the raw materials, potassium chloride is abundant in resources and low in cost.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments
All the parts and percentages in examples are provided by mass.
1. PREPARATION OF THE SLOW AND CONTROLLED-RELEASE POLYMERIC FERTILIZER WITH MULTIPLE NUTRIENTS OF THE INVENTION
The feeding weights of potassium chloride and phosphoric acid were calculated according to the demand for potassium, then put these raw materials into a acid-proof reactor having stirring device and hydrogen chloride-absorbing device, heated till no more hydrogen chloride was generated and the reaction solution I was obtained. Cooled the reaction solution I to about 60° C. for further use.
The feeding weights of carbamide and formaldehyde were calculated according to the demand for nitrogen, then put these raw materials into another stainless steel reactor having stirring device. Adjusted the pH value to 8˜9, heated the system to 80° C. and then reacted for 1 hour to get reaction solution II. Cooled the reaction solution II to about 60° C. for further use.
Solution I and solution II were dumped together into a reactor with powerful stirring device. They reacted instantly and formed a soft solid mass. The mass was sent directly into a granulator to pelltize the fertilizer, dried the fertilizer granule and then got the slow and controlled-release polymeric fertilizer with multiple nutrients of the invention.
The adding methods for the microelements of iron, copper, manganese and zinc etc. is to turn these microelements into dihydric phosphate at first and then add them to reaction polycondensation.
Example 1
Preparation of Special Fertilizer with m=5 and all M is K
2.3 kg of 85% industrial phosphoric acid were put into a 10-liter enamel reactor, then 1.05 kg of potassium chloride Were added. Heated the system untill no more hydrogen chloride was released. 2 kg of water is added and followed by addition of 0.34 kg of potassium hydroxide. Heated the system to 80° C. for further use.
8.1 kg of 37% industrial formaldehyde were added into a 30-liter stainless steel reactor having stirring device. Adjusted the pH value to 8˜9, heated the system to 60° C. Then 7.2 kg of carbamide were added in batches. Raised the reaction temperature to 80° C., reacted for 0.5 hours to obtain the product for further use.
The two above-mentioned reaction solutions were mixed together while they were still hot, the mixture was pelltized in a granulator and dried. 11.4 kg of product was got. In the product, the content of N is 29.4%, P 2 O 5 is 12.5% and K 2 O is 8.2%.
Example 2
Preparation of Special Fertilizer with m=3 and all M is K
The same method in Example 1 was used to prepare potassium dihydrogen phosphate solution except that 4.9 kg of 37% industrial formaldehyde were added into a 30-liter stainless steel reactor with stirring device. Adjusted the pH value to 8˜9, heated the system to 60° C., and then 4.8 kg of carbamide were added in batches. Raised the temperature to 80° C., reacted for 0.5 hours to obtain the product for further use.
The two above-mentioned reaction solutions were mixed together while they were still hot, the mixture was pelltized in a granulator and dried. 7.8 kg of product was obtained. In the product, the content of N is 28.7%, P 2 O 5 is 18.2% and K 2 O is 12%.
Example 3
Preparation of Special Fertilizer with m=0 and all M is K
6.9 kg of 85% industrial phosphoric acid were added into a 30-liter enamel reactor having stirring device and hydrogen chloride-absorbing device, 3.15 kg of potassium chloride were added. Heated the system till no more hydrogen chloride was released. 3 kg of water and then 1 kg of potassium hydroxide were added. The reaction system was removed into a reactor with high length-diameter ratio while it was still hot. Then 3.6 kg of carbamide were added. The reaction system became a clear and transparent solution when it was heated to above 60° C. When the heating continued to a proper temperature, the system will boil because the polycondensation reaction was a exothermal reaction. When the reaction system became viscous, removed the heater and cooled the obtained product to semi-solid state, then pelltized the product in a granulator and dried. 10.1 kg of product were obtained. In this product, the content of N is 16.6%, P 2 O 5 is 42.0% and K 2 O is 27.9%.
Example 4
Preparation of Special Fertilizer with m=0 and all M is NH 4
6.9 kg of 85% industrial phosphoric acid were added into a stainless steel reactor with high length-diameter ratio, then 4.8 kg of ammonium bicarbonate were added in batches when stirring. Heated the system to 60° C. till no more CO 2 was generated, then 3.6 kg of carbamide were added. Raised the temperature untill the reaction solution was in boiling state. When the reaction solution became viscous, removed the heater and cooled the reaction solution to semi-solid state, then pelltized the product in a granulator and dried. 8.8 kg of product were got. In this product, the content N is 28.6%, and P 2 O 5 is 48.4%.
Example 5
Preparation of Special Fertilizer with m=3 and all M is NH 4
4.6 kg of 85% industrial phosphoric acid were added into a 10-liter stainless steel reactor, and 3.2 kg of industrial ammonium bicarbonate were added in batches when stirring. Heated the system to 60° C. till no more CO 2 was generated, and then kept for use.
9.8 kg of 37% industrial formaldehyde were added into a stainless steel reactor having stirring device. Adjusted the pH value to 8˜9, raised the temperature to 60° C. 9.6 kg of carbamide were added in batches, and then raised the temperature to 80° C., reacted for 0.5 hours to obtain product for further use.
the two above-mentioned reaction solutions were mixed while they were still hot, then the mixture was pelltized in a granulator and dried. 14.6 kg of product were obtained. In this product, the content of N is 34.5% and P 2 O 5 is 19.5%.
Example 6
Preparation of Fertilizer Special for Maize
3.5 kg of 85% industrial phosphoric acid were added into a 40-liter enamel reactor, then 1.6 kg of potassium chloride were added. Heated the system till no more hydrogen chloride was released. Then 0.7 kg of ammonium bicarbonate were added in batches, and the reaction continued till no more CO 2 was generated. 5.4 kg of carbamide were added and the following-on operations were carried out according to Example 4. 6.8 kg of product were got. In this product, the content of N is 35.7%, P 2 O 5 is 31.3% and K 2 O is 6.1%.
Example 7
Preparation of Fertilizer Special for Potato
5.8 kg of 85% industrial phosphoric acid were added into a 40-liter enamel reactor, then 2.6 kg of potassium chloride were added. Heated the system till no more hydrogen chloride was released. Then 8 kg of carbamide were added and the following-on operations were carried out according to Example 4. 12 kg of product were got. In this product, the content of N is 28%, P 2 O 5 is 29.6% and K 2 O is 9.8%.
Example 8
Preparation of Special Fertilizer with Microelements
4.6 kg of 85% industrial phosphoric acid were added into a 40-liter stainless steel reactor, then 68 g of magnesium oxide and 40 g of zinc oxide were added. After they were dissolved, new prepared 50 g copper hydroxide and 50 g ironic hydroxide were added. After these two components were dissolved, 2.7 kg of potassium carbonate were added. Heated the system till no more CO 2 was generated. 3.6 kg of carbamide were added and the following-on operations were carried out according to Example 4. 6.4 kg of slight green product were got. In this product, the content of N is 16.0%, P 2 O 5 is 42.0%, K 2 O is 27.0% and the microelement magnesium, zinc, copper and iron were 0.64%, 0.5%, 0.5% and 0.48%, respectively.
2. Fertilizer Effect Experiments of the Slow and Controlled-Release Polymeric Fertilizer with Multiple Nutrients of the Invention
(1) Field Experiment for Maize
{circle around (1)} Materials and Methods
Soil for experiment: an empty soil in the blank area of Shanxi Agriculture University's experimental seeding nursery was selected as the experimental soil. It was flat, has convenient transportation and irrigation conditions, and was convenient for management and observation. The experimental soil was brown earth of carbonate type with a nature of medium soil and medium fertility. Its representative area was about 1,000 hm 2 . The prior crops were maize, with 22,500 kg of cattle manure and 1,200 kg of SV fertilizer special for maize applied in each hectare of the field, and the output was about 9,900 kg/hm 2 .
Fertilizer for the experiment: the slow and controlled-release polymeric fertilizer with multiple nutrients special for maize of the invention.
Crops for the experiment: maize (Jin Dan 42).
Experiment scheme and method: The experiment was made with four arrangements:
(I) Arrangement 1: the fertilizer for the experiment; 0.03 kg/m 2 (1.5 kg/plot)
(II) Arrangement 2: the fertilizer for the experiment plus farmyard manure (cattle manure); 0.03 kg/m 2 (1.5 kg/plot) of the fertilizer for the experiment plus 2.25 kg/M 2 (112.5 kg/plot) of farmyard manure
(III) Arrangement 3: Conventional fertilization; 0.12 kg/m 2 (6 kg/plot) of SV fertilizer special for maize plus 2.25 kg/M 2 (112.5 kg/plot) of farmyard manure
(IV) Arrangement 4: control; with no fertilizer applied.
Each of the four arrangements was repeated four times.
The experimental field was divided into four regions (four repeats) by the method of partial control, and then each region was divided into four plots of 10 m×5 m (four arrangements) with the plot area of 50 m 2 . The plots were arranged randomly in each region, and the arrangements for this experiment were:
Repeat 1
Repeat 2
Repeat 3
Repeat 4
Arrangement 1
Arrangement 3
Arrangement 4
Arrangement 4
Arrangement 4
Arrangement 4
Arrangement 2
Arrangement 2
Arrangement 3
Arrangement 2
Arrangement 1
Arrangement 3
Arrangement 2
Arrangement 1
Arrangement 3
Arrangement 1
Before sowing, soil samples were collected from the field by 5-spot sampling method and brought to the laboratory for test and analysis.
Cultivating and sowingg were conducted on 20 May 2004. Ploughing and sowing were carried out after applying determined amount of fertilizer and marking the boundaries and plots with wooden signs. The quantity of seeds was 90 kg/hm 2 and weedicide “ETHOXALAMINE” was applied after sowing. The crops were irrigated twice on 24 June and 30 July by plot independent irrigating method and earthed up on 26 July. There were few weeds in the field with weedicide being applied and there was no disaster in 2004. The corns were harvested plot by plot on 13 October and threshed at the site. The output of each plot was weighed. The results were recorded in tables.
{circle around (2)} Result and Analysis
(I) the results of laboratory test and analysis for soil samples of the experiment field were shown in table 1.
TABLE 1
Analysis result of soil sample of the experiment soil
organic
available
available
substance
alkali nitrogen
phosphorus
potassium
(g/kg)
(g/kg)
(mg/kg)
(mg/kg)
pH
8.8
0.90
35.77
209.47
8.0
(II) The experimental results of the output of each plot were shown in Table 2.
TABLE 2
Maize output of experiment plot
plot output (kg)
experiment
plot area
Repeat
Repeat
Repeat
Repeat
arrangement
(m 2 )
1
2
3
4
average
fertilizer for
50
32.4
32.7
27.6
30.5
30.8
experiment
fertilizer for
50
58.8
58.4
62.0
57.2
59.1
experiment +
farmyard
manure
conventional
50
47.3
53.1
50.7
50.9
50.5
fertilization
control
50
26.5
24.4
25.0
26.9
25.7
(III) The hectare yield in maize experiment were shown in Table 3.
TABLE 3
Hectare yield of each plot in maize experiment
output (kg/hm 2 )
experiment
Repeat
Repeat
Repeat
Repeat
increase
arrangement
1
2
3
4
average
ratio (%)
fertilizer for
6480
6540
5520
6100
6160
16.56
experiment
experiment
11760
11680
12400
11440
11820
56.51
fertilizer +
farmyard
manure
conventional
9460
10620
10140
10180
10100
49.11
fertilizer
control
5300
4880
5000
5920
5140
(IV) The four arrangements caused little effect on maize's biological properties. There was no obvious differences in the aspects of budding time, the color and growth of the seedling parts above soil surface, tasseling time, the number of ears on a single plant, array and color of seeds. Therefore, the four arrangements caused little effect on maize's biological properties.
(V) The four arrangements caused great effect on maize's yields and the value of output. As shown in Table 2 and Table 3, the yield differences were great among the plots with and without fertilizing. The yield of corn increased by 16.56% using the fertilizer for experiment, by 56.51% applying the fertilizer for experiment plus farmyard manure and by 49.11% using conventional fertilizing. The output increase effects were all very obvious.
(VI) In light of input-output ratio, only arrangement 2 and arrangement 3 were compared with each other because the other input items were same but the applied fertilizers were different:
In arrangement 2, 300 kg of the fertilizer for the experiment were applied for each hectare, then the corresponding cost is 5 Yuan×300=1,500 Yuan (calculated on the basis of the fact that the cost of the fertilizer is 5 yuan per kg). The 22,500 kg of farmyard manure were applied, then corresponding cost is 0.05 Yuan×22,500=1125 Yuan (calculated on the basis of the fact that the cost of the farmyard manure is 0.05 yuan per kg), the total is 2,625 Yuan. The value of output is 1 Yuan×11,820=11,820 Yuan (calculated according to the price of 1 yuan per kg of the maize this year). The input-output ratio is 1:4.50.
In arrangement 3, 1,200 kg of SV special fertilizer were applied for maize, the corresponding cost is 1,400×1.2=1,680 Yuan, and the cost of farmyard manure is 1125 Yuan, the sum is 2,805 Yuan. The output value is 1 Yuan×10,100=10,100 Yuan. The input-output ratio is 1:3.54.
(VII) statistic analysis about the data in Table 2
TABLE 4
Statistic analysis about experimental results in maize field test
Repeat
Arrangement
1
2
3
4
average
sum
1
32.4
32.7
27.6
30.5
30.8
123.2
2
58.8
58.4
62.0
57.2
59.1
236.4
3
47.3
53.1
50.7
50.9
50.5
202.0
4
26.5
24.4
25.0
26.9
25.7
102.8
average
41.3
42.1
41.3
41.4
sum
165.0
168.6
165.3
165.5
664.4
The data in the table were statistically calculated and carried out variance analysis, as the results were shown in Table 5.
TABLE 5
Variance analysis of random group design
variance source
DF
SS
S 2
F
F 0.05
F 0.01
inter-arrangement
3
3019.55
1006.52
187.09
3.86
6.99
inter-repeat
3
2.115
0.705
0.13
error
9
48.445
5.38
total variance
15
3070.11
Because in inter-arrangement, F=187.09>>F 0.01 =6.69, the difference among inter-arrangement was very obvious, but in inter-repeat, F=0.13<F 0.05 =3.86, so the difference among inter-repeat was not obvious.
The difference significance of the four arrangements were compared by LSR method, and the results were shown in Tables 6 and 7. SE=1.160
TABLE 6
LSR table
P
2
3
4
SSR 0.05
3.20
3.34
3.41
SSR 0.01
4.60
4.86
4.99
LSR 0.05
3.71
3.87
3.96
LSR 0.01
5.34
5.64
5.79
TABLE 7
Contrast of the difference significance among the four arrangements
average plot output
difference significance
four arrangement
(kg)
α = 0.05
α = 0.01
fertilizer for
59.1
a
A
experiment + farmyard
manure
conventional
50.5
b
B
fertilization
fertilizer for
30.8
c
C
experiment
control
25.7
d
C
It was shown in Table 7 that the result difference among the four arrangements were all obvious, of which the fertilizer effect of the mixture of the slow and controlled-release polymeric fertilizer with multiple nutrients of the invention special for maize plus farmyard manure is obviously higher than that of the other arrangements.
(2) Field Experiment of Potato
{circle around (1)} Materials and Methods
Soil for experiment: a soil north to Qingyanglin Village, Lijiaping Township, Wuzhai County, Xinzhou Prefecture was selected as the experimental soil. That soil mainly grows potato and was flat, convenient for transportation, management and observation. The experimental soil was mountain brown earth with a nature of medium soil and medium fertility. Its representative area was about 100 hm 2 . The prior crops were potato, with 15,000 kg of farmyard manure, 1,125 kg of carbamide and 375 kg of calcium superphosphate applied in each hectare of the field, and the output was about 14,250 kg/hm 2 .
Fertilizer for the experiment: the slow and controlled-release polymeric fertilizer with multiple nutrients special for potato of the invention.
Crops for the experiment: potato (DiXi-rui).
Experiment scheme and method: The experiment was made with four arrangements:
(I) Arrangement 1′: the fertilizer for the experiment; 0.03 kg/m 2 (1.5 kg/plot)
(II) Arrangement 2′: the fertilizer for the experiment plus farmyard manure; 0.03 kg/m 2 (1.5 kg/plot) of the fertilizer for the experiment plus 1.58 kg/M 2 (79 kg/plot) of farmyard manure
(III) Arrangement3′: conventional fertilization; 0.11 kg/m 2 (5.5 kg/plot) of carbamide plus 0.04 kg/m 2 (2 kg/plot) of calcium superphosphate plus 1.58 kg/m 2 (79 kg/plot) of farmyard manure
(IV) Arrangement 4′: control; with no fertilizer applied.
Each of the four arrangements was repeated four times.
The experimental field was divided into four regions (four repeats) by the method of partial control, and then each region was divided into four plots of 10 m×5 m (four arrangements), with the plot area of 50 m 2 . The plots were arranged randomly in each region, and the arrangements for this experiment were:
Repeat 1′
Repeat 2′
Repeat 3′
Repeat 4′
Arrangement 2′
Arrangement 3′
Arrangement 3′
Arrangement 4′
Arrangement 1′
Arrangement 4′
Arrangement 1′
Arrangement 2′
Arrangement 4′
Arrangement 1′
Arrangement 2′
Arrangement 3′
Arrangement 3′
Arrangement 2′
Arrangement 4′
Arrangement 1′
Before sowing, soil samples were collected from the field by 5-spot sampling method and brought to the laboratory for test and analysis.
Cultivating and sowing were conducted on 16 May 2004. Ploughing and sowing were carried out after applying determined amount of fertilizer and marking the boundaries and plots with wooden signs. The quantity of seed was 840 kg/hm 2 . The field is dry land and cannot be irrigated. The field was weeded twice respectively on 25 June and 22 July and the crops were earthed up on 9 August. There was no disaster in 2004. The potatoes were harvested plot by plot on 10 Oct. 2004 and weighed for every plot. The results were recorded in tables.
{circle around (2)} Result and Analysis
(I) The results of laboratory test and analysis for soil samples of the experimental soil were shown in Table 8.
TABLE 8
Analysis result of soil sample of the experiment soil
organic
available
available
substance
alkali nitrogen
phosphorus
potassium
(g/kg)
(g/kg)
(mg/kg)
(mg/kg)
pH
11.03
1.22
44.48
110.56
6.8
(II) The experimental results of the yield of each plot were shown in Table 9.
TABLE 9
Potato output of experiment plots
plot output (kg)
experiment
plot area
Repeat
Repeat
Repeat
Repeat
arrangement
(m 2 )
1′
2′
3′
4′
average
fertilizer for
50
48.1
45.7
45.2
49.8
47.2
experiment
fertilizer for
50
83.6
87.1
84.8
84.5
85.0
experiment +
farmyard
manure
conventional
50
75.4
72.3
73.6
76.7
74.5
fertilization
control
50
40.1
39.4
37.9
41.4
39.7
(III) The hectare yield in potato experiment were shown in Table 10
TABLE 10
Hectare yield of each plot in potato experiment
output (kg/hm 2 )
experiment
Repeat
Repeat
Repeat
Repeat
increase
arrangement
1′
2′
3′
4′
average
ratio (%)
fertilizer for
9620
9140
9040
9960
9440
15.89
experiment
experiment
16720
17420
16960
16900
17000
53.29
fertilizer +
farmyard
manure
conventional
15080
11460
14720
15340
14900
46.71
fertilizer
control
8020
7880
7580
8280
7940
(IV) The four arrangements caused little effect on potato's biological properties. There was no obvious differences in the aspects of budding time, the color and growth of the seedling parts above soil surface, or florescence time, and there was neither obvious differences in color, surface smoothness and shape of the potato tubers underground. Therefore, the four arrangements caused little effect on potato's biological properties.
(V) The four arrangements caused great effect on potato's yields and the value of output. As shown in Table 9 and Table 10, the yield differences were great among the plots with and without fertilizing. The yield of potato increased by 15.89% using the fertilizer for experiment, by 53.29% applying the fertilizer for experiment plus farmyard manure and by 46.71% using conventional fertilizer. The yield increase effects were all very obvious.
(VI) In light of input-output ratio, only arrangement2′ and arrangement 3′ were compared with each other because the other input items were same but the applied fertilizers were different.
In arrangement 2′, 300 kg of the fertilizer for the experiment were applied per hecture, the corresponding cost is 5 Yuan×300=1,500 Yuan (calculated on the basis of the fact that the cost of the fertilizer is 5 yuan per kg). The cost of farmyard manure is 0.05 Yuan×15,800=790 Yuan (calculated on the basis of the fact that the cost of the farmyard manure is 0.05 yuan per kg), the sum is 2290 Yuan. The value of output is 0.6 Yuan×17,000=10,200 Yuan (calculated according to the price of 0.6 yuan per kg of the photo this year). The input-output ratio is 1:4.45.
In Arrangement 3′, 1,100 kg of carbamide were applied in each hectare, the corresponding cost is 1,500×1.1=1,650 Yuan; the amount of phosphorus fertilizer for each hectare was 400 kg, and the cost is 600×0.4=240 yuan; and the cost of farmyard manure is 790 Yuan, thus the sum is 3470 Yuan. The output value is 0.6 Yuan×14,900=8,940 Yuan. The input-output ratio is 1:3.34.
(VII) statistic analysis about the data in Table 11
TABLE 11
Statistic analysis about the experimental results in potato field test
Repeat
Arrangement
1
2
3
4
average
sum
1
48.1
45.7
45.2
49.8
47.2
188.8
2
83.6
87.1
84.8
84.5
85.0
340.0
3
75.4
72.3
73.6
76.7
74.5
298.0
4
40.1
39.4
37.9
41.4
39.7
158.8
average
61.8
61.1
60.4
63.1
sum
247.2
244.5
241.5
252.4
T = 985.6
The data in the table were statistically calculated and carried out variance analysis about the results. The results were shown in Table 12.
TABLE 12
Variance analysis of random group design
variance source
DF
SS
S 2
F
F 0.05
F 0.01
inter-arrangement
3
5603.76
1867.92
794.86**
3.86
6.99
inter-repeat
3
17.025
5.675
2.41
error
9
21.135
2.35
total variance
15
5641.92
Because in inter-arrangement, F=794.86>>F 0.01 =6.69, the difference among the inter-arrangement was very obvious, but in inter-repeat, F=2.41<F 0.05 =3.86, so the difference among the inter-repeat was not obvious.
The difference significance of the four arrangements were compared by LSR method, and the results were shown in Tables 13 and 14. SE=0.766
TABLE 13
LSR table
P
2
3
4
SSR 0.05
3.20
3.34
3.41
SSR 0.01
4.60
4.86
4.99
LSR 0.05
2.45
2.56
2.61
LSR 0.01
3.52
3.72
3.82
TABLE 14
The contrast of the difference significance among the four arrangements
average plot output
difference significance
four arrangements
(kg)
α = 0.05
α = 0.01
fertilizer for
85.0
a
A
experiment + farmyard
manure
conventional
74.5
b
B
fertilization
fertilizer for
47.2
c
C
experiment
control
39.7
d
D
It was shown in Table 14 that the result difference among the four arrangements were all obvious, of which the fertilizer effect of the mixture of the slow and controlled-release polymeric fertilizer with multiple nutrients special for potato of the invention plus farmyard manure is obviously higher than that of the other arrangements. And the effect of the fertilizer applied independently was much better than that of the control with no fertilizer applied.
Although some preferably embodiments of this invention are disclosed in the description, the skilled person should understand that these embodiments are not limitative, and the present invention does not intent to be limited by any specific example or embodiment for the reason that there will be improvement about the invention. Undoubtedly, the skilled person in the art will know other embodiments according to principle of the invention. Therefore, the scope of this invention will be covered by the intention, spirit and scope of the claims. | This invention relates to a slow and controlled-release polymeric fertilizer with multiple nutrients having the following general formula:
wherein n, m and M are defined in the description.
The polymeric fertilizer of this invention is an environment-friendly slow and controlled-release fertilizer. Its slow and controlled release action lies in self-degradation and hydrolysis. This invention also relates to the preparing process for the fertilizer and the use method of the fertilizer in agriculture. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
This claims the benefit of copending U.S. Provisional Patent Application No. 60/709,448, filed Aug. 19, 2005.
BACKGROUND OF THE INVENTION
This invention relates to a system and method for controlling the spindle of an electric motor, and more particularly to a system and method for controlling the spindle of a motor that rotates the platter of a disk drive.
Controlling the speed at which the platter of a disk drive rotates is very important, particularly as storage densities increase and platter size decreases. Thus, in a microdrive—i.e., a drive having a platter diameter of about 1 inch or less—even a small error in angular position resulting from an error in speed control may result in an incorrect sector being read or written. It is therefore a nominal goal to determine disk speed to within 0.01%.
Position, and therefore speed, of a disk drive platter is commonly determined by detecting the back electromagnetic field (back-EMF) generated when one of the rotor poles passes one of the stator poles. For example, it is typical for a disk drive motor to have six poles, so that each pole-pair interaction theoretically signifies 60° of motor rotation. However, in practice, it is difficult during manufacturing to accurately position the poles. Therefore, in practice, some sets of adjacent poles may be closer together than 60°, and other sets of adjacent poles may be further apart than 60°. These offsets may be slight, but may be enough to prevent achieving the desired 0.01% accuracy.
Copending, commonly-assigned U.S. patent application Ser. No. 11/104,683, filed Apr. 12, 2005, which is hereby incorporated by reference herein in its entirety, describes a method and apparatus for deriving calibration data for a motor, and a method and apparatus for controlling a motor using that calibration data. In accordance with those methods and apparatus, one phase of the motor power supply is suppressed (i.e., tristated) during a time duration when back-EMF is expected to be detected, and at the same time one of the other phases is grounded and the third phase is pulled high. If the back-EMF is detected outside that duration, the duration is expanded. This is iterated until the back-EMF falls within the expanded duration.
It has been found that when the one phase of the motor power supply is tristated during back-EMF detection, corresponding current spikes occur in the phases that have not been tristated. Thus, there may be a positive current spike in the phase that has been pulled high, and a negative current spike in the phase that has been grounded. These spikes cause spindle speed jitter and acoustic noise, and moreover increase the peak supply current.
It therefore would be desirable to be able to minimize current variations in the phases of a motor power supply during back-EMF detection.
SUMMARY OF THE INVENTION
The current variations in the phases of a motor power supply during back-EMF detection can be minimized by regulating the power supply voltage during the back-EMF detection period. Providing a lower power supply voltage drop during that time reduces the current spikes in the power supply. By choosing the lowered power supply voltage drop properly, the spikes in the current can be reduced to barely detectable irregularities. In order to allow any transients resulting from the tristating of the phase that is tristated to settle out, that phase preferably is tristated at least 2 μs to 5 μs prior to the back-EMF detection period. The amount of time ahead of the T freeze period that that phase is tristated is a function of many factors, including motor form factor and inductance and other variables, and may be programmable.
The power supply voltage preferably is adjusted to about the average voltage across the motor during a complete power supply cycle. The power supply may be pulse-width modulated and the pulse width modulation may be trapezoidal or sinusoidal. In the trapezoidal mode, the supply voltage is substantially constant when turned on, so the average is determined by multiplying the supply voltage by the duty cycle, as derived from a digital-to-analog converter that programs the spindle drive current (spindle DAC). In the sinusoidal mode, the voltage varies, so the duty cycle as derived from the spindle DAC is further modified by a drive pattern factor. The drive pattern factor varies continually between 0 and 1, so preferably it is approximated as a constant, such as about 0.5. Preferably, an adjustment is provided so that the user can fine-tune the constant drive pattern value to minimize the actual current spike.
In one preferred embodiment, the voltage drop across the motor is regulated by setting the supply voltage as the high voltage and regulating the low voltage. In another preferred embodiment, the voltage drop across the motor is regulated by setting the low voltage to ground and regulating the high voltage.
Therefore, in accordance with the present invention, there is provided a method for controlling an electric motor of a type whose speed is measured by detecting back-EMF from pole-pair interaction. The method includes establishing a back-EMF detection period, reducing voltage drop across the motor at least during the detection period, tristating a first phase of the motor at least while the voltage drop is reduced, pulling power to a second phase of said motor up to an upper end of the reduced voltage drop, and pulling power to a third phase of the motor down to a lower end of the reduced voltage drop. Apparatus for carrying out the method, including drivers for the respective phases of the motor, is also provided.
There is also provided apparatus for controlling a motor of a type whose speed is measured by detecting back-EMF from pole-pair interaction. The apparatus comprises means for establishing a back-EMF detection period, means for reducing voltage drop across said motor at least during the detection period, means for tristating a first phase of said motor at least while said voltage drop is reduced, means for pulling power to a second phase of said motor to an upper end of said reduced voltage drop, and means for pulling power to a third phase of said motor to a lower end of said reduced voltage drop.
In one embodiment, the means for tristating tristates the first phase prior to the detection period.
In another embodiment, the means for reducing comprises means for regulating lower end of the voltage drop such that the voltage across the motor ranges between the supply voltage and a voltage above ground.
In another embodiment, the means for regulating comprises means for feeding back the lower end of the voltage drop, and means for comparing the fed back lower end of the voltage drop to a reference voltage above ground.
In another embodiment, the apparatus further comprises means for determining the reference voltage above ground including means for applying a duty cycle factor to the supply voltage.
In another embodiment, the voltage drop across the motor varies trapezoidally over time, and the duty cycle factor comprises a ratio of a user motor speed setting to a maximum motor speed setting.
In another embodiment, the voltage drop across said motor varies sinusoidally over time; and said duty cycle factor comprises a product of (a) a ratio of a user motor speed setting to a maximum motor speed setting, and (b) a factor representing sinusoidal variation of said time-varying voltage.
In another embodiment, the factor representing sinusoidal variation of the time-varying voltage is approximated as a constant.
In another embodiment, the constant is about 0.5.
In another embodiment, the apparatus further comprises means for adjusting the constant.
In another embodiment, the means for reducing comprises means for regulating the upper end of the voltage drop such that the voltage drop across the motor ranges between ground and a voltage below the supply voltage.
In another embodiment, the means for regulating comprises means for feeding back the upper end of the voltage drop, and means for comparing the fed back upper end of the voltage drop to a reference voltage below the supply voltage.
In another embodiment, the apparatus further comprises means for determining the reference voltage below the supply voltage including means for applying a duty cycle factor to the supply voltage.
In another embodiment, the voltage drop across the motor varies trapezoidally over time, and the duty cycle factor comprises a ratio of a user motor speed setting to a maximum motor speed setting.
In another embodiment, the voltage drop across the motor varies sinusoidally over time, and the duty cycle factor comprises a product of (a) a ratio of a user motor speed setting to a maximum motor speed setting, and (b) a factor representing sinusoidal variation of the time-varying voltage.
In another embodiment, the factor representing sinusoidal variation of the time-varying voltage is approximated as a constant.
In another embodiment, the constant is about 0.5.
In another embodiment, the apparatus further comprises means for adjusting the constant.
In another embodiment, the voltage drop across the motor varies over time, and said means for reducing comprises means for reducing the voltage drop to an average value of the time-varying voltage drop.
In another embodiment, the means for reducing comprises means for applying a duty cycle factor to the supply voltage.
In another embodiment, the time-varying voltage varies trapezoidally, and the duty cycle factor comprises a ratio of a user motor current setting to a maximum motor current setting.
In another embodiment, the time-varying voltage varies sinusoidally, and the duty cycle factor comprises a product of (a) a factor representing sinusoidal variation of the time-varying voltage, and (b) a ratio of a user motor current setting to a maximum motor current setting.
In another embodiment, the factor representing sinusoidal variation of the time-varying voltage is approximated as a constant.
In another embodiment, the constant is about 0.5.
In another embodiment, the apparatus further comprises means for adjusting the constant.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other advantages of the invention will be apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which like reference characters refer to like parts throughout, and in which:
FIG. 1 is a schematic view of a three-phase motor;
FIG. 2 is a graphical representation of current in the motor of FIG. 1 in trapezoidal drive mode without the present invention;
FIG. 3 is a graphical representation of current in the motor of FIG. 1 in sinusoidal drive mode without the present invention;
FIG. 4 is a graphical representation of the total current in the motor of FIG. 1 in sinusoidal mode without the present invention;
FIG. 5 is a graphical representation of current in the motor of FIG. 1 in trapezoidal drive mode with the present invention;
FIG. 6 is a graphical representation of current in the motor of FIG. 1 in sinusoidal drive mode with the present invention;
FIG. 7 is a graphical representation of the total current in the motor of FIG. 1 in sinusoidal mode with the present invention;
FIG. 8 is a schematic diagram of motor drive circuitry in accordance with the present invention;
FIG. 9 is a schematic diagram of a drive circuit for a first phase of the motor of FIG. 1 in accordance with the present invention;
FIG. 10 is a schematic diagram of a drive circuit for a second phase of the motor of FIG. 1 in accordance with a first preferred embodiment of the present invention;
FIG. 11 is a schematic diagram of a drive circuit for a third phase of the motor of FIG. 1 in accordance with a first preferred embodiment of the present invention;
FIG. 12 is a schematic diagram of a drive circuit for a second phase of the motor of FIG. 1 in accordance with a second preferred embodiment of the present invention;
FIG. 13 is a schematic diagram of a drive circuit for a third phase of the motor of FIG. 1 in accordance with a second preferred embodiment of the present invention;
FIG. 14 is a block diagram of an exemplary hard disk drive that can employ the disclosed technology;
FIG. 15 is a block diagram of an exemplary digital versatile disc that can employ the disclosed technology;
FIG. 16 is a block diagram of an exemplary high definition television that can employ the disclosed technology;
FIG. 17 is a block diagram of an exemplary vehicle that can employ the disclosed technology;
FIG. 18 is a block diagram of an exemplary cellular telephone that can employ the disclosed technology;
FIG. 19 is a block diagram of an exemplary set top box that can employ the disclosed technology; and
FIG. 20 is a block diagram of an exemplary media player that can employ the disclosed technology.
DETAILED DESCRIPTION OF THE INVENTION
The invention will now be described with reference to FIGS. 1–13 .
FIG. 1 shows, schematically, the three phases A ( 11 ), B ( 12 ) and C ( 13 ) of a three-phase motor 10 with which the present invention may be used It should be remembered that the view of FIG. 1 is theoretical, notwithstanding that it looks like the rotor of a three pole-pair motor. The number of pole-pairs in the motor is completely independent of the number of power supply phases and the present invention will work with substantially any three-phase motor regardless of the number of pole-pairs.
As seen in FIG. 1 , each phase A ( 11 ), B ( 12 ), C ( 13 ) of motor 10 may be modeled as a motor resistance R motor 14 , a motor inductance L motor 15 and back-EMF voltage V BEMF 16 in series between a respective power supply phase SPA ( 110 ), SPB ( 120 ), SPC ( 130 ) and a central tap C tap 17 to which all phases are connected. Although the order of these components 14 , 15 , 16 is reversed in phase C ( 13 ) as compared to phases A ( 11 ) and B ( 12 ), the result would be the same if phase C ( 13 ) were identical to phases A ( 11 ) and B ( 12 ).
The motor power supply can be driven in linear or pulse width modulation (PWM) mode. For power efficiency, PWM mode is preferred. As described above and in above-incorporated application Ser. No. 11/104,683, motor speed can be measured by detecting back-EMF voltage resulting from pole-pair interactions. In accordance with application Ser. No. 11/104,683, during back-EMF detection, a period known as T freeze is introduced, during which there is no current switching activity. During this period, the phase to be detected is tristated, a first one of the other phases is driven high and the second one of the other phases is driven low.
It has been found that if such a speed detection method is used, current in the phases driven high and low is affected. Specifically, as one phase is driven high, current in that phase spikes sharply positive, and as the other phase is driven low, the current in that phase spikes sharply negative.
FIG. 2 illustrates this effect in the case of a trapezoidal drive current. Trace 21 is a representation of an exemplary normalized trapezoidal current waveform in phase B, while trace 22 is a representation of an exemplary normalized trapezoidal current waveform in phase C. Circle 20 represents the T freeze period of phase A (waveform 23 ). As can be seen, during that period there is a sharp positive spike 210 in current waveform 21 , and a sharp negative spike 220 in current waveform 22 .
Similarly, FIG. 3 illustrates this effect in the case of a sinusoidal drive current. Trace 30 is a representation of an exemplary normalized sinusoidal current waveform in phase A, trace 31 is a representation of an exemplary normalized sinusoidal current waveform in phase B, and trace 32 is a representation of an exemplary normalized sinusoidal current waveform in phase C. Circle 300 represents the T freeze period of phase A. As can be seen, during that period there is a sharp positive spike 310 in current waveform 31 , and a sharp negative spike 320 in current waveform 32 .
In either mode, these sharp current spikes cause spindle speed jitter and acoustic noise. Moreover, they increase the peak supply current. For example, FIG. 4 shows the normalized total motor current 40 (sum of phases A, B, C) in motor 10 . As can be seen, during the T freeze period, the peak current is more than 25% higher than the current at any other time.
It has been found that this spiking of the motor current is at least partly the result of applying the full power supply voltage V dd across motor 10 during the T freeze period. However, if the voltage drop across motor 10 is reduced to a regulated voltage V reg at least during the T freeze period, the current spikes during the T freeze period can be substantially reduced.
It should be noted at this point that any of the three phases can be the phase that is tristated during the T freeze period, just as any of the phases can be the phase that is pulled high or pulled low during the T freeze period.
Without the present invention, the spindle motor currents in the different phases during the T freeze period (where phase B is the phase pulled high and phase C is the phase pulled low) may be given by:
I spb =( V dd −V bemf(spb) −V ctap )/( R spb +R ON(PMOS) +SL spb )
I spc =( V ctap −V bemf(spc) )/( R spc +R ON(NMOS) +SL spc )
where:
V ctap =(V dd /2)+V bemf(spa) +V bemf(spb) +V bemf(spc) , R spb and R spc are the respective values of R motor 14 in phases B and C, R ON(PMOS) and R ON(NMOS) are the respective values of the ON resistance of transistors in the respective phase drivers, and SL spb and SL spc are the respective values of impedance L motor 15 in phases B and C.
With the present invention, the spindle motor currents in the different phases during the T freeze period (where phase B is the phase pulled high and phase C is the phase pulled low) may be given by:
I spb =( V reg −V bemf(spb) −V ctap )/( R spb +R ON(PMOS) +SL spb )
I spc =( V ctap −V bemf(spc) )/( R spc +R ON(NMOS) +SL spc )
where:
V ctap =(V reg /2)+V bemf(spa) +V bemf(spb) +V bemf(spc) , and V reg is the regulated voltage during the T freeze period.
It is apparent that the denominators of all the expressions for the two cases are the same, while in the numerators, V reg is substituted for V dd . The factor by which the current spikes are reduced can be approximated as V reg /V dd , assuming that the various V bemf terms are small compared to V reg , which would depend on motor speed, and well as motor characteristics such as form factor and the nature of the motor windings.
Although the voltage drop across motor 10 is reduced from V dd to V reg only during the T freeze period, phase A preferably is already tristated for some period ahead of the T freeze period as well as during the T freeze period, and this longer period may be referred to as the “tristate period.” Thus the only change that occurs during the T freeze period is the driving of phase B high and phase C low. This allows time for all transient effects of the tristating of phase A to settle out before the back-EMF measurement.
Preferably, V reg is chosen to approximate the average voltage across the motor during a power supply cycle, obtained by multiplying the supply voltage V dd by the duty cycle. In PWM trapezoidal mode, this is relatively straightforward. Motor speed is specified by the user, resulting in the setting of a value in the spindle DAC. For an n-bit spindle DAC, the maximum value is 2 n , otherwise referred to as the spindle DAC range. The user motor speed setting is the spindle DAC value. The duty cycle is ratio of actual ON-time to maximum possible ON-time, which in PWM trapezoidal mode is equal to the ratio of the spindle DAC value to the spindle DAC range—i.e., SP_DAC/2 n , where SP_DAC is the value encoded by the spindle DAC. In other words, V reg =(V dd )(SP_DAC)/2 n .
The resulting current (normalized) in the various phases is seen in FIG. 5 , which is similar to FIG. 2 . Trace 51 is a representation of an exemplary normalized trapezoidal current waveform in phase B, while trace 52 is a representation of an exemplary normalized trapezoidal current waveform in phase C. Ellipse 500 represents the tristate period of phase A (waveform 53 ), while circles 50 on all three waveforms represent the T freeze period. As can be seen, during that period there no detectable change in current waveform 51 (compare sharp positive spike 210 in current waveform 21 of FIG. 2 ), and no detectable change in current waveform 52 (compare sharp negative spike 220 in current waveform 22 of FIG. 2 ).
Approximating the average voltage across the motor during a power supply cycle in PWM sinusoidal mode is somewhat more complicated. Because the voltage varies over time, the duty cycle is equal to the ratio of the product of the spindle DAC value and a drive pattern (DP) to the spindle DAC range, where the drive pattern takes into account the time-varying nature of the waveform. Thus, duty cycle=(SP_DAC)(DP)/2 n , and V reg =(V dd )(SP_DAC)(DP)/2 n . DP is generally not a constant and may not even be linear. However, for purposes of approximating the average voltage, it is sufficient to assign to DP a constant value, preferably about 0.5. In order to compensate for the approximate nature of using a constant value for DP, preferably an adjustment is provided to allow users to fine-tune V reg . In one preferred embodiment, this adjustment can be implemented by an offset DAC, which preferably is small, preferably having 5 or 6 bits. The value in the offset DAC will generally be the same for all motors of a particular model, unless motor parameters vary from motor to motor during manufacture.
The resulting current (normalized) in the various phases is seen in FIG. 6 , which is similar to FIG. 3 . Trace 61 is a representation of an exemplary normalized sinusoidal current waveform in phase B, while trace 62 is a representation of an exemplary normalized sinusoidal current waveform in phase C. Circle 60 on phase A (waveform 63 ) represents the T freeze , while ellipse 69 represents the tristate period. As can be seen, during those periods, whose starting times and durations preferably are programmable by the user—e.g., through firmware, there is only a minor deviation 610 of current waveform 61 from its sinusoidal form (compare sharp positive spike 310 in current waveform 31 of FIG. 3 ), and only a minor deviation 620 of current waveform 62 from its sinusoidal form (compare sharp negative spike 320 in current waveform 32 of FIG. 3 ). Of course, phase A is tristated so that waveform 63 does deviate from sinusoidal, assuming a flat zero-current state 630 .
As seen in FIG. 7 , the normalized total sinusoidal current 70 (sum of phases A, B, C) in motor 10 during the T freeze period barely deviates from its pattern during other parts of the operational cycle. The large increase in peak supply current seen in FIG. 4 is no longer present in FIG. 7 .
What is important for purposes of this invention is that the total voltage drop across motor 10 be reduced during the T freeze period from a magnitude of V dd to a magnitude of V reg . It does not matter whether the minimum voltage or the maximum voltage is adjusted. It is possible to lower the maximum voltage to some value V dd −δ and to raise the minimum voltage to V dd −V reg −δ. However, the most preferable cases are the case where the minimum voltage remains at ground while the maximum voltage is reduced to V reg , and case where the maximum voltage is maintained at V dd while the minimum voltage is raised from ground to V dd −V reg . FIGS. 8–13 show motor drive circuitry that can be used to implement those two cases.
As seen in FIG. 8 , motor 10 is connected to motor drive circuitry 80 that includes separate drivers 81 , 82 , 83 for the three phases A, B and C respectively. Each of those drivers 81 , 82 , 83 is also connected to back-EMF detection circuitry 84 , which also is connected to the central tap C tap 17 of motor 10 , and which outputs a back-EMF voltage signal V bemf0 840 .
FIGS. 9–11 show preferred embodiments 90 , 100 , 110 of drivers 81 , 82 , 83 for the implementation where the minimum voltage remains at ground while the maximum voltage is reduced to V reg .
FIG. 9 shows a preferred embodiment 90 of a driver 81 for phase A, which tristates phase A during the tristate period, as signalled by the application of a tristate signal 91 . Driver 90 preferably includes a PMOS transistor 92 in series with an NMOS transistor 93 between the supply voltage V dd 94 and ground 95 . The output of driver 90 is node 96 between transistors 92 , 93 .
The gate 920 of PMOS transistor 92 is connected to the output of a multiplexer 921 , having two inputs 922 , 923 and a control input 924 on which the tristate signal 91 can be asserted during the tristate period to select input 923 , which is connected to supply voltage V dd 925 . When tristate signal 91 is not asserted, multiplexer 921 selects input 922 , to which is connected PWM generator 926 and pre-driver 927 , which receive input from spindle DAC 97 .
The gate 930 of NMOS transistor 93 is connected to the output of a multiplexer 931 , having two inputs 932 , 933 and a control input 934 on which the tristate signal 91 can be asserted during the tristate period to select input 933 , which is connected to ground 935 . When tristate signal 91 is not asserted, multiplexer 931 selects input 932 , to which is connected PWM generator 936 and pre-driver 937 , which receive input from spindle DAC 97 .
It can be seen that when tristate signal 91 is not asserted, multiplexers 921 , 931 output the respective PWM signals generated by PWM generators 926 , 936 and pre-drivers 927 , 937 to drive motor 10 in accordance with the speed determined by the user setting in spindle DAC 97 . However, when tristate signal 91 is asserted, multiplexer 921 outputs supply voltage V dd 925 , turning off PMOS transistor 92 and disconnecting output node 96 from supply voltage V dd 94 . Similarly, multiplexer 931 outputs ground 935 , turning off NMOS transistor 93 and disconnecting output node 96 from ground. Thus, during the tristate period, output node 96 is disconnected both from supply voltage V dd 94 and from ground 95 —i.e., it is tristated, as expected.
FIG. 10 shows a preferred embodiment 100 of a driver 82 for phase B, which drives phase B high during the T freeze period, as signalled by the application of a T freeze signal 101 . Driver 100 preferably includes a PMOS transistor 102 in series with an NMOS transistor 103 between the supply voltage V dd 104 and ground 105 . The output of driver 100 is node 106 between transistors 102 , 103 .
The gate 1020 of PMOS transistor 102 is connected to the output of a multiplexer 1021 , having two inputs 1022 , 1023 and a control input 1024 on which the T freeze signal 101 can be asserted during the T freeze period to select input 1023 , which is connected to output transconductance amplifier OTA 1025 . When T freeze signal 101 is not asserted, multiplexer 1021 selects input 1022 , to which is connected PWM generator 1026 and pre-driver 1027 , which receive input from spindle DAC 97 .
The gate 1030 of NMOS transistor 103 is connected to the output of a multiplexer 1031 , having two inputs 1032 , 1033 and a control input 1034 on which the T freeze signal 101 is asserted during the T freeze period to select input 1033 , which is connected to ground 1035 . When T freeze signal 101 is not asserted, multiplexer 1031 selects input 1032 , to which is connected PWM generator 1036 and pre-driver 1037 , which receive input from spindle DAC 97 .
It can be seen that when T freeze signal 101 is not asserted, multiplexers 1021 , 1031 output the respective PWM signals generated by PWM generators 1026 , 1036 and pre-drivers 1027 , 1037 to drive motor 10 in accordance with the speed determined by the user setting in spindle DAC 97 . However, when T freeze signal 101 is asserted, multiplexer 1031 outputs ground 1035 , turning off NMOS transistor 103 and disconnecting output node 106 from ground 105 . Similarly, multiplexer 1021 outputs the output of OTA 1025 , driving PMOS transistor 102 . The output of OTA 1025 is regulated to avoid turning on PMOS transistor 102 so strongly that output 106 is V dd , and instead turning on PMOS transistor 102 only strongly enough that output 106 is V reg <V dd . This is accomplished by feeding back output 106 to input 1028 of OTA 1026 . The other input 1029 receives the output of reference generator 107 , which itself receives the output of spindle DAC 97 which determines the duty cycle used to determine V reg as discussed above. This feedback keeps output 106 from exceeding V reg . As discussed above, offset DAC 108 is provided to allow fine-tuning of V reg by the user, if necessary. Thus, during the T freeze period, output node 106 is driven to V reg as desired.
Phase B output 106 is the upper limit of the voltage drop across motor 10 during the T freeze period. The lower limit of the voltage drop across motor 10 during the T freeze period is output 116 of phase C driver 110 , shown in FIG. 11 . Driver 110 preferably includes a PMOS transistor 112 in series with an NMOS transistor 113 between the supply voltage V dd 114 and ground 115 . The output of driver 110 is node 116 between transistors 112 , 113 .
The gate 1120 of PMOS transistor 112 is connected to the output of a multiplexer 1121 , having two inputs 1122 , 1123 and a control input 1124 on which the T freeze signal 111 can be asserted during the T freeze period to select input 1123 , which is connected to supply voltage V dd 1125 . When T freeze signal 111 is not asserted, multiplexer 1121 selects input 1122 , to which is connected PWM generator 1126 and pre-driver 1127 , which receive input from spindle DAC 97 .
The gate 1130 of NMOS transistor 113 is connected to the output of a multiplexer 1131 , having two inputs 1132 , 1133 and a control input 1134 on which the T freeze signal 111 can be asserted during the T freeze period to select input 1133 , which is connected to supply voltage V dd 1135 . When T freeze signal 111 is not asserted, multiplexer 1131 selects input 1132 , to which is connected PWM generator 1136 and pre-driver 1137 , which receive input from spindle DAC 97 .
It can be seen that when T freeze signal 111 is not asserted, multiplexers 1121 , 1131 output the respective PWM signals generated by PWM generators 1126 , 1136 and pre-drivers 1127 , 1137 to drive motor 10 in accordance with the speed determined by the user setting in spindle DAC 97 . However, when T freeze signal 111 is asserted, multiplexer 1121 outputs supply voltage V dd 1125 , turning off PMOS transistor 112 and disconnecting output node 116 from supply voltage V dd 114 . Similarly, multiplexer 1131 outputs supply voltage V dd 1135 , turning on NMOS transistor 113 and connecting output node 116 to ground 115 . Thus, during the T freeze period, output node 116 is driven to ground 115 , as expected.
Thus, in the implementation shown in FIGS. 9–11 , phase A is tristated during the tristate period, and during the T freeze period, phase C is grounded while phase B is regulated to V reg <V dd , so that the voltage drop across motor 10 is V reg as desired.
FIGS. 12 and 13 show preferred embodiments 120 , 130 , of drivers 82 , 83 for the implementation where the maximum voltage remains at V dd while the minimum voltage is raised above ground to V dd −V reg . In this implementation, embodiment 90 of driver 81 ( FIG. 9 ) may be used as it is in the implementation where the minimum voltage remains at ground while the maximum voltage is reduced to V reg .
In this implementation, the upper limit of the voltage drop across motor 10 during the T freeze period is output 126 of phase B driver 120 , shown in FIG. 12 . Driver 120 preferably includes a PMOS transistor 122 in series with an NMOS transistor 123 between the supply voltage V dd 124 and ground 125 . The output of driver 120 is node 126 between transistors 122 , 123 .
The gate 1220 of PMOS transistor 122 is connected to the output of a multiplexer 1221 , having two inputs 1222 , 1223 and a control input 1224 on which the T freeze signal 121 can be asserted during the T freeze period to select input 1223 , which is connected to ground 1225 . When T freeze signal 121 is not asserted, multiplexer 1221 selects input 1222 , to which is connected PWM generator 1226 and pre-driver 1227 , which receive input from spindle DAC 97 .
The gate 1230 of NMOS transistor 123 is connected to the output of a multiplexer 1231 , having two inputs 1232 , 1233 and a control input 1234 on which the T freeze signal 121 can be asserted during the T freeze period to select input 1233 , which is connected to ground 1235 . When T freeze signal 121 is not asserted, multiplexer 1231 selects input 1232 , to which is connected PWM generator 1236 and pre-driver 1237 , which receive input from spindle DAC 97 .
It can be seen that when T freeze signal 121 is not asserted, multiplexers 1221 , 1231 output the respective PWM signals generated by PWM generators 1226 , 1236 and pre-drivers 1227 , 1237 to drive motor 10 in accordance with the speed determined by the user setting in spindle DAC 97 . However, when T freeze signal 121 is asserted, multiplexer 1221 outputs ground 1125 , turning on PMOS transistor 122 and connecting output node 126 to supply voltage V dd 124 . Similarly, multiplexer 1231 outputs ground 1135 , turning off NMOS transistor 123 and disconnecting output node 126 from ground 125 . Thus, during the T freeze period, output node 126 is driven to supply voltage V dd 124 , as expected.
Phase B output 126 is the upper limit of the voltage drop across motor 10 during the T freeze period. The lower limit of the voltage drop across motor 10 during the T freeze period is output 136 of phase C driver 130 , shown in FIG. 13 . Driver 130 preferably includes a PMOS transistor 132 in series with an NMOS transistor 133 between the supply voltage V dd 134 and ground 135 . The output of driver 130 is node 136 between transistors 132 , 133 .
The gate 1320 of PMOS transistor 132 is connected to the output of a multiplexer 1321 , having two inputs 1322 , 1323 and a control input 1324 on which the T freeze signal 131 can be asserted during the T freeze period to select input 1323 , which is connected to supply voltage V dd 1325 . When T freeze signal 131 is not asserted, multiplexer 1321 selects input 1322 , to which is connected PWM generator 1326 and pre-driver 1327 , which receive input from spindle DAC 97 .
The gate 1330 of NMOS transistor 133 is connected to the output of a multiplexer 1331 , having two inputs 1332 , 1333 and a control input 1334 on which the T freeze signal 131 can be asserted during the T freeze period to select input 1333 , which is connected to output transconductance amplifier OTA 1335 . When T freeze signal 131 is not asserted, multiplexer 1331 selects input 1332 , to which is connected PWM generator 1336 and pre-driver 1337 , which receive input from spindle DAC 97 .
It can be seen that when T freeze signal 131 is not asserted, multiplexers 1321 , 1331 output the respective PWM signals generated by PWM generators 1326 , 1336 and pre-drivers 1327 , 1337 to drive motor 10 in accordance with the speed determined by the user setting in spindle DAC 97 . However, when T freeze signal 131 is asserted, multiplexer 1321 outputs supply voltage V dd 1325 , turning off PMOS transistor 132 and disconnecting output node 136 from supply voltage V dd 134 . Similarly, multiplexer 1331 outputs the output of OTA 1335 , driving NMOS transistor 133 . The output of OTA 1335 is regulated to avoid turning on NMOS transistor 133 so strongly that output 136 is ground, and instead turning on NMOS transistor 133 only strongly enough that output 136 is pulled down to V dd −V reg >0. This is accomplished by feeding back output 136 to input 1338 of OTA 1335 . The other input 1339 receives the output of reference generator 137 , which itself receives the output of spindle DAC 96 which determines the duty cycle used to determine V reg as discussed above. This feedback keeps output 136 from falling below V dd −V reg . As discussed above, offset DAC 138 is provided to allow fine-tuning of V reg by the user, if necessary. Thus, during the T freeze period, output node 136 is driven to V dd −V reg as desired.
Thus, in the implementation shown in FIGS. 9 , 12 and 13 , phase A is tristated during the tristate period, and during the T freeze period, phase B is pulled to V dd while phase C is regulated to V dd −V reg so that the voltage drop across motor 10 is V reg as desired.
Thus it is seen that a method and apparatus for minimizing current variations in the phases of a motor power supply during back-EMF detection, allowing more accurate control of the speed of a motor, particularly in a disk drive, has been provided.
Referring now to FIGS. 14 and 15 , two exemplary implementations of the present invention are shown.
Referring now to FIG. 14 the present invention can be implemented in a hard disk drive 600 . The present invention may implement either or both signal processing and/or control circuits, which are generally identified in FIG. 14 at 602 . In some implementations, the signal processing and/or control circuit 602 and/or other circuits (not shown) in the HDD 600 may process data, perform coding and/or encryption, perform calculations, and/or format data that is output to and/or received from a magnetic storage medium 606 .
The HDD 600 may communicate with a host device (not shown) such as a computer, mobile computing devices such as personal digital assistants, cellular telephones, media or MP3 players and the like, and/or other devices, via one or more wired or wireless communication links 608 . The HDD 600 may be connected to memory 609 such as random access memory (RAM), low latency nonvolatile memory such as flash memory, read only memory (ROM) and/or other suitable electronic data storage.
Referring now to FIG. 15 the present invention can be implemented in a digital versatile disk (DVD) drive 700 . The present invention may implement either or both signal processing and/or control circuits, which are generally identified in FIG. 15 at 712 , and/or mass data storage of the DVD drive 700 . The signal processing and/or control circuit 712 and/or other circuits (not shown) in the DVD drive 700 may process data, perform coding and/or encryption, perform calculations, and/or format data that is read from and/or data written to an optical storage medium 716 . In some implementations, the signal processing and/or control circuit 712 and/or other circuits (not shown) in the DVD drive 700 can also perform other functions such as encoding and/or decoding and/or any other signal processing functions associated with a DVD drive.
DVD drive 700 may communicate with an output device (not shown) such as a computer, television or other device, via one or more wired or wireless communication links 717 . The DVD drive 700 may communicate with mass data storage 718 that stores data in a nonvolatile manner. The mass data storage 718 may include a hard disk drive (HDD). The HDD may have the configuration shown in FIG. 14 The HDD may be a mini-HDD that includes one or more platters having a diameter that is smaller than approximately 1.8″. The DVD drive 700 may be connected to memory 719 such as RAM, ROM, low-latency nonvolatile memory such as flash memory, and/or other suitable electronic data storage.
Referring now to FIG. 16 , the present invention can be implemented in a high definition television (HDTV) 800 . The present invention may implement either or both signal processing and/or control circuits, which are generally identified in FIG. 16 at 822 , a WLAN interface and/or mass data storage of the HDTV 800 . The HDTV 800 receives HDTV input signals in either a wired or wireless format and generates HDTV output signals for a display 826 . In some implementations, signal processing circuit and/or control circuit 822 and/or other circuits (not shown) of the HDTV 820 may process data, perform coding and/or encryption, perform calculations, format data and/or perform any other type of HDTV processing that may be required.
The HDTV 800 may communicate with mass data storage 827 that stores data in a nonvolatile manner such as optical and/or magnetic storage devices. At least one HDD may have the configuration shown in FIG. 14 and/or at least one DVD drive may have the configuration shown in FIG. 15 . The HDD may be a mini-HDD that includes one or more platters having a diameter that is smaller than approximately 1.8″. The HDTV 800 may be connected to memory 1028 such as RAM, ROM, low-latency nonvolatile memory such as flash memory, and/or other suitable electronic data storage. The HDTV 800 also may support connections with a WLAN via a WLAN network interface 829 .
Referring now to FIG. 17 , the present invention implements a control system of a vehicle 900 , a WLAN interface and/or mass data storage of the vehicle control system. In some implementations, the present invention may implement a powertrain control system 932 that receives inputs from one or more sensors such as temperature sensors, pressure sensors, rotational sensors, airflow sensors and/or any other suitable sensors and/or that generates one or more output control signals such as engine operating parameters, transmission operating parameters, and/or other control signals.
The present invention may also be implemented in other control systems 940 of the vehicle 900 . The control system 940 may likewise receive signals from input sensors 942 and/or output control signals to one or more output devices 944 . In some implementations, the control system 940 may be part of an anti-lock braking system (ABS), a navigation system, a telematics system, a vehicle telematics system, a lane departure system, an adaptive cruise control system, a vehicle entertainment system such as a stereo, DVD, compact disc and the like. Still other implementations are contemplated.
The powertrain control system 932 may communicate with mass data storage 946 that stores data in a nonvolatile manner. The mass data storage 946 may include optical and/or magnetic storage devices for example hard disk drives HDD and/or DVDs. At least one HDD may have the configuration shown in FIG. 14 and/or at least one DVD drive may have the configuration shown in FIG. 15 . The HDD may be a mini-HDD that includes one or more platters having a diameter that is smaller than approximately 1.8″. The powertrain control system 932 may be connected to memory 947 such as RAM, ROM, low latency nonvolatile memory such as flash memory, and/or other suitable electronic data storage. The powertrain control system 932 also may support connections with a WLAN via a WLAN network interface 948 . The control system 940 may also include mass data storage, memory and/or a WLAN interface (none shown).
Referring now to FIG. 18 , the present invention can be implemented in a cellular telephone 1000 that may include a cellular antenna 1051 . The present invention may implement either or both signal processing and/or control circuits, which are generally identified in FIG. 18 at 1052 , a WLAN interface and/or mass data storage of the cellular phone 1050 . In some implementations, the cellular telephone 1050 includes a microphone 1056 , an audio output 1058 such as a speaker and/or audio output jack, a display 1060 and/or an input device 1062 such as a keypad, pointing device, voice actuation and/or other input device. The signal processing and/or control circuits 1052 and/or other circuits (not shown) in the cellular telephone 1050 may process data, perform coding and/or encryption, perform calculations, format data and/or perform other cellular telephone functions.
The cellular telephone 1050 may communicate with mass data storage 1064 that stores data in a nonvolatile manner such as optical and/or magnetic storage devices—for example hard disk drives (HDDs) and/or DVDs. At least one HDD may have the configuration shown in FIG. 14 and/or at least one DVD drive may have the configuration shown in FIG. 15 . The HDD may be a mini-HDD that includes one or more platters having a diameter that is smaller than approximately 1.8″. The cellular telephone 1000 may be connected to memory 1066 such as RAM, ROM, low-latency nonvolatile memory such as flash memory, and/or other suitable electronic data storage. The cellular telephone 1000 also may support connections with a WLAN via a WLAN network interface 1068 .
Referring now to FIG. 19 , the present invention can be implemented in a set top box 1100 . The present invention may implement either or both signal processing and/or control circuits, which are generally identified in FIG. 19 at 1184 , a WLAN interface and/or mass data storage of the set top box 1180 . Set top box 1180 receives signals from a source 1182 such as a broadband source and outputs standard and/or high definition audio/video signals suitable for a display 1188 such as a television and/or monitor and/or other video and/or audio output devices. The signal processing and/or control circuits 1184 and/or other circuits (not shown) of the set top box 1180 may process data, perform coding and/or encryption, perform calculations, format data and/or perform any other set top box function.
Set top box 1100 may communicate with mass data storage 1190 that stores data in a nonvolatile manner. The mass data storage 1190 may include optical and/or magnetic storage devices for example hard disk drives HDD and/or DVDs. At least one HDD may have the configuration shown in FIG. 14 and/or at least one DVD drive may have the configuration shown in FIG. 15 . The HDD may be a mini-HDD that includes one or more platters having a diameter that is smaller than approximately 1.8″. Set top box 1100 may be connected to memory 1194 such as RAM, ROM, low-latency nonvolatile memory such as flash memory, and/or other suitable electronic data storage. Set top box 1100 also may support connections with a WLAN via a WLAN network interface 1196 .
Referring now to FIG. 20 , the present invention can be implemented in a media player 1200 . The present invention may implement either or both signal processing and/or control circuits, which are generally identified in FIG. 20 at 1204 , a WLAN interface and/or mass data storage of the media player 1200 . In some implementations, the media player 1200 includes a display 1207 and/or a user input 1208 such as a keypad, touchpad and the like. In some implementations, the media player 1200 may employ a graphical user interface (GUI) that typically employs menus, drop down menus, icons and/or a point-and-click interface via the display 1207 and/or user input 1208 . Media player 1200 further includes an audio output 1209 such as a speaker and/or audio output jack. The signal processing and/or control circuits 1204 and/or other circuits (not shown) of media player 1200 may process data, perform coding and/or encryption, perform calculations, format data and/or perform any other media player function.
Media player 1200 may communicate with mass data storage 1210 that stores data such as compressed audio and/or video content in a nonvolatile manner. In some implementations, the compressed audio files include files that are compliant with MP3 format or other suitable compressed audio and/or video formats. The mass data storage may include optical and/or magnetic storage devices for example hard disk drives HDD and/or DVDs. At least one HDD may have the configuration shown in FIG. 14 and/or at least one DVD drive may have the configuration shown in FIG. 15 . The HDD may be a mini-HDD that includes one or more platters having a diameter that is smaller than approximately 1.81″. Media player 1200 may be connected to memory 1214 such as RAM, ROM, low-latency nonvolatile memory such as flash memory, and/or other suitable electronic data storage. Media player 1200 also may support connections with a WLAN via a WLAN network interface 1216 . Still other implementations in addition to those described above are contemplated.
It will be understood that the foregoing is only illustrative of the principles of the invention, and that the invention can be practiced by other than the described embodiments, which are presented for purposes of illustration and not of limitation, and the present invention is limited only by the claims which follow. | In a method for measuring motor speed and position by detecting the back-EMF generated during pole-pair interactions, fluctuations of a three-phase motor power supply that may affect back-EMF detection are reduced. One phase of the power supply is tristated for a certain interval preceding and during back-EMF detection. For a shorter interval during back-EMF detection, the voltage drop across the motor is reduced from the full power supply voltage. This preferably is accomplished either by pulling a first of the other two power supply phases low, while pulling a second of the other two power supply phases up to a regulated voltage below the power supply voltage, or by pulling the second of the other two phases up to the power supply voltage and pulling the first of the other two phases down to a regulated voltage above ground. | 7 |
This is a division of application Ser. No. 379,844, filed May 20, 1982.
BACKGROUND OF THE INVENTION
The present invention relates to vacuum operated fluid pressure signal controllers and to controlling of exhaust gas recirculation (EGR) in an internal combustion engine by a vacuum actuated control valve.
In providing EGR for controlling emissions in automotive internal combustion engines, it is known to provide a valve for permitting exhaust gas to enter the engine induction manifold, which valve is controlled by a pressure responsive actuator receiving a fluid pressure control signal derived from an onboard source of subatmoshperic pressure such as manifold vacuum.
It has been found that different amounts of EGR are required at the various engine speeds and loads encountered in automotive engine service. Where engine manifold vacuum has been the primary source of fluid pressure control signal for effecting EGR, it has been found that the high vacuum or low manifold absolute pressure (MAP) which occurs at idle or nearly closed throttle engine operation requires that the vacuum signal be cut off to the EGR Actuator in order to prevent an excess amount of EGR at low engine operating speeds.
Where engine manifold vacuum has been utilized as a primary control signal for EGR valve actuation, it has been found convenient to invert the sense of the change of vacuum with variations in engine speed and load by means of a vacuum inverter. An example of such a device which has been heretofore employed is that shown and described in the copending application Ser. No. 185,467, filed Sept. 9, 1980, now U.S. Pat. No. 4,365,608, in the names of Cyril Bradshaw and Martin Uitvlugt and assigned to the Assignee of the present invention. The aforementioned device provides, (once a threshold operating level of input signal is achieved), for a decreasing vacuum output signal in response to increasing manifold vacuum, or decreasing MAP.
However, even where a vacuum inverter is employed, the inverted manifold vacuum signal is sufficiently large in magnitude as to cause the actuator to provide opening of the EGR valve and thus excess EGR at idle or low operating engine speeds.
Furthermore, engine manifold vacuum can have identical values for two different engine operating speeds, for example, idle and moderate road speeds. Thus, if manifold vacuum is employed for a control signal, the same amount of EGR would be provided at two different engine speeds where different amounts of EGR are required.
In conjunction with utilizing engine manifold vacuum as a controller signal source, it has been desired to also utilize a secondary vacuum source for controlling EGR at idle or low engine operating speed. Such a source is found in present day gasoline spark ignited automotive engines in the so-called "ported" signal tap provided in the carburetor throat at the throttle plate. A ported vacuum signal is so named because it is vented or "ported" to the atmosphere above the throttle plate in the closed position and is exposed to carburetor throat vacuum in the throttle plate open position. Ported vacuum exhibits zero gauge or atmospheric pressure at engine idle and increases vacuum, or decreases MAP, rapidly with a relatively small amount of throttle opening until the ported signal equals engine manifold vacuum.
However, if a ported vacuum signal is employed for each EGR valve actuator control, the control signal is at the requisite null or atmospheric pressure for engine idle, but increases too rapidly with throttle opening to be useful for a control signal over a broad range of engine operating conditions.
Thus, it has long been desired to find a way of providing a fluid pressure control signal for an EGR valve actuator over a broad range of engine operating conditions beginning with idle and progressing through wide open throttle, at various engine speeds and provide the desired amount of EGR for the engine instantaneous engine operating condition. It has particularly been desired to find a way of utilizing the available ported vacuum signal in conjunction with an engine manifold vacuum, or MAP, to provide a suitable control signal over the entire regime of engine operating conditions.
SUMMARY OF THE INVENTION
The present invention provides a solution to the above described problem by enabling an EGR valve actuator to be controlled by a subatmospheric fluid pressure control signal provided from onboard vehicle engine sources. The present invention enables control of the amount of EGR throughout the engine operating range encompassing idle and off-idle operation through wide open throttle at all normally encountered engine operating speeds.
The present invention provides a fluid pressure control signal for EGR valve actuation such that engine manifold vacuum or MAP is inverted with respect to the sense of change with increasing engine load. The inverted signal is used for controlling the EGR valve actuator. At idle and nearly closed throttle engine operating conditions, the ported carburetor throat vacuum signal is employed.
The signal controller of the present invention is capable of discriminating between the manifold vacuum signal and the carburetor throat signal and switching to the lesser of the two signals in order to effect the desired amount of EGR valve actuation.
The EGR valve actuator signal controller of the present invention employs a ball type switchover valve received in closely fitting sliding arrangement in a bore having a primary vacuum signal port at one end of the bore and a secondary vacuum signal port at the other end. The intermediate region of the bore is ported to provide an output vacuum control signal to the EGR valve actuator. A check ball moves between the position isolating the primary vacuum signal from the bore in which position the secondary vacuum signal comprising ported carburetor throat vacuum is applied to the actuator, and a second position in which the secondary vacuum signal is isolated from the bore and the primary signal comprising inverted manifold vacuum is applied to the actuator port.
The present invention thus provides a controller having the capability of switching between a primary and a secondary vacuum signal source in a manner as to select the lesser of the source signals.
The present invention incorporates a comparator function and is capable of transmitting the lesser vacuum signal. The controller has integrally an inverter for conditioning one of the vacuum source input signals, for example, engine manifold vacuum.
The present invention provides for controlling the amount of EGR in an engine proportional to carburetor throttle blade angle at idle and low off-idle engine operating condition and provides EGR proportional to changes in engine manifold vacuum throughout the remaining portion of the engine operating regime.
The present invention thus provides a unique and compact fluid pressure signal controller for effecting desired control of EGR throughout the full range of normal engine operation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is schematic showing a cross-section of the signal controller of the present invention and the fluid signal connections for EGR valve operation; and;
FIG. 2 is a graphical representation of the primary vacuum input signal plotted as the abscissa and the controller output signal plotted as the ordinate.
DETAILED DESCRIPTION
Referring now to FIG. 1, an EGR valve indicated generally as 10 has a housing 12 adapted for mounting on an engine to receive exhaust gas through orifice 14 and for recirculating exhaust gas through passage 16 upon opening of the valve. The EGR valve 10 is actuated by rod 18 connected to a pressure responsive member (not shown) such as a diaphragm disposed within housing 20 and having a signal inlet port 22. The signal inlet port 22 is connected by a suitable conduit indicated, by dashed lines in FIG. 1, to the output of a signal controller indicated generally at 24.
The signal controller 24 has a housing comprising an upper cover member 26, a central portion 28 joined to the upper cover at parting line 30 such that a flange indicated generally at 32 is formed the upper and central housing portions adjacent to parting line. In the presently preferred practice the invention the upper housing portion 26 and central portion 28 are formed of plastic material and joined about parting line 30 by a suitable expedient such as ultrasonic welding.
A lower housing portion 34 is received in the central housing portion 28 and is retained therein by any suitable technique as for example ultrasonic welding about the cylindrical parting line 36.
The lower housing portion 34 has an insert cup 38 received therein and suitably bonded as, for example, by sonic welding about the periphery of the cup to the lower housing portion 34. The cup 38 has a central tubular portion 40 extending downwardly therefrom and which is received in a recess 42 formed in the lower housing portion 34 and defining therebetween a fluid pressure chamber 44.
An orifice 46 is formed in the upper end of chamber 44 and a secondary fluid inlet port 48 is provided in the lower end of chamber 44. The port 48 extends externally of the housing through an attachment fitting 50 that is adapted for connection to a secondary vacuum supply hose.
A signal output attachment fitting 52 is provided on the lower housing portion 34 and has a port 54 provided therethrough which communicates via passage 56 formed in the tubular portion 40 of the insert cup with the fluid pressure chamber 44 intermediate the upper and lower ends thereof. A movable valve member 58 in the form of a checkball is received in closely fitting sliding engagement with the walls of chamber 44. The ball moves between a lower position indicated in solid outline in FIG. 1 contacting a secondary supply port seat 60 disposed about the port 48 and an upper position illustrated in dashed outline. In the upper position ball valve 58 engages a valve seat 62 formed in the interior of tubular portion 40 of the cup 38 and surrounding the orifice 46.
Upper housing portion 26 has a primary vacuum signal inlet attachment fitting 64 extending upwardly therefrom which has a port 66 provided therethrough and which is adapted for connection to a primary vacuum source hose.
An upper pressure responsive diaphragm 68 and a lower pressure responsive diaphragm 70 are received in the lower housing portion 34. The diaphragms are spaced vertically in FIG. 1 and individually sealed about the periphery thereof against their respective adjacent housing portions by a preferably "C" shaped spacer ring 72. A variety of vent ports 74 are provided about the spacer ring and the interior region of the spacer ring between the diaphragms is vented to the atmosphere via a plurality of slots 76 disposed about the periphery of the central housing portion 28. A packing 78 of suitable air filter material is disposed about the spacer ring 72 to prevent entry of foreign material to the space between the diaphragms.
The upper diaphragm 68 has an insert cup 80 received against the central portion thereof with the cup having a valve member 82 depending therefrom and extending downward through an aperture in the central portion of diaphragm 68. The diaphragm aperture has a sealing bead 84 disposed about the periphery thereof which seals against a corresponding groove in the cup 80.
The valve member 82 in the preferred practice of the invention has a tapered configuration with a fluid passage 86 provided centrally therethrough. A bias spring 88 has the lower end thereof received in cup 80 with the upper end registering against a shoulder provided peripherally about plate 90 which registers against an adjustable stop screw 92 provided in port 66.
Lower diaphragm 70 has an insert cup 94 received centrally therein and has a central opening therein with a downwardly turned flange 96 provided thereabout. The diaphragm 70 has a valve seat at 98 formed about a lip portion 100 which extends downwardly through the cup 94 and engages about the flange 96.
A bias spring 102 has the upper end thereof registering against the under surface of cup 94 with the lower end of the spring registering against the housing insert 38 for biasing the lower diaphragm and valve seat 98 in a vertically upward direction in FIG. 1 for contacting valve 82.
In operation, the controller 24 of FIG. 1 has the inlet fitting 64 connected to a vacuum hose supplied with a source of engine manifold vacuum. The secondary input attachment 50 is connected to a vacuum hose receiving a ported suction signal from the carburetor throat.
Referring to FIGS. 1 and FIG. 2, in operation, as the engine is running at idle with the throttle plate closed, a high vacuum is applied to the primary input port 66 which causes the pressure on the topside of diaphragm 68 and a slight vacuum to be formed below diaphragm 70 by bleed through the passage 86.
However, at high input vacuum levels through port 66, the pressure differential across upper diaphragm 68 causes valve 82 to open and vent atmospheric air to the chamber 44 through orifice 46 inversely as the vacuum varies in the input port 66.
With the ball 58 in the lower position shown in FIG. 1 in solid outline, the pressure in chamber 44 would be transmitted to output port 54 in accordance with the solid line plot of FIG. 2 and would continue to increase linearly from idle to point A on the graph of FIG. 2 in a manner inverted in the sense of change of manifold vacuum with increasing engine load. At point A on the graph of FIG. 2, the controller is no longer able to invert the input signal through port 66; and, thereafter at lighter engine loads the output to port 54 drops off in accordance with further decay in manifold vacuum as higher engine loads are encountered and reaches atmospheric pressure at wide open throttle.
As the primary input signal through port 66 decreases, diaphragm 68 and valve 82 are lowered to decrease the atmospheric bleed through valve seat 98 and thus increase the pressure below diaphragm 70 for increasing the signal to port 54.
With reference to FIG. 2, it will be seen that as the throttle plate is opened from closed position, the ported vacuum increases very rapidly from 0 to a value somewhat greater than the vacuum in chamber 44 and thus causes the ball 58 to move downwardly and remain in the position shown in solid outline in FIG. 1. In the presently preferred practice of the invention the clearance between ball 58 and chamber 44 is chosen so that a 0.3 inches of Hg pressure difference between the signal through orifice 46 and the signal in port 48 causes the ball to switch from the upper position, shown in dash lined FIG. 1, to the lower position shown in solid outline.
It will be understood that at or near the throttle plate closed position the check ball 58 is initially in the position shown in dashed outline in FIG. 1 closing off orifice 46 from the chamber 44 thereby causing the secondary or ported vacuum signal to be applied to chamber 44 and controller output port 54. Thus, at high manifold vacuum levels indicative of closed or nearly closed throttle plate position, the input control signal through port 54 is either 0 (atmospheric pressure) or is at a vacuum level provided through the secondary input port 48 from the carburetor ported vacuum source.
When the ported vacuum signal exceeds the inverted manifold vacuum signal present at orifice 46 by the selected differential, the check ball 58 moves downwardly or "switches" to thereafter apply the inverted manifold vacuum signal from orifice 46 to the controller output port 54.
From the foregoing description it will be seen that the present invention provides a unique method of controlling EGR to an engine by providing a control signal that utilizes the vacuum level of a ported carburetor throat vacuum signal at or near the closed throttle position and switches to an inverted manifold vacuum signal as the throttle opens to provide the desired control signal for an EGR valve actuator. The present invention thus provides a unique manner of controlling the EGR program of an engine over the range operating speeds and loads encountered in automotive service.
Although the invention here and above has been described in the presently preferred practice, it will be understood to those skilled in the art that modifications and variations may be made and the invention is limited only by the following claims. | Engine exhaust gas is recirculated by a fluid pressure actuated valve receiving a control signal from a controller which receives and modulates engine induction vacuum to provide a primary source and receives a carburetor throttle-blade controlled suction as a secondary source and compares the primary and secondary sources and discriminates therebetween to provide the lesser as the outward control signal. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photoprinter provided with margin paper receiving device that receives a margin cut off from a continuous paper.
2. Description of the Related Art
Photoprinters use a roll paper to be able to continuously print photographs having different sizes such as normal size, panorama size, etc. without replacing sheets. In photoprinters, when a picture is formed on a roll paper, that portion (a trailing end of a portion, on which the picture is formed), on which the picture is not formed, is in some cases exposed to light. Therefore, with conventional photoprinters, such portion (margin paper) exposed to light is cut/ejected and a portion (picture formed paper), on which a picture is formed, is cut/ejected.
Conventional photoprinters include a container that recovers therein a margin paper. There has been proposed a photoprinter provided with a weight detector that detects a weight of a container that recovers a margin paper (see, for example, JP-A-2002-86827 (pages 3 to 4, FIGS. 1 and 2), JP-A-2002-86827 describes an apparatus capable of stacking pieces of paper (margin paper) orderly to recover the same in a paper piece recovering device and using a weight detector to detect a weight of the paper piece recovering device to issue an alarm before pieces of paper overflow the paper piece recovering device.
With the apparatus described in JP-A-2002-86827, when the weight detector detects a weight of the paper piece recovering device, an alarm is issued as by lighting a LED, but a user overlooks lighting of the LED in some cases. Therefore, the apparatus involves a problem that pieces of paper (margin paper) overflow the paper piece recovering device to cause lodgment of paper and failure.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a photoprinter free from generation of lodgment of paper and failure caused by overflowing of recovered margin paper even when a plurality of sheets of picture formed paper are formed.
The invention includes the following constitution as measure for solving the above problem.
(1) The constitution has a feature in a photoprinter including
a picture forming device to form a picture on a roll paper,
a cutting device to cut off a picture formed paper, on which a picture has been formed, and a margin paper, which constitutes a margin between the picture formed papers, from a continuous paper,
a margin paper receiving device to receive therein a margin paper, the photoprinter being characterized by the counting device to count the number of times, in which the cutting device performs cutting, and
an ejection device to eject the margin paper from the margin paper receiving device when the number of times counted by the counting device reaches a set value.
With such constitution, the number of times, in which the cutting device cuts a number of sheets to avoid overflowing of the margin paper received in the margin paper receiving device, is beforehand set as a set value, whereby the margin paper received in the margin paper receiving device can be ejected periodically without causing the margin paper to overflow the margin paper receiving device to cause lodgment of paper and failure. Accordingly, a user of the photoprinter can use the photoprinter without caring about that timing, at which the margin paper should be discarded.
(2) The constitution has a feature in that the margin paper receiving device is in the form of a box having an opening at an upper portion thereof and pivotally born by a rotating shaft arranged substantially horizontal, and the ejection device includes turning device to turn the margin paper receiving device.
With such constitution, when the margin paper is cut by the cutting device, it is received from the opening at the upper portion of the box-shaped margin paper receiving device to accumulate successively. Also, by setting the turning device to turn the margin paper receiving device to a position, in which the opening of the margin paper receiving device is directed obliquely downward, or downward, the margin paper received in the margin paper receiving device can be ejected when the number of times counted by the counting device reaches a set value. Accordingly, a user can easily discard the margin paper. Also, with the photoprinter, the margin paper receiving device is not removed but turned to eject the margin paper, so that there is no fear that a user erroneously inserts a hand into the vicinity of the cutting device, whereby it is possible to prevent a user from getting hurt by the cutter device.
(3) The constitution has a feature in that the margin paper receiving device is in the form of a box having an opening at an upper portion thereof and includes an openable lid at a bottom surface or a side thereof, and the ejection device includes opening and closing device to open and close the lid.
With such constitution, when the number of times counted by the counting device reaches a set value, the turning device is actuated to turn the margin paper receiving device whereby the margin paper received in the margin paper receiving device can be easily ejected. Also, with the photoprinter, the margin paper receiving device is not removed but the lid is opened to eject the margin paper, so that there is no fear that a user erroneously inserts a hand into the vicinity of the cutting device, whereby it is possible to prevent a user from getting hurt by the cutter device.
(4) The constitution has a feature in that the ejection device includes a fan to blow the wind inside the margin paper receiving device.
With such constitution, the fan is set to blow the wind inside the margin paper receiving device when the margin paper should be ejected from the margin paper receiving device, so that the wind from the fan can be made use of in order to eject the margin paper and the margin paper can be ejected from the margin paper receiving device in a short period of time. Accordingly, a user can form a picture in the photoprinter without caring about that timing, at which the margin paper accumulated in the photoprinter should be discarded.
(5) The constitution has a feature in that the margin paper receiving device is provided on at least one of the bottom surface and the side thereof with a plurality of gaps sized not to allow the margin paper to pass therethrough.
With such constitution, the plurality of gaps are provided at least on the bottom surface of the margin paper receiving device, so that the fan can blow the wind inside the margin paper receiving device from the bottom surface thereof. Accordingly, freedom in a position, in which the fan is arranged, is increased, so that it is possible to install the fan in a position, in which assembly is easy, and to reduce manhour in assembling. Also, by arranging the fan in a position suited for ventilation in the photoprinter, the fan can serve for ejection of the margin paper and for ventilation in the photoprinter, which makes it possible to prevent an increase in cost.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and advantages of this invention will become more fully apparent from the following detailed description taken with the accompanying drawings in which:
FIG. 1 is a front, perspective view schematically showing a constitution of a photoprinter according to an embodiment of the invention;
FIG. 2 is a view schematically showing a constitution of a turning mechanism for a margin paper receiving section;
FIG. 3 is a flowchart illustrating a margin-paper ejecting operation of the photoprinter;
FIG. 4 is a view schematically showing a constitution of a partial modification of the margin paper receiving section shown in FIG. 2 ;
FIG. 5 is a view schematically showing a constitution of a turning mechanism of a margin paper receiving section that is configured differently from those in FIGS. 2 and 4 ; and
FIG. 6 is a view schematically showing a constitution of a turning mechanism of a margin paper receiving section that is configured differently from those in FIGS. 4 and 5 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a front, perspective view schematically showing a constitution of a photoprinter according to an embodiment of the invention. In the following descriptions, a printer of the TA system (also called a thermo-autochrome system or a light fixing type direct thermal recording system) will be explained by way of example. Here, the TA system is one that forms a full color picture by repeating heating by a thermal head and fixing by irradiation of ultraviolet rays on a special purpose paper, which is called TA paper, and on which three thermal color development layers for color development of three primary colors of Y (yellow)•M (magenta)•C (cyanogen) are laminated.
As shown in FIG. 1 , a photoprinter 1 includes a paper feeding section 2 , a picture forming section 3 , a fixing unit 4 , a cutting section 5 , a margin paper receiving section 6 , and a control unit 7 . The paper feeding section 2 includes a roll-paper holding member 12 that supports a roll paper 11 formed by winding a continuous TA paper on a columnar core, a paper guide 13 that guides the roll paper 11 , and synchronous gears 16 a to 16 d for synchronism of rotations of a pair of conveyance rollers 14 ( 14 a , 14 b )•a conveyance roller 15 , the pair of conveyance rollers 14 , the conveyance roller 15 , and the roll-paper holding member 12 to control feed of the roll paper 11 . In addition, the roll-paper holding member 12 is driven by a motor (not shown).
The picture forming section 3 includes a thermal head 21 that heats the roll paper to form a picture, and a temperature controller 22 (not shown) that adjusts temperature of the thermal head 21 .
The fixing unit 4 includes fluorescent tubes 31 a , 31 b for fixation of magenta, a reflector 32 that covers surroundings of the fluorescent tubes 31 a , 31 b , fluorescent tubes 33 a , 33 b for fixation of yellow, a reflector 34 that covers surroundings of the fluorescent tubes 33 a , 33 b , a shutter 35 that moves above the fluorescent tubes 31 a , 31 b and the fluorescent tubes 33 a , 33 b to intercept light so that a portion of the roll paper 11 formed with no picture is not exposed to light, a guide member 36 that assists the shutter 35 , gears 37 a to 37 c that move the shutter 35 , a clutch 38 that interlocks movements of the shutter 35 with feeding of the roll paper 11 , a pair of ejection rollers 39 that eject the roll paper 11 , and a fluorescent-tube lighting circuit 40 (not shown) that lights the fluorescent tubes 31 a , 31 b and the fluorescent tubes 33 a , 33 b . In addition, the fluorescent tubes 31 a , 31 b and the fluorescent tubes 33 a , 33 b irradiate ultraviolet rays having different wavelengths.
The cutting section 5 includes a cutter 41 that cuts the roll paper 11 , and a cutter moving mechanism 42 that moves the cutter 41 in a direction perpendicular to a direction, in which the roll paper 11 is fed.
The margin paper receiving section 6 is in the form of a box having an opening in an upper portion thereof, and includes a casing 51 that receives a margin paper inside through the opening, and a turning mechanism 52 that turns the casing 51 in order to direct the upward directed opening of the casing 51 downward or obliquely downward to eject the margin paper received in the casing 51 . The control unit 7 controls operations of respective parts of the photoprinter 1 , details of which are omitted.
Before a picture is formed in the photoprinter 1 , the control unit 7 causes a motor (not shown) to rotate the roll-paper holding member 12 to feed a predetermined length of the roll paper 11 , and thereafter stops rotation of the roll-paper holding member 12 . Then, the control unit 7 causes the cutter moving mechanism 42 to move the cutter 41 to cut a margin paper being a non-picture formed portion that has been exposed to light at the time of picture formation at the last time. The cut margin paper drops to be received in the casing 51 . In addition, it suffices that the margin paper be preset to an appropriate length corresponding to sizes of the photoprinter and the roll paper 11 on the basis of experiments or the like.
Subsequently, the control unit 7 causes a motor (not shown) to rotate the roll-paper holding member 12 to move a leading end of the roll paper 11 . Then, the control unit 7 controls the temperature controller 22 (not shown), the fluorescent-tube lighting circuit 40 (not shown), and the motor (not shown) that controls conveyance of the roll paper 11 , to perform the following processings. That is, (1) the thermal head 21 is used to heat the roll paper 11 at a low temperature to form a yellow picture. (2) The fluorescent tubes 33 a , 33 b irradiate ultraviolet rays to fix the yellow picture. (3) The thermal head 21 is used to heat the roll paper 11 at a medium temperature to form a magenta picture. (4) The fluorescent tubes 31 a , 31 b irradiate ultraviolet rays to fix the magenta picture. (5) The thermal head 21 is used to heat the roll paper 11 at a high temperature to form a cyanogen picture. In addition, no ultraviolet rays are irradiated since there is no need of fixing the cyanogen picture.
When formation of a picture on the roll paper 11 is completed, the control unit 7 feeds the roll paper 11 and stops feeding of the roll paper 11 in a position, in which a trailing end of the picture formed on the roll paper 11 is opposed to the cutter 41 . Then, the control unit 7 causes the cutter moving mechanism 42 to move the cutter 41 to cut a picture formed paper being a picture formed portion. The picture formed paper as cut is ejected from an eject port 10 by the pair of ejection rollers 39 . In this manner, whenever a sheet of the picture formed paper is formed, a single sheet of margin paper is received in the casing 51 .
FIG. 2 is a view showing an outline of the turning mechanism in the margin paper receiving section. As shown in FIG. 2(A) , the turning mechanism 52 includes a shaft 61 and a motor 62 . The shaft 61 is mounted substantially horizontally at the bottom of the casing 51 . That is, the shaft 61 is mounted perpendicularly to a direction, in which the roll paper 11 is conveyed, and when the shaft 61 is turned, the casing 51 is turned. Also, the shaft 61 is connected to the motor 62 directly or via gears.
As described above, when the margin paper overflows the casing 51 , paper lodgment is generated to be responsible for failure. Hereupon, with the photoprinter 1 according to the invention, when a predetermined number of sheets of margin paper are received in the casing 51 , the margin paper is automatically ejected outside the photoprinter 1 . Concretely, the photoprinter 1 operates in the following manner. FIG. 3 is a flowchart illustrating a margin-paper ejecting operation of the photoprinter.
With the photoprinter 1 , the number of times, in which the cutter moving mechanism 42 for operating the cutter 41 acts, is in proportion to the number of sheets of margin paper received in the casing 51 , and thus the control unit 7 counts the number of times, in which the cutter moving mechanism 42 acts. Also, a predetermined set value is preset in the control unit 7 so that the margin paper received in the casing 51 does not overflow. Set as the set value is the number of times, in which the cutter moving mechanism 42 is caused to act until the number of sheets of margin paper received in the casing 51 overflows since the casing 51 is vacant. For example, in the case where an upper limit of the number of sheets of margin paper received in the casing 51 is 100, the control unit 7 must actuate the cutter moving mechanism 42 two hundred times (precisely, 199 times) in order to cut one hundred sheets of margin paper. Accordingly, in this case, k=200 is appropriate as a set value set in the control unit 7 .
As shown in FIG. 3 , when the cutter 41 in the cutting section 5 first cuts the margin paper, or when a count value is reset, the count value is set in the control unit 7 to be 0 (s 1 ). When actuating the cutter moving mechanism 42 in order to cut the roll paper 11 with the use of the cutter 41 (s 2 ), the control unit 7 counts a count value k of the number of times, in which the cutter moving mechanism 42 acts, and adds 1 to the count value (s 3 ). The control unit 7 judges whether the count value k corresponds to a set value n (s 4 ), and repeatedly implements the processings of the steps s 2 to s 4 until the count value k reaches the set value n.
When the number of times, in which the cutter moving mechanism 42 acts, reaches the set value n (n 4 ), the control unit 7 outputs a signal (ejection command signal) to the motor 62 to turn the casing 51 (s 5 ). When the motor 62 is actuated by an ejection command signal from the control unit 7 , power of the motor 62 is transmitted to the casing 51 via the shaft 61 , so that the casing 51 is turned from an initial state, in which the opening of the casing 51 is disposed upward, to direct the opening of the casing 51 obliquely downward, or downward as shown in FIG. 2(B) . The control unit 7 stops issuance of an ejection command signal and stops the motor 62 in this state (s 6 ). Thereby, the margin paper received in the casing 51 falls due to gravity, and so is ejected from the casing 51 .
When a preset predetermined time has elapsed (s 7 ), the control unit 7 outputs a signal (reset command signal) to the motor 62 to turn the casing 51 (s 8 ). Receiving the signal, the motor 62 turns the casing 51 to return the same to the initial state (s 8 ). Also, the control unit 7 resets the count value k (s 9 ). Then, the control unit 7 repeatedly implements the above processings in the order from the step s 1 on.
In addition, it suffices that experiments or the like be conducted to beforehand confirm the housing capacity (the number of sheets being possibly received) of the margin paper received in the casing 51 , on the basis of results of which the set value is set.
FIG. 4 is a view showing an outline of a partial modification of the margin paper receiving section shown in FIG. 2 . As shown in FIG. 4 , a fan 66 may be provided to blow the wind into the casing 51 when the upper surface of the casing 51 is directed obliquely downward, or downward, thereby forcibly ejecting the margin paper received in the casing 51 . At this time, a plurality of gaps sized to allow an air to easily pass therethrough but not to allow the margin paper to pass therethrough are provided at a bottom surface 51 c and a part of sides of the casing 51 in, for example, a latticed manner. Further, the fan 66 is preferably arranged in a manner to blow the wind into the casing 51 from a bottom side of the casing 51 when the casing 51 is turned to have the upper surface thereof directed obliquely downward, or downward.
Also, by arranging the fan 66 in a position shown in FIG. 4 , the fan can be used as a fan that serves for ventilation in the photoprinter 1 , that is, discharges heat generated from the thermal head 21 , the fluorescent tubes 31 a , 31 b , and the fluorescent tubes 33 a , 33 b , to the outside. Accordingly, the fan 66 can serve as two uses, so that it is possible to prevent an increase in cost.
Subsequently, an explanation will be given to another configuration of the margin paper receiving section 6 . The margin paper receiving section 6 in the photoprinter 1 may be configured differently provided that the margin paper received in the margin paper receiving section 6 is ejected when the number of times, in which the cutting section 5 acts, reaches the set value. FIG. 5 is a view showing an outline of a turning mechanism of a margin paper receiving section that is configured differently from those in FIGS. 2 and 4 . A turning mechanism 52 that serves to eject the margin paper from a casing 53 may use a solenoid 71 as shown in FIG. 5 . With this configuration, when the control unit 7 outputs an ejection command signal, the solenoid 71 is actuated to have a moving iron core 71 a pushing a side 53 d of the casing 53 , an opening of which is directed upward, so that the casing 53 is turned and the opening of the casing 53 is directed obliquely downward. The casing 53 is provided at a bottom thereof with a shaft 72 that pivotally bears the casing 53 . Also, a weight 53 f is arranged in the vicinity of a corner 53 e on the bottom of the casing 53 so that when the solenoid 71 is not actuated, the casing 53 is stationary in a state (normal state) to receive the margin paper therein. Further, the moving iron core 71 a of the solenoid 71 is arranged in a manner to abut against the side 53 d of the casing 53 .
When the solenoid 71 is actuated by an ejection command signal from the control unit 7 , an upper portion of the side 53 d of the casing 53 is pushed by the moving iron core 71 a , so that the casing 53 is turned and the upper surface of the casing 53 is directed obliquely downward, or downward. Thereby, the margin paper received in the casing 53 falls due to gravity, and so is ejected from the casing 51 .
Also, when the control unit 7 outputs a reset command signal, the moving iron core 71 a is received in the solenoid 71 and the casing 53 is returned to a normal state, in which the opening thereof is directed upward.
In addition, with the configuration, in which the solenoid 71 is used to turn the casing 53 , a side 53 b of the casing 53 is preferably inclined at a predetermined angle because a turning angle of the casing 53 is restricted. Thereby, when the casing 53 is turned, the margin paper slides down the side 53 b and can be quickly ejected.
Also, with this configuration, in order to expedite ejection of the margin paper received in the casing 53 , a plurality of gaps sized to allow an air to easily pass therethrough but not to allow the margin paper to pass therethrough may be provided on the side 53 d and a part of the bottom of the casing 53 and the fan 66 is preferably arranged in a manner to blow the wind into the casing 53 as shown in FIG. 5(B) . Thereby, the margin paper can be ejected by gravity and wind, so that ejection can be terminated in a short period of time.
FIG. 6 is a view showing an outline of a turning mechanism of a margin paper receiving section that is configured differently from those in FIGS. 4 and 5 . With the configuration shown in FIG. 6 , a casing 54 is not turned but an opening and closing mechanism 81 is provided to open and close a side or a bottom surface of the casing 54 . More specifically, mounted on a side 54 d of the casing 54 as shown in FIG. 6(A) is a lid 83 , one end of which is pivotally born by a shaft 82 mounted perpendicular to a direction of conveyance of the roll paper 11 . Also, a bottom surface 54 c in the casing 54 is inclined to become low toward the lid 83 . Further, the shaft 82 is connected to a motor 84 , and when the control unit 7 outputs an ejection command signal, the motor 84 is actuated, so that the lid 83 is opened via the shaft 82 by power of the motor 84 . Thereby, the margin paper received in the casing 54 slides down the bottom surface 54 c of the casing to be ejected from the side of the casing 54 .
Also, when the control unit 7 outputs a reset command signal to the motor 84 after the lapse of a predetermined period of time since the lid 83 is opened, the lid 83 is closed.
On the other hand, a lid 92 pivotally born by a shaft 91 to be able to open and close may be provided close to an end of a bottom surface 55 c of a casing 55 as shown in FIG. 6(B) . With the configuration, the shaft 91 is connected to a motor 93 , and when the control unit 7 outputs an ejection command signal to actuate the motor 93 , power of the motor 93 is transmitted to the lid 92 via the shaft 91 and the lid 92 is opened. Since the bottom surface 55 c is inclined in a manner to become low toward the lid 92 . the margin paper received in the casing 55 slides down the bottom surface 55 c to be ejected from the bottom of the casing 55 .
Also, when the control unit 7 outputs a reset command signal to the motor 93 after the lapse of a predetermined period of time since the lid 92 is opened, the lid 92 is closed.
In addition, with the configuration shown in FIG. 6(A) and 6(B) , in order to terminate ejection of the margin paper in a short period of time when the lid 83 or the lid 92 is opened, a fan 67 that blows the wind into the casing 51 may be provided above the casing 54 or the casing 55 .
As described above, with the photoprinter 1 , when the number of sheets of margin paper received in the margin paper receiving section 6 reaches a predetermined number, the margin paper is automatically ejected, so that it is possible to prevent the margin paper from overflowing the casing 51 to cause lodgment of paper and failure. Also, since the photoprinter 1 ejects the margin paper by turning the margin paper receiving section or opening and closing the lid instead of removing the margin paper receiving device, there is no fear that a user erroneously inserts a hand into the vicinity of the cutting section 5 , whereby it is possible to prevent a user from getting hurt by the cutter 41 .
In addition, a garbage box having a large capacity, or a bag having a large capacity is preferably mounted below the casing 51 of the photoprinter 1 . Thereby, it is possible to prevent the margin paper ejected from the casing 51 from scattering.
The invention produces the following effects.
Since the margin paper received in the margin paper receiving device can be ejected periodically, a user of the photoprinter can use the photoprinter without caring about that timing, at which the margin paper should be discarded.
Since when ejecting the margin paper, the photoprinter 1 turns the margin paper receiving section or opens the lid instead of removing the margin paper receiving device, there is no fear that a user erroneously inserts a hand into the vicinity of the cutting device, whereby it is possible to prevent a user from getting hurt by the cutting device.
Further, the wind from the fan can be made use of to eject the margin paper, so that it is possible to eject the margin paper from the margin paper receiving device in a short period of time. Also, the fan can serve for ejection of the margin paper and for ventilation in the photoprinter, so that it is possible to prevent an increase in cost.
The foregoing description of the preferred embodiments of the 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, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The embodiments were chosen and described in order to explain the principles of the invention and its practical application to enable one skilled in the art to utilize the invention in 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. | When a margin paper constituting a margin between pictured formed sheets, on which pictures have been formed, is cut by a cutter, it is received in a casing. The number of times, in which cutting means cuts a number of sheets to avoid overflowing of the margin paper received in the casing, is beforehand set as a set value, and the number of times, in which the cutter cuts a roll paper, is counted. When a count value reaches the set value, a control unit turns the casing so that an upper opening of the casing is directed downward, and causes the margin paper in the casing to be ejected. When a predetermined period of time has elapsed, the casing is again turned to be returned to an original state. The number of times as counted is reset and counting is again performed. | 6 |
This is a division of application Ser. No. 299,096 filed Sept. 3, 1981 now issued as U.S. Pat. No. 4,518,940.
BACKGROUND, FEATURES OF INVENTION
This invention relates to the manufacture of magnetic recording heads and particularly to the attachment of back-bars to core legs therein and to an improved technique therefor and an associated fixture.
Workers in the art of manufacturing magnetic digital recording heads (sliders) for certain digital recording are aware of serious difficulties associated with positioning and attaching magnetic "back-bars" between protruding core legs. It is presently conventional to use spring-applied clamping action; but this is too rough and all too often, and too easily, distorts or snaps-off the core legs (typically a few grams of pressure can do so; and the careless flick of a finger can destroy a leg). This technique requires ultra-careful handling and application of pressure while the clamp is brought into contact--moreover the clamp must be held in place while the adhesive is curing--a very delicate, near-impossible operation unless a large percentage of breakage is to be tolerated (breakage is, of course, very expensive, since the parts themselves have already had a great deal of time and money invested in them).
The present invention eliminates this potentially costly and difficult procedure by substituting a "magnetic fixture" which applies a back-bar-attracting magnetic flux through the magnetic circuit of the core legs themselves and employs magnetic flux (rather than spring tension) to attract and retain the back-bar in place for bonding. As a preferred form, I teach the use of an ordinary U-shaped permanent magnet combined with a "gapped keeper" to project this magnetic flux.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other features and advantages of the present invention will be appreciated by workers as they become better understood through reference to the following detailed description of presently preferred embodiments which should be considered in conjunction with the accompanying drawings wherein like reference symbols denote like elements:
FIG. 1 is a very schematic side view of a "slider" workpiece shown in operative relation with a "back-bar-to-be attached", together with functionally-indicated magnetic flux projecting means according to the subject invention; FIG. 1A shows the slider in plan view;
FIG. 2 is an upper perspective, and
FIG. 3 an elevational view, of one embodiment of a preferred magnetic back-bar attachment fixture embodiment, and
FIGS. 4 and 5 show a typical slider-spring mount in planned elevation views respectively.
DESCRIPTION OF PREFERRED EMBODIMENTS
The problem and functional-indication of my solution:
Workers will recognize the rather schematically-shown magnetic recording slider SL in FIG. 1 (plan view in FIG. 1A) as of a type adapted for high performance digital recording, e.g., with floppy disks. Protruding from the slider body are a pair of tiny frangible core legs CP, CP', while convergent portions thereof are shown in phantom within the body of the slider, these being assumed as meeting along a prescribed magnetic center-line CL--CL as is well known in the art (core-gap g c defines this center line). Workers understand that these core legs are adapted for wrapping with tiny inductor coils and that a magnetic back-bar BB is to be attached between the legs to complete the magnetic circuit being of relatively high reluctance, relatively magnetic (preferably ferrous) material. Back-bar BB must, of course, be carefully brought up into relatively planar contact with both of the core legs CP, CP' and held there while an epoxy, or other bonding material, is cured to complete the permanent connection. In many cases the epoxy or like adhesive material is disposed as a film on one or both of the core legs and at associated attachment sites d, d' on the back-bar BB. Workers will recognize that a great problem exists in the art whereby breakage of the core legs can readily occur unless an extreme, almost unreasonable, degree of care is exercised in carefully bringing back-bar BB into contact with them and retaining it there while the adhesive cures.
The invention solution to this problem, dispensing with such spring-clamping action, is indicated rather schematically by the U-shaped permanent magnet MG and associated flux-focusing "gapped keeper" FA in FIG. 1. It will be remembered that the implementing structure is intended to be applied to slider SL at the face thereof opposite the core legs (adjacent lower core-edge D). These are to be positioned such that the flux emanating from and returning to magnet MG, via keeper FA, will enter slider SL on different respective sides of the magnetic center line CL--CL. Thus, for instance as depicted the exit flux may be applied to only a first core leg CP on one side of gap g c , while the return flux will return only via the other leg CP'. This, of course, assures that a maximum flux is sent to, and through, back-bar BB as it is brought adjacent the projecting ends of these core legs to achieve the inventive results. More particularly, when the slider SL is disposed in an appropriate fixture such as fixture F x in FIGS. 2 and 3 (e.g., held there by its spring mount as detailed below) and preparatory to attaching back-bar BB, the "magnetic block" MG/FA may be pressed firmly against slider SL (e.g., held in place by a retaining means like clamp RP in FIGS. 2 and 3), so that the external portion of the flux emanating from keeper FA, or a good portion thereof, may be sent up one core leg and returned down the other core leg. Then, when back-bar BB is brought closely adjacent the two core legs, to span the flux path between them and complete their magnetic circuit, as workers in the art will understand, it may be "attached magnetically".
Thus, with the magnetic means FA/MG so pressed against slider SL, an operator may then bring back-bar BB up into reasonable propinquity with the slider legs so that respective portions thereof confront corresponding end-portions of a respective core leg (e.g., site d adjacent the end of leg CP, site d' adjacent the end of leg CP'). Once the back-bar is relatively close to the core legs the magnetic flux can attract it and pull it into relatively intimate contact with the leg ends and retain it there while bonding is effected (e.g., while the customary epoxy is being cured).
This technique takes unusual and inventive advantage of the pre-existing magnetic circuit formed by the core legs and of the low reluctance characteristic of the back-bar, while requiring no particular complexity in tooling means (e.g., essentially just a "magnetic block" as opposed to delicate spring positioning means or the like); it allows one to be relatively casual in positioning the back-bar adjacent the core legs since the flux will pull it into contact through the last several mils or so and retain it there, requiring no springs, no delicate contact, pressure carefully measured, etc.
Workers in the art will appreciate how much less susceptible this technique is to breaking or bending core legs and how relatively more convenient it is, as well as how relatively inexpensive is the fixture therefor (no moving parts, no position determining or translation means, either).
Fixture embodiment; FIGS. 2, 3:
A preferred embodiment-fixture for this technique is indicated in FIG. 2 as fixture F x where a U-shaped permanent magnet MG is affixed on one end of a mounting plate B and adapted to be magnetically coupled to a superposed flux-focusing keeper FA (shown exploded-away for clarity). Magnet MG may be any convenient source of magnetic flux adapted to direct flux up into the slider (gap g c ) SL so as to result in alternative flux through core legs CP, CP'. Here, the magnet is U-shaped and directs opposite-polarity flux to legs CP, CP' (with the focus-assistance of keeper FA). Workers will visualize other equivalent arrangements--e.g. one source of unidirectional flux adjacent core-edge d and an oppositely-poled second source of flux adjacent legs CP, CP' (opposite bar BB). Obviously electro-magnet means may be substituted in certain cases (e.g., even another magnetic R/W head possibly!)
Keeper FA could be dispensed with if the flux source could, by itself, project flux properly into slider SL (legs CP, CP' thereof)--e.g., if keeper FA could be magnetized to so direct the required flux by itself. Since the keeper FA only need provide a good low-reluctance flux path to and from slider SL it, should not, by itself, be magnetizable (e.g., so one needn't worry about reversing FA into opposite polarity with MG--workers will know of suitable ferrous keepers; e.g., of soft steel with intermediate gap g a formed by a brazing nickel alloy bond or the like).
As indicated also in FIG. 3 a U-shaped retaining clamp RP is attached to the end of plate B adjacent magnet MG and adapted to retain keeper FA in good frictional contact with MG (FA may be slid in between MG and the lip of clamp RP and adjusted for registration of its gap g a with the associated slider gap g c ). Fixture F x is also adapted to retain a slider SL with its gap g c so registered, being removably attached to the typical spring mount (indicated at mount SL-P).
Thus, at the opposite end of plate B a mounting block MB is attached on which the other end of spring SL-SP (see FIGS. 4, 5) may be mounted, position-aligned and retained in a position to best orient slider SL relative to the magnetic keeper FA. While various other retaining means may be used, I prefer to use a relatively simple spring clamp S comprised of flexure spring material (steel) and adapted to be attached, via a clamping slot OP and associated screw, detachably to mounting block MB. Clamp S may be selectively moved up and down, into and out of engagement with the end of slider spring SL-SP, as indicated in FIG. 3 and understood in the art. Alignment means such as pin rp is preferably provided to help properly align the spring and its slider.
Thus, in operation, one may simply insert the keeper bar FA in place over magnet MG and place the slider SL in contact therewith with core legs CP, CP' protruding upward in position for attachment of the back-bar and with core gap g c registered with keeper gap g a . The opposite end of the slider spring SL-SP is positioned atop mounting block MB, being registered as pin rp, then clamp S is depressed onto the end thereof to retain it during back-bar attachment.
Now, using tweezers or any other convenient tool, one may simply grip the associated back-bar (e.g., precoated with epoxy or like adhesive preferably) and bring it up adjacent core legs CP, CP'--so that its ends lie adjacent the contact points of the respective ends of the core legs--whereupon the magnetic flux will pull the back-bar into good contact with the legs and hold it there so bonding may proceed (e.g., by next touching the pieces with a bead of epoxy, as well known in the art). The structure may be left until the adhesive is cured (or alternatively heat applied as necessary, since the fixture can be made to survive the temperatures and atmosphere of a curing oven if necessary). With back-bar attachment complete, the workpiece may be removed simply by displacing clamp-spring S.
Results:
As suggested above, excellent results have been achieved with surprising ease and with very little "scrap".
Alternative techniques, structure:
This method (and fixture) may also be used for other workpieces where tiny frangible magnetic parts are to be bonded together.
It will be understood that the preferred embodiments described herein are only exemplary, and that the invention is capable of many modifications and variations in construction, arrangement and use without departing from the spirit of the invention.
Further modifications of the invention are also possible. For example, the means and methods disclosed herein are also applicable to other like slider structures and with other like fixtures. Also, the present invention is applicable for coupling magnetic parts on other like structures.
The above examples of possible variations of the present invention are merely illustrative. Accordingly, the present invention is to be considered as including all possible modifications and variations coming within the scope of the invention as defined by the appended claims. | A method and associated fixture for magnetically attracting and holding back-bar to respective magnetic core-leg portions of a typical magnetic slider assembly. A plurality of embodiments constructed in accordance with different fabrication techniques are described. | 8 |
FIELD OF THE INVENTION AND RELATED ART
This invention relates to a container and a loading device for the same. More particularly, the invention is concerned with a mask cassette and a mask cassette loading device suitably usable, for example, in an X-ray exposure apparatus for exposing a semiconductor wafer to a mask with X-rays contained in a synchrotron radiation beam to print, on the semiconductor wafer, a pattern prepared on the mask for manufacture of semiconductor microcircuit devices.
In semiconductor device manufacturing exposure apparatuses, usually each reticle or mask (hereinafter simply "mask") is held in a container (hereinafter "cassette casing") for keeping or protection of the same against dust. Cassette casings accommodating respective masks are adapted to be mounted into a mask loader, attached to the exposure apparatus and having portions of a number as required for the exposure process.
In the exposure operation, for sequential loading of the masks from the mask loader, first, the exposure apparatus operates to select a desired cassette casing in the mask loader. The selected cassette casing removed from the mask loader by means of a mask conveying mechanism. Thereafter, an access window of the cassette casing is opened by means of a part of the mask conveying mechanism, and the mask in the thus opened cassette casing is taken out by a mask changer of the mask conveying mechanism and is conveyed to a predetermined position. After the exposure is completed, the mask is conveyed by the mask conveying mechanism back into the cassette casing, and the next cassette casing is prepared.
The mask loader is actuated in a specified atmosphere. The masks are stored in respective cassette casings, one by one. Accordingly, such a cassette casing in which a desired mask is accommodated is selected by a selecting device and, then, a door of the selected cassette casing is opened by means of an opening device which is a part of the conveying mechanism. Then, the mask in the cassette casing is taken out of the casing by the conveying mechanism and is conveyed to the predetermined position.
On the other hand, each mask to be used in a semiconductor device manufacturing exposure apparatus such as, for example, a stepper or an aligner, comprises a square glass plate on which a pattern is provided by chromium plating. Mask cassettes for accommodating such masks can be classified into two types. One is a type which is used, for example, when each mask is to be directly, by the hands of an operator, introduced into a semiconductor device manufacturing apparatus. Such type of cassette comprises a resin container of a simple structure and is arranged so that plural masks are inserted into and kept in the container, in upstanding attitude.
The other one is a type which is used, for example, when the cassette is to be directly loaded to the semiconductor device manufacturing apparatus. Such a cassette is arranged to accommodate only one mask, laying down therein The cassette has a cover which can be operationally associated with a cassette opening/closing mechanism within the semiconductor device manufacturing apparatus, so that it can be opened and closed Such a cassette is disclosed, for example, in Japanese Laid-Open Patent Application Sho 61-130127, and a resin container is used.
FIG. 7 shows a known type mask cassette.
Denoted in this Figure at CF is a cassette frame; at CM is a major part (base) of the cassette; and at RM is a mask. Each cassette of the described type can accommodate therein one mask, only. Further, it is not structured to provide a completely sealed container.
SUMMARY OF THE INVENTION
In the example described above, the exposure apparatus operates in an atmospheric ambience and only the temperature and humidity of the ambience are controlled. The pressure of the ambience depends on the atmospheric pressure On the other hand, the exposure ambience of an X-ray exposure apparatus, among various exposure apparatuses, is a low vacuum (or low pressure) inert gas. Therefore, there is a difficulty in using the conveying mechanism of the conventional apparatus as a conveying mechanism in an X-ray exposure apparatus.
Further, combining a load locking mechanism for sample replacement in vacuum with the known type conveying mechanism as described, disadvantageously makes the structure complicated.
Additionally, although in a reduction optical exposure apparatus it is relatively easy to take measures for dust or foreign particles, it raises a very serious problem in the X-ray exposure apparatus. The reason for this is as follows:
For example, in the case of a reduction optical exposure apparatus having a reducing magnification of 1/5, a pattern on a mask to be transferred to a wafer has a size five times larger than the size of a pattern to be printed on the wafer. Therefore, the size to be required in the control of dust or foreign particles is relatively large and thus, the control on the mask is relatively easy. However, in current X-ray exposure apparatuses, a pattern of a mask is transferred to a wafer by unit magnification, whereas the linewidth of the pattern to be reproduced on the wafer is narrower (e.g. 1/4) than that of a pattern printed in a conventional exposure method. This necessitates control for dust or foreign particles, to a small size (e.g 1/20, on the mask surface) as compared with that in the past This raises a problem that such dust or foreign particles, with which no inconvenience is caused in conventional apparatuses, cannot be disregarded.
As an example, in the conventional apparatus, for loading masks from cassette casings for each mask, a corresponding cassette casing has to be opened. Thus, there arises a possibility that dust or foreign particles produced at that time from a hinge, for example, or dust or foreign particles blown off from a part adjacent the opening are attached to the mask. The dust or foreign particles produced on that occasion, even if they are of a small size, raise a problem in an X-ray exposure apparatus.
It is accordingly a primary object of the present invention to provide a mask cassette and a mask cassette loading device by which, even in an environment as an X-ray exposure apparatus, for example, wherein the atmosphere is intercepted, the mask cassette loading can be made with a simple structure and without causing deposition of dust or foreign particles even of small size to the mask.
In accordance with an aspect of the present invention, to achieve this object, there is provided a mask cassette and a mask cassette loading device which can be used in a chamber isolated from the atmosphere. The mass cassette is adapted to keep a plurality of masks therein and is held by a specific means which is adapted to open/close a cover for a major part (base) of the mask cassette This specific means is made as a unit with a conveying means for conveying the major part of the mask cassette to a predetermined site. Such a site is set above the position at which the mask cassette is held before its cover is opened. The chamber is equipped with pressure measuring means and an introducing, inlet port for introducing into the chamber, at least one type of gas.
This arrangement can reduce the number of areas or portions that provide a possibility of the creation of dust or foreign particles and, therefore, is effective to maintain cleanness in the chamber. Further, after the mask cassette is opened, the mask is placed at such a site above the preceding position thereof and comes far away from the loader having a high possibility of production of dust or foreign particles. Therefore, the possibility of the contamination of the mask by the dust or foreign particles can be reduced significantly.
Additionally, with this arrangement, it is possible to execute the mask storing or mask loading, without contacting the same with the atmosphere. As a result, it is possible to avoid deterioration of the mask due to reactive gases contained in the atmosphere.
A mask for use in an X-ray exposure apparatus has a structure that an SiN thin film on an Si wafer is held by a ring-like supporting member or an organic film is stretched over a ring-like supporting member, wherein a pattern is formed by a metal such as gold, tungsten or otherwise.
The exposure operation of the X-ray exposure apparatus is made in a reduced pressure on He gas, of an order of 100-200 Torr. The line-and-space (L/S) in X-ray lithography is and an order of 0.25 micron, for example. Because of the unit-magnification exposure, the admitted size of dust or foreign particles becomes smaller with the line-and-space, and even those particles of a diameter of about 0.25 micron are to be considered in relation to the protection to dust.
When a known type mask cassette is used as a cassette for an X-ray mask, the following inconveniences arise.
(1) If, during the mask cassette replacement, a mask is exposed to the atmosphere, there occurs a disadvantage of oxidization due to vapor and O 2 in the atmosphere. This causes deterioration of the mask.
(2) The operation of the X-ray exposure apparatus is made in an He chamber, as described. Therefore, it is necessary that the cassette loading is done within the chamber. At this time, as in the example of FIG. 7, if the cassette is of the type for accommodation of a single mask, there is a possibility that each time the cassette loading is made, dust or foreign particles are produced in the chamber.
(3) Protection of the mask cassette against entrance of dust or foreign particles thereinto, during storage thereof, is insufficient.
Accordingly, it is a second object of the present invention to provide a mask cassette suitably usable in an X-ray exposure apparatus, for allowing mask loading isolated from the atmosphere, while reducing to, as small as possible the production of dust or foreign particles while, on the other hand, during mask storing, the atmosphere is intercepted to prevent entrance of dust or foreign particles into the cassette.
In accordance with an aspect of the present invention, to achieve this object, a mask cassette usable in an X-ray exposure apparatus comprises three parts, that is, a cassette major part (base) adapted to keep and hold therein at least two X-ray masks at once, a over part effective to substantially close the cassette major part, and a locking mechanism part for coupling the cassette major part with the cover part at the time of closure.
The cassette major part and the cover part can be accessed only in one direction, and a sealing member is provided at an abutment side. The sealing member providing substantial sealing is designed to withstand at least an external pressure in the closed state. Further, at least one valve is provided for introduction/exhaustion of gas within the cassette.
With this structure, the inside of the cassette can be substantially isolated from the outside gas. Thus, by filling the inside of the cassette with a non-reactive gas, for example, it is possible to avoid deterioration of the mask within the cassette, such as oxidization or otherwise, even if it is kept therein for a long period.
The mask cassette can accommodate therein a plurality of masks, and only one cassette loading operation is required in the chamber of the X-ray exposure apparatus. Therefore, the possibility of dust creation by the loading can be reduced.
Further, since the sealing property is high, entrance of external dust or foreign particles into the cassette can be substantially completely avoided.
These and other objects, features and advantages of the present invention will become more apparent upon a consideration of the following description of the preferred embodiments of the present invention taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a mask cassette loading mechanism according to a first embodiment of the present invention.
FIGS. 2A and 2B are perspective views, respectively, specifically illustrating the sequence of the mask cassette loading operation.
FIG. 3 is a perspective view of a mask cassette loading mechanism according to a second embodiment of the present invention.
FIG. 4 is a perspective view, showing the appearance of an X-ray mask cassette according to an embodiment of the present invention.
FIG. 5 is a plan view, showing a locking mechanism of the mask cassette.
FIG. 6 is a perspective view, showing the appearance of an X-ray mask cassette according to another embodiment of the present invention.
FIG. 7 is a perspective view showing a known type mask cassette.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a sectional view showing a mask cassette portion and a mask loader portion of an X-ray exposure apparatus into which a mask cassette loading device according to an embodiment of the present invention is incorporated.
Denoted in FIG. 1 at MF is a mask (reticle). The mass MF comprises a ring-like supporting member and a thin film member attached to the ring member. A pattern to be transferred to a semiconductor wafer for manufacture of semiconductor chips, is formed at a central part of the thin film member. The mask MF may have a shape other than a circle.
Denoted at MCM is a major part (base) of a mask cassette for accommodating therein masks MF. In this major part MCM of the mask cassette, a plurality of masks MF, of a number 20, for example, can be accommodated. These masks MF are placed upstanding (with the pattern bearing surface of each mask held parallel to the Y axis) and radially on the X-Z plane. Usually, each mask MF is held immovable by means of a magnetic unit mounted to the mask cassette major part MCM. However, the manner of disposition of the masks MF is not limited to the disclosed example, rather they may be placed so as to lay down. Further, with regard to the holding method, they may be held mechanically.
Denoted at MCC is a cassette cover which covers the mask cassette major part MCM to close the same. In FIG. 1, the mask cassette major part MCM and the cassette cover MCC are illustrated as being separated from each other. However, normally the cassette is closed to provide an integral, hermetically-sealed structure. In this embodiment, the mask cassette has a cylindrical shape. However, it may have a rectangular parallelepiped shape. The sealing is provided by using an O-ring or a U-shaped packing. Thus, when the mask cassette provides an integral structure, there is substantially no flow of gas between the inside and the outside. Details of the mask cassette will be explained in a later part of this Specification.
Denoted at TT is a turn table coupled to the mask cassette major part MCM, for allowing selection of a desired mask MF. Since the masks MF are disposed radially on the mask cassette major part MCM, with respect to the X-Z plane, for selection of masks MF, the mask cassette major part MCM is rotationally moved in the direction indicated by arrow A, about an axis parallel to the Y axis. As a matter of course, a different mechanism for the mask MC selection may be used if the manner of disposition of the masks MF is different.
Denoted at ER is an elevator rod which is attached to the turn table TT and which is arranged to separate the mask cassette major part MCM from the cassette cover MCC to move the same to a predetermined site, along the Y axis (vertically) at which site the mask MF transfer and reception is to be made.
In this embodiment, the mask cassette major part MCM is moved upwardly in the Y-axis direction while the cassette cover MCC is held immovable. However, the manner of separation differs, in accordance with the structure of the mask cassette, and the vertical separation is not a requisition.
Denoted at EA is an elevator for driving the elevator rod ER, which comprises an air cylinder in this embodiment. However, a hydraulic or other type driving mechanism may be used.
Further, while in this embodiment the turn table TT is moved in the Y-axis direction through the elevator rod ER, the elevator EA may be disposed within a mask chamber MCH. The mask chamber MCH is adapted to isolate the mask or masks MF from the atmosphere, even when the mask cassette major part MCM and the cassette cover MCC are separated.
Denoted at WMC is a main chamber in which X-ray exposure is to be made. The mask chamber MCH and the elevator EA are attached to the main chamber WMC. However, the elevator EA may be attached to the mask chamber MCH.
Denoted at MCHD is a door of the mask chamber MCH. By opening/closing the door MCHD, the loading/unloading or replacement of the mask cassette can be made. Usually, the door MCHD is equipped with an interlocking function.
Denoted at GP1 and GP2 are gas ports connected to the mask chamber MCH. Denoted at V1 and V2 are valves for the gas ports GP1 and GP2, respectively. These valves may be operated manually or electrically.
Denoted at EP is an evacuation port of the mask chamber MCH. The port EP communicates with a vacuum pump, not shown. Evacuation valve EV operates to control the evacuation.
Denoted at PG is a pressure gauge for monitoring the pressure in the mask chamber MCH. Denoted at GV is a gate valve provided between the main chamber WMC and the mask chamber MCH. Each mask MF is conveyed through this gate valve GV into the main chamber WMC.
Denoted at MH is a mask hand which is movable in the X-axis direction to covey each mask MF into the main chamber WCM and to move the same back to the mask cassette main part MCM. The configuration of the mask hand MH can be modified with the shape of the mask MF and, therefore, it is not limited to the disclosed example. For the handling of the mask MF by the mask hand MH, either mechanical clamping or vacuum-chuck clamping may be used. Also, the direction of motion of the mask hand MH can be modified with the shape and structure of the mask cassette.
FIGS. 2A and 2B are perspective views, respectively, of the device of the FIG. 1 embodiment. Referring to FIGS. 1, 2A and 2B, the operation of the device of the present embodiment will be explained in accordance with the sequence.
In FIG. 2A, first the door MCHD of the mask chamber MCH is opened. Then, the mask cassette having the mask cassette major part MCM coupled with the cassette cover MCC is placed on the turn table TT in the mask chamber MCH. Then, the mask cassette major part MCM is secured to the turn table TT, while the cassette cover MCC is secured to the mask chamber MCH. The fixation may be made by using actuator means or, alternatively, it may be made manually. Also, any fixation method is usable. In this embodiment, they are fixed and locked manually.
Subsequently, the door MCHD is closed to close the structure. Then, the evacuation valve EV shown in FIG. 1 is opened and, by using the vacuum pump, the mask chamber MCH is evacuated. The degree of vacuum (pressure) is monitored by using the pressure gauge PG. When the degree of vacuum becomes to a predetermined value, the evacuation valve EV is closed Thereafter, the solenoid valve V2 is opened to allow the flow of a nitrogen (N 2 ) gas from the gas port GP2. The pressure in the mask chamber MCH is thus brought to a predetermined pressure. In the present embodiment, this predetermined pressure is equal to the pressure in the mask cassette, and is set to be equal to the atmospheric pressure (760 Torr), for example. The inside of the mask cassette is set in advance to the atmospheric pressure It will be understood that, in this embodiment, at a moment when the pressure gauge PG detects that the pressure in the mask chamber MCH is at or close to the atmospheric pressure, that is, when the differential pressure between the mask chamber MCH and the mask cassette becomes equal to zero, the solenoid valve V2 is closed. Although the predetermined pressure may be any value, a pressure close to the atmospheric pressure is desirable. If it is close to the atmospheric pressure, only a small force is necessary to hold the cover MCC of the mask cassette.
The aforementioned predetermined pressure of the mask chamber MCH may be set to be slightly lower (e.g. 700 Torr) than that in the mask cassette. On that occasion, the solenoid valve V2 is closed when the pressure gauge PG detects that the pressure in the mask chamber MCH becomes approximately equal to 700 Torr. With this arrangement, when the cover MCC is separated from the cassette major part MCM, a flow of gas round the mask cassette occurs, in a direction outwardly of the cassette major part MCM. Therefore, the possibility of entrance of dust into the cassette major part MCM reduces advantageously.
Subsequently, the elevator EA is actuated to move the elevator rod ER upwardly. The stop position is adjusted in advance by means of the actuator (air cylinder in this embodiment) of the elevator EA. As the elevator ER moves upwardly, as shown in FIG. 2B, the mask cassette major part MCM and the cassette cover MCC are separated from each other and, additionally, the mask MF is brought to a position as shown in FIG. 1, at which it can be handled by the mask hand MH.
Then, in order to evacuate the mask chamber MCH filled with nitrogen N 2 the evacuation valve EV is opened and evacuation is made by means of the vacuum pump (not shown) until a predetermined pressure is established. After it is confirmed through the pressure gauge PG that the pressure in the mask chamber MCH becomes to the predetermined pressure, the evacuation valve EV is closed, and the solenoid valve V1 is opened. Then, from the gas port GP1, helium (He) is introduced into the mask chamber MCH. When it is confirmed through the pressure gauge PG that the pressure in the mask chamber MCH becomes substantially equal to that in the main chamber WMC, the solenoid valve V1 is closed to stop the introduction of the helium (He).
After completion of a series of operations described above, the gate valve GV for communicating the main chamber WMC and the mask chamber MCH is opened. The mask hand MH in the main chamber WMC moves into the mask chamber MCH so as to convey, into the main chamber WMC, the mask MF set at the selection position by the turn table TT. After the hand grasps the mask MF, it brings the mask into the main chamber WMC.
Next, description will be made of the procedure for taking the mask cassette out of the mask chamber MCH, for replacement of the same after the X-ray exposure or for the shut-down of the apparatus.
First, a mask MF which is in the main chamber WMC is moved back to a predetermined mounting position in the mask cassette major part MCM and, thereafter, the gate valve GV for communicating the main chamber WMC with the mask chamber MCH is closed.
Then, the evacuation valve EV is opened and, by means of a vacuum pump (not shown) the mask chamber MCH is evacuated. When the pressure gauge PG detects a predetermined pressure, the evacuation valve EV is closed and promptly, the solenoid valve V2 is opened to introduce nitrogen (N 2 ) into the mask chamber MCH. When the pressure gauge PG detects that the pressure in the mask chamber MCH becomes a predetermined pressure, the solenoid valve V2 is closed. In this embodiment, this pressure is set to be equal to the atmospheric pressure (760 Torr). This is because, in order to separate the mask cassette major part MCM from the mask cassette cover MCC as the mask cassette is placed outside the mask chamber MCH, if the difference between the inside pressure and the atmospheric pressure is large, a large force is required for the separation, resulting in a difficulty. However, it is not always necessary that the inside pressure is set to be equal to the atmospheric pressure.
Subsequently, the elevator EA is actuated to move the elevator rod ER downwardly. As a result of the downward movement of the elevator rod ER, the mask cassette major part MCM is coupled with the cassette cover MCC, such that the inside of the mask cassette is sealingly filled with a nitrogen (N 2 ) ambience of 760 Torr. After the inside of the mask chamber MCH is rendered to be at the outside pressure, the door MCHD is opened. In this embodiment, a purge valve is provided, while not shown in the drawings The locking of the mask cassette major part MCM and the turn table TT as well as the locking of the cassette cover MCC and the mask chamber MCH are released, and the mask cassette is taken out of the mask chamber MCH.
It is a possible alternative that, after the mask cassette major part MCM is coupled with the cassette cover MCC, the pressure in the mask chamber MCH is adjusted to be slightly higher (e.g. by about 10 Torr) than the outside pressure. On that occasion, after the mask cassette major part MCM is coupled with the cassette cover MCC, the solenoid valve V2 is opened so that nitrogen (N 2 ) is supplied from the gas port GP2. As the pressure gauge PC detects that the pressure in the mask chamber MCH becomes higher, by 10 Torr, for example, than the outside pressure, the solenoid valve V2 is closed. Also, on that occasion, the solenoid valve V2 is opened as the door MCHD is opened, whereby the nitrogen (N 2 ) can be continuously supplied into the mask chamber MCH from the gas port GP2. This is done so as to prevent mixture of the external gas into the mask chamber, as the door MCHD is opened, to avoid introduction of dust or foreign particles into the mask chamber MCH.
While the present embodiment uses helium (He) gas and nitrogen (N 2 ) gas, the nitrogen (N 2 ) gas may be replaced by an inert gas such as argon (Ar), for example. Although only helium (He) may be used to simplify the gas line to a one-line system to thereby allow omission of a part of the procedure, it is not so desirable, because the sealing of helium (He) is not easy. In the present embodiment, nitrogen (N 2 ) is used in consideration of cost and danger.
The mechanism and the sequential operation according to the present embodiment, described hereinbefore provide the following advantageous effects:
(1) From beginning to end, each mask MF does not contact the atmosphere. This reduces deterioration or otherwise of the mask MF. This is because the ambience contains substantially no vapor, reactive gas and the like which are included in the atmosphere.
(2) Each mask can be protected against dust or foreign particles. As described hereinbefore, the mask MF should be protected with certainty against dust or foreign particles. In this embodiment, a plurality of masks MF are kept, as a group, in the mask cassette major part MCM. In the conventional example, plural cassettes should be prepared for the respective masks. Therefore, each time a mask MF is accessed, a corresponding cassette should be opened and closed. In the present embodiment, as compared therewith, the opening/closing is made only at the time of loading of the mask cassette and, in the course of the operation, the cassette opening/closing is not necessary. Therefore, the production of dust can be reduced. As a result, it is possible to maintain the cleanness in the mask chamber MCH.
(3) The position of the mask hand MH for transfer and reception of a mask MF is set above the mechanism for loading the mask cassette cover MCC, and therefore, any dust or foreign particles produced from the mask cassette MCC during loading by the mask hand MH are difficult to be deposited to the mask MF. As a result, the possibility of mask MF deterioration due to the loading of the cassette cover MCC is reduced.
(4) The opening and closing of the mask cassette in the described sequence makes it easy to control the gas and pressure in the mask cassette.
Next, description will be made of a mechanism for loading a mask cassette of a type different from that described in the foregoing.
FIG. 3 is a perspective view of a cassette loading mechanism according to a second embodiment of the present invention. Denoted at MCH is a mask chamber which is illustrated in this Figure in a partial view.
Explanation will be mainly made to the features different from the FIG. 1 embodiment.
In FIG. 3, denoted at MCM is a mask cassette major part. In this embodiment, a plurality of masks MF are held to be laid down (with the pattern bearing surface of each mask MF extending parallel to the X-Z plane namely, a horizontal plane), with a predetermined interspacing in the Y-axis direction maintained between adjacent masks. A mechanical holding mechanism is used. Denoted at T is a table for carrying thereon the mask cassette major part MCM. Denoted at ER is an elevator rod which is a supporting rod for moving the table T upwardly and downwardly along the Y axis. Denoted at EA is an elevator which provides a driving mechanism for the elevator rod ER. In this embodiment, a ball-screw feeding mechanism is used, the ball-screw being driven by a stepping motor (not shown). Denoted at BM is a motor base plate to which the step motor is mounted. In the present embodiment, a large part of the elevator EA is disposed outside the mask chamber MCH, and a drive is transmitted through the elevator rod ER into the mask chamber MCH.
Denoted at MH is a mask hand. In the present embodiment, the mask hand MH executes a gripping action, by using a plunger, for handling a mask MF. Denoted at WMC is a main chamber, and at G is a gate opening. Through this gate opening G, the mask chamber MCH and the main chamber WMC communicate with each other. Each mask MF is conveyed through this gate opening G into the main chamber WMC. At this time, the mask hand MH is actuated by means of a wire and an operationally associated guide.
Further, those elements corresponding to the gas port GP, evacuation port EP, pressure gauge PG and the like of the FIG. 1 embodiment, are attached to a main chamber wall WMC, although they are not illustrated.
The operation procedure of the mechanism shown in FIG. 3 will be explained, mainly with respect to the differences from the foregoing embodiment.
First, the door MCHD of the mask chamber MCH is opened, and the mask cassette having its mask cassette major part MCM and mask cassette cover MCC coupled to each other to seal the inside, is placed on the table T. Thereafter, the door MCHD is closed and the main chamber WMC is evacuated by vacuum to a predetermined pressure. Since the main chamber WMC is in communication with the mask chamber MCH through the gate opening G, these chambers are always controlled at the same pressure. Therefore, as a result of the evacuation of the main chamber WMC, the mask chamber MCH is also evacuated. Thereafter, a helium (He) gas is introduced from a gas inlet (not shown) until a predetermined pressure is established. Subsequently, the elevator EA starts the upward movement of the table T. At this time, the position of mask MF transfer with the hand MH is at a predetermined height, and, to this position, a desired mask MF is moved. Since, in this embodiment, the elevator EA comprises a ball-screw feeding mechanism, it can also serve as a positioning mechanism. Namely, it has both the function of a separation mechanism for the mask cassette major part MCM and the mask cassette cover MCC and the function of a selection mechanism for masks MF.
After a predetermined exposure operation in the main chamber WMC is completed, all the masks MF are kept in the mask cassette major part MCM. Then the elevator EA moves the mask cassette major part MCM downwardly so as to couple the same with the mask cassette cover MCC. Then, the main chamber WMC is opened to the atmosphere. The mask cassette of the present embodiment is designed to be resistive to the external pressure, and after the mask cassette cover MCC is coupled with the mask cassette major part MCM, the cassette is substantially hermetically sealed. Therefore, the inside of the mask cassette can be held by a helium (He) gas of a predetermined pressure. Subsequently, the door MCHD of the mask chamber MCH is opened, and the mask cassette is taken out. With the procedure described above, the loading is accomplished.
In the second embodiment, in addition to the advantageous effects of the first embodiment, the main chamber WMC and the mask chamber MCH communicate with each other. Therefore, there is an advantage that each of the evacuation system and the gas introduction system comprises a one-line system. Also, since no gate valve is provided, the number of areas having a possibility of dust creation is reduced.
Additionally, since the elevator EA also serves as a mask selecting mechanism, no mask cassette loading mechanism is present in the mask chamber MCH. This results in a reduction in power of the mechanism as well as a reduction in the number of areas having a possibility of dust creation. Therefore, it is possible to maintain high cleanness in the mask chamber MCH.
The cassette loading mechanism according to the present embodiment, described in the foregoing, provides the following advantageous effects:
(1) The possibility of deposition of dust or foreign particles to a mask can be reduced, with an advantage of prevention of mask deterioration as well as the prolongation of the lifetime of the mask.
(2) The mask cassette loading mechanism can be simplified in the chamber, with an advantage with regard to space and cost.
FIG. 4 is a partially broken perspective view, showing the appearance of a mask cassette according to an embodiment of the present invention. The mask cassette of this example, can be incorporated into the mask cassette loading device having been described with reference to FIG. 1.
In FIG. 4, denoted at MCM is a cassette major part, and at MCC is a cover. The separation of the cassette major part MCM and the cover MCC is made either by upward detachment of the cassette major part MCM from the cover MCC or by downward detachment of the cover MCC from the cassette major part MCM. Denoted at MS are mask stages, and at MF are X-ray masks.
In the present embodiment, twenty mask stages MS are disposed upstanding, radially on the X-Z plane (with each mask MF holding surface being parallel to the Y axis), so that masks MF of a number 1-20 can be accommodated on the mask stages MS. The manner of disposition of the mask stage MS is not limited to the radial form, and they may be juxtaposed on the X-Z plane. Further, they may be disposed either upstanding or laid down (with each holding surface extending in parallel to the X-Z plane). Moreover, mask stages of a number more than 20 may be used. While in the present embodiment, the masks MF are held in accordance with a magnetic attraction method, they may be held mechanically or by any other method.
Character CR denotes the location at which a cassette locking mechanism is accommodated. Details of this will be explained later.
Character S1 denotes a sealing member at the top of the cover MCC, and character S2 denotes a sealing member at the bottom of the cover MCC. Each of these sealing members S1 and S2 are provided along the circumference of a corresponding opening of the cover MCC. As illustrated in enlarged parts of FIG. 4, the sealing members S1 and S2 are adapted to be resistive to the external pressure. This is desirable for the following reason: First, once the cassette major part MCM and the cover MCC are coupled to provide a closed casing, the pressure in the cassette is determined. If, in this case, the outside pressure is higher than the inside pressure of the cassette, due to the differential pressure, the outside gas is going to enter into the cassette. If, however, it is designed to be resistive to the outside pressure, the hermetically sealed state in the cassette can be retained If, on the other hand, the outside pressure is lower than the inside pressure of the cassette, due to the differential pressure, the gas in the cassette is going to leak outwardly. However, although the external pressure resisting design involves a possibility of outward emission of gas of a small amount, it is different from the entrance of the outside gas into the cassette. Further, the motion of dust or otherwise resulting from such a flow resides in a direction, raising no practical problem with respect to the protection of the mask MF. Accordingly, in this embodiment, the orientation of the sealing member is designed to be resistive to the outside pressure.
Each of the sealing members S1 and S2 has a sealing surface which faces, such as shown in FIG. 4, in the direction (Y-axis direction) in which the cassette major part MCM and the cover MCC are separated or coupled. Namely, no sealing surface is provided at the side of sliding motion therebetween. This is effective to avoid sliding contact of the sealing members S1 and S2 to any portion, until the sealing surface is abutted. As a result, production of dust does not occur.
Denoted at CV is a purge valve which, in this embodiment is opened and closed manually Also, by using a joint, it can be connected to an introducing/evacuating system. Although for replacement of the mask MF during storage, the cassette major part MCM and the cover MCC are separated from each other, they are coupled again after the replacement. On that occasion, the purge valve CV can be used for the replacement of the gas within the cassette. The cover MCC may be provided with a plurality of purge valves.
FIG. 5 is a plan view showing details of a cassette locking mechanism CR. FIG. 5 shows the cassette major part MCM of the FIG. 4 embodiment, as viewed from below in FIG. 4, the left-hand half of FIG. 5 depicting the cassette with its outer shell being removed.
In FIG. 5, denoted at RO is a pawl for coupling the cover MCC with the cassette major part MCM; and at RI is a pawl for coupling the cassette major part MCM with the table TT (FIG. 1) on which the cassette major part MCM is to be placed. The pawl RO is provided to couple the cassette major part MCM with the cover MCC to maintain them in a sealed state, but any other means such as screws may be used. While one pawl RO and two pawls RI are shown in this Figure, actually there are provided three pawls RO and three pawls RI, disposed equidistantly. Further, although the present embodiment uses pawls RI, they may be omitted.
Denoted at RL are levers for actuating the pawls RO and RI. As the lever RL rotates, the pawls RO and RI are caused to be moved, in an inverse positional relationship, so that they go out and come back into the cassette major part MCM. When the pawl RI is accommodated in the cassette major part MCM, the pawl RO goes into a groove CL below the cover MCC, shown in FIG. 4, such that the cassette major part MCM and the cover MCC are coupled to each other and the sealed state is retained.
While in this embodiment the pawls RI and RO are actuated simultaneously by the rotation of the levers RL, any other means may be used as such an associating mechanism. Further, these levers RL or any other means to be used in place of the levers RL, may be actuated manually or by using an actuator. Further, when the actuator drive is used, the actuator may be disposed in the cassette major part MCM or outside thereof. In the present embodiment, an actuator is provided outside the cassette, and the levers RL are actuated through a transmission pin (not shown).
The cassette locking mechanism CR is provided at a position, distinguished from the closed part of the cassette. Since the cassette locking mechanism CR includes a portion having a possibility of dust production, desirably it is disposed below the cassette major part MCM, as in the present embodiment.
The sequence of the loading operation for the mask cassette of the present embodiment, will now be explained. The cassette is filled in advance with an N 2 gas or otherwise and is hermetically sealed, and masks MF of a required number are prepared inside the cassette.
First, the cassette is separated in the chamber MCH shown in FIG. 1 into the cassette major part MCM and the cover MCC. Then, only the cassette major part MCM is moved to a site to which the mask hand MH shown in FIG. 1 is accessible. Here, the actuator (not shown) provided in the chamber MCH and for driving the lever RL, serves to assist the separation of the cassette major part MCM and the cover MCC. After the exposure is completed, once the chamber MCH is filled with N 2 (to a pressure 760 Torr equal to the atmospheric pressure). After this, the cassette major part MCM and the cover MCC are coupled to each other. Accordingly, at this moment, the inside of the cassette can be filled with a desired gas and pressure, and is sealed. The coupling is assisted by the actuator (not shown) in the chamber MCH. Subsequently, the door MCHD of the chamber MCH is opened and the cassette is taken out for storage.
The present embodiment provides the following advantageous effects:
(1) Use of the sealing members S1 and S2 can substantially isolate the inside of the mask cassette from the atmosphere. Therefore, by filling the cassette with a non-reactive or non-harmful gas such as N 2 , deterioration of an X-ray mask MF such as oxidization or otherwise does not occur even if it is kept in the cassette for a long period.
(2) A plurality of masks MF can be accommodated, as a group, in the cassette. Thus, the separation or coupling of the cassette major part MCM and the cover MCC has to be done only once within the chamber. This reduces the possibility of dust production and maintains cleanness in the chamber and in the cassette.
(3) The cassette has a external pressure resisting design and has a high reliability with regard to the degree of hermetic sealing. Therefore, any external dust or foreign particles do not enter the cassette.
(4) In the present embodiment, the masks MF are held upstanding by using a magnetic attraction method. This is particularly advantageous, because any dust or foreign particles are difficult to be deposited on the mask MF.
FIG. 6 is a partially broken perspective view, showing the appearance of a mask cassette according to a further embodiment of the present invention. This embodiment differs from the foregoing embodiment with respect to the manner of holding the X-ray masks. The mask cassette of the present embodiment can be incorporated into the device shown in FIG. 3.
In FIG. 6, character MCM denotes a mask cassette major part and character MS denotes mask stages. Character MF denotes X-ray masks used in this embodiment, and character MCC denotes a cover. Character S1 denotes a sealing member which is provided at the top of the cover MCC, and character S2 denotes a sealing member provided at the bottom of the cover MCC. These sealing members serve to hermetically seal the cassette major part MCM.
Denoted at SV is a purge valve, and at CR is a cassette locking mechanism accommodating portion for coupling the cassette major part MCM and the cover MCC after the closure.
The sequence of operation of the present embodiment is substantially the same as that of the foregoing embodiment.
In the present embodiment, the masks MF are laid down and are simply placed on respective mask stages MS. A mask hand MH (see FIG. 3) is inserted into a groove formed in a corresponding mask stage MS, to lift a corresponding mask MF upwardly and convey the same.
As compared with the foregoing embodiment, the present embodiment is advantageous in the point that: As described, each mask MF is laid down and, therefore, in contrast to the magnetic attraction method, there is no necessity of providing a magnetic unit in the mask stage MS.
As described in the foregoing, a mask cassette according to the present invention provides the following advantages:
(1) Since the cassette can be hermetically sealed against the atmosphere, deterioration of a mask due to the atmosphere or contamination of the mask by dust or otherwise can be reduced, with an advantage of prolongation of the lifetime thereof.
(2) Accommodating masks as a group is effective to reduce the cassette loading operations in the chamber and, therefore, the cleanness in the chamber can be maintained.
While the invention has been described with reference to the structures disclosed herein, it is not confined to the details set forth and this application is intended to cover such modifications or changes as may come within the purposes of the improvements or the scope of the following claims. | A mask cassette and mask cassette loading device, suitably usable in an X-ray exposure apparatus for exposing a wafer to a mask with X-rays contained in synchrotron radiation, to print a pattern of the mask on the wafer, are disclosed. The mask cassette includes a base for accommodating a plurality masks and a cover which can be separated from and coupled to the base only in one direction. When the two are coupled by a locking mechanism, the cassette can be completely closed against atmospheric pressure. The mask cassette loading device includes a common mechanism which serves to release the locking mechanism of the cassette and also, to move the cassette base relative to the cover. Thus, with a simple and compact structure, the protection and replacement of X-ray masks are ensured with certainty. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This device is intended for, though not limited to, the collection and subsequent disposal of small domestic animal solid refuse, and is related to those devices employing a long handled scoop or shovel, with or without a fixed or removable receptacle.
2. Description of the Related Art
A wide variety of methods and devices have long been employed for the unpleasant task of collecting and disposing of domestic animal solid wastes. With more and more communities passing ordinances and levying fines for failure of pet owners to adequately collect and dispose of their pet's excrement, the need for a simple, clean, and efficient method of compliance is clearly demonstrated.
Current methods in general use involve collection with paper towels, plastic bags, rubber gloves, trowels, long handled scoops, shovels, or almost any combination of the above. Disadvantages are present with all of the aforementioned. The direct (or hands-on) approach brings the pet owner into tactile and olfactory contact with the offending matter, a prospect deemed unpleasant by many as evidenced by the vast number of scoop-type devices sold in pet stores. These scoops only postpone the unpleasantness, for the scoop itself comes in contact with the waste and then requires careful handling and subsequent cleaning.
An example of a typical prior art solution to the problem may be found in the refuse retrieval device of the Hastings U.S. Pat. No. 4,248,468. While this device makes the pet waste pick-up task more convenient by enabling it to be performed remotely, without stooping, it is still subject to the disadvantage of the scoops described above, in that it must be carefully cleaned of the residue of collected waste before it is stored until further use, or it will result in the offensive odors and dirt being brought inside from outdoors. Like all of the other known prior arrangements, this device does not provide for collection in a disposable container, which is really the only completely satisfactory solution to the problem.
None of the currently available devices or methods which are known is as satisfactory in use as the invention disclosed herein. This device fills a long-felt need, for it eliminates contact with the waste on the part of both the operator pet owner and the reusable portion of the collection device, all the while collecting and packaging the waste in a sealable container for convenient disposal.
SUMMARY OF THE INVENTION
In brief, arrangements in accordance with the present invention provide for the collection and packaging for subsequent disposal of solid pet wastes by way of a remotely and manually operated, reusable pair of jaws mounted at the end of a shaft. At the end opposite the jaws are a pair of handles, providing the means of carrying the device and of operating the jaws. The jaws are specially shaped to hold and manipulate a sealable, disposable container formed of styrofoam or some similar material. The jaws manipulate the container by means of a protrusion in the form of a ridge, running along the outer surface of the inside of each jaw and angled slightly inward (much like a row of teeth), which fits into a corresponding recessed groove along the top and bottom of the container.
The container is similar in construction to those widely used in the fast-food hamburger industry. It can be sealed by employing two "tab into slot" locking assemblies molded into its sides. Once sealed as such, the container can be easily removed from the rest of the device by squeezing the handles together to open the jaws. With the locking assemblies now holding the container closed, the motion of opening the jaws serves to disengage the jaws' "teeth" from the grooves on the container, allowing the container to be simply dropped into a proper waste receptacle. Latching the used container and positioning a new container in the jaws is the closest the user need come to the waste materials.
Embodiments of the invention permit the user to open the waste container, thus readying it for collection, by squeezing the two handles together. This action depresses a rod located inside the length of the shaft and connected at the other end to the hinge mechanism of the jaws. Each jaw is held in place by one side of a surrounding, fixed, Y-shaped armature, mounted orthogonally to the jaws' hinge, and a rigid link member pivotably connected between the end of the armature and the outer side of the jaw. Pressure on the hinge forces the jaws forward, while the armature and its attached members combine to translate the motion to open the jaws. The container held by the jaws also opens. The operator is now able to use the open container to collect pet waste.
When pressure on the handle grips is released, a spring inside the shaft withdraws the rod and closes the jaws and the container until needed again. The collected waste is held securely and safely inside the container. The pet owner has to only secure the locking assemblies on either side of the container, open the jaws, and drop it in a convenient waste receptacle.
Ease of installation and ejection of the disposable container in the implement of the present invention is facilitated by a particular structural configuration of the preferred embodiment of the container disclosed herein. The rearward face of the recess or pocket of the container which is formed to receive the protrusion extending from each jaw of the implement is relieved slightly at points cross the surface, leaving a thin, irregular zig-zag or "washboard" appearance. Since the container is fabricated of foamed polyurethane or similar crushable material, installing a fresh container in the jaws of the collection implement results in a slight crushing of the outer portions of the relieved surface of the pockets. Very little force is required to produce this deformation, which advantageously compensates for manufacturing tolerances of the dimensions of the mating portions of the container and the jaws of the implement. The result is a snug fit of the container into the jaws with very easy release thereof when the container is closed for ejection from the implement.
BRIEF DESCRIPTION OF THE DRAWING
A better understanding of the present invention may be realized from a consideration of the following detailed description, taken in conjunction with the accompanying drawing in which:
FIG. 1 is a schematic side view, partially broken away, of one particular arrangement in accordance with the invention;
FIG. 2 is a schematic side view, partially broken away, of the apparatus of FIG. 1 showing the collector portion in the closed and, in phantom, the open positions;
FIG. 3 is a top view, partially broken away, of the jaw assembly of the apparatus of FIG. 1;
FIG. 4 is a view depicting disposition of a filled container by ejection from the apparatus of FIG. 1;
FIG. 5 is a plan view of one particular arrangement of a disposable container for use with the arrangement of FIG. 1;
FIG. 6 is a side view, seen in cross-section, of the container of FIG. 5;
FIG. 7 is a partial view showing one closure of the container of FIGS. 5 and 6;
FIG. 8 is a partial view showing an alternative closure for the container of FIGS. 7 and 8;
FIG. 9 is a perspective view of an alternative arrangement of the disposable container for use with the implement of FIG. 1;
FIG. 10 is a view of a portion of the container of FIG. 9, showing the arrangement prior to installation in the implement of FIG. 1; and
FIG. 11 is a view similar to that of FIG. 10 showing the same portion of the container after it has once been installed in the implement of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIGS. 1 and 2, an implement 10 embodying the present invention is shown, comprising a pair of handles 12, one of which is attached to a plunger rod 14 running down the center of the main shaft 16. Contained inside the shaft 16 is a spring assembly 17 comprised of a spring 18 and a pair of spring stops 20 and 21, designed to return the handles 12 to the position shown in FIG. 1. The spring stop 20 is attached to the main shaft 16, while spring stop 21 is affixed to the plunger rod 14. An end cap 22 limits the return travel of the plunger rod.
At the opposite end of the rod 14 is attached a hinge 23 for a pair of jaws 24. A rigid, Y-shaped armature 26 and rigid bifurcated link members 28 support and align the jaws. The link members 28 are pivotably mounted at both ends, where attached to the end of the fixed armature 26 and where attached to the outside of the jaws 24. Each jaw 24 has an outwardly protruding element for connecting to an associated link member 28. Each jaw 24 has along its outer edge a ridge 32 angled inward to hold a disposable container 40 in place for manipulation. The size and angle of the ridges 32 have been exaggerated for detail.
FIG. 2 shows the operative elements of the implement 10 with the disposable container 40 in place in both the closed position (solid outline) and open position (broken line outline). The armature 26 and link members 28 have been omitted for clarity. The container 40 has, molded into its top and bottom surfaces, grooves 42 corresponding in shape to the angled ridges 32 on the inner faces of the jaws 24. These ridges 32 and grooves 42 interlock to allow the jaws 24 a grip sufficiently tenacious to open and close the container 40 easily while still permitting the release of the container from the jaws under appropriate circumstances.
FIG. 3 shows one possible configuration of the implement 10 for the attachment of the armature 26, link member 28, and jaw 24. It also shows, in breakaway, a possible positioning of the location of the angled ridge 32 inside the jaws 24. Ridges 25 are molded along the outer surface of the jaws 24 for reinforcement.
FIG. 4 is a schematic view illustrating the disposition of a container after it has been used in the implement 10 for picking up various residues. Following the collection mode, the edges of the container 40 are secured together in a manner which will be described hereinafter. The combination of implement 10 and container 40 is then strategically positioned over a garbage can and/or some other waste receptacle, here designated by the reference numeral 60 with the lid 62 open, and the handles 12 are squeezed together. This extends the internal shaft 14 and attached hinge member 23. The interconnection of the fixed armature 26, link members 28 and jaws 24 forces the jaws to their open position. Since the container 40 is sealed closed, the ridges 32 withdraw from the grooves in the container 40, and the container is released to drop in the trash container 60. Thus, the generally disagreeable task of collecting animal residues and disposing of them properly is rendered less unpleasant by the use of arrangements in accordance with the use of the present invention. There is now no need to touch any residue being collected, and the collection container can also be disposed of in a neat and sanitary manner without any handling of the collected residues. The entire process from pick -up to disposal is conducted at arms' length distance.
FIG. 5 shows a possible configuration for the construction of the disposable container 40. Tabs 44 and corresponding slots 46 have been designed into the molded lips 48 constituting the boundary of the container halves, permitting the container 40 to be latched closed after use. In a preferred embodiment, the container 40 is molded of a foamed polyurethane which renders the container cheap to manufacture, lightweight, and stackable to facilitate shipping and storage in bulk, and sufficiently rigid for the purpose here intended. Such a container very closely resembles the containers used for packaging hamburgers and other sandwiches in the fast food industry. Also shown is a possible location of the grooves 42 in the surfaces of the container 40.
FIG. 6 shows, in cross section, one possible configuration of the grooves 42 in the surfaces of the container 40. The shape of these grooves 42 is designed to correspond in mating relationship with the shape of the ridges 32 on the inside of the jaws 24 (FIGS. 1 and 2). The size and angle of these grooves 42 have been exaggerated for detail.
FIGS. 7 and 8 illustrate particular details of two alternative arrangements for sealing the container 40 when it is ready for disposal. The arrangement depicted in FIG. 7 corresponds to the container shown in FIG. 5, wherein the two halves of the container 40 are latched together by inserting the tongue 44 through the slit 46 in the edge 48. FIG. 5 shows a pair of these latching arrangements on opposite sides of the container 40; if need be for added security, additional pairs of interlocking members may be provided about the periphery of the two halves of the container 40.
FIG. 8 shows a container 40A having boundary edges 48A arranged to be sealed together by adhesive. An adhesive layer 50 is affixed along the lower boundary edge 48A covered with a release liner in the form of a protective strip or tape 52. This release tape 52 is removed by peeling away from the adhesive layer 50 when the container is ready to be sealed closed in preparation for disposal. The adhesive layer 50 then adheres to both the edges 48A and secures them together. The adhesive layer 50 and release liner 52 may be positioned substantially about the periphery of the container 40 or, if desired, it may be positioned as a series of individual strips, approximately one to two inches in length, spaced about the periphery of the container.
The alternative embodiment of a container 60 which is depicted in FIGS. 9-11 presents particular structural feature which improves the operation of the device and the facility with which the disposable container may be installed and ejected. Like the container depicted in FIGS. 5 and 6, container 60 is formed with pockets 62 for receiving the projecting ridges 32 on the inner sides of the jaws 24 (FIGS. 1 and 2). Each pocket 62 has a region 64 (best seen in FIG. 10) along its rearward face 66 which is relieved at intervals 67 to form a series of corrugations 70 (the rearward face of the pocket 62 is that which is nearest the hinge 23 of the jaws 24).
For the combination of the present invention to perform effectively, a close fit is required between that portion of each half of the container extending between a pocket 42 or 62 and the container hinge and the mating portion of the jaws 24 extending between a ridge 32 and the jaw hinge 23. The fit must be tight enough that the container halves are held by the jaws to open and close therewith but not so tight that the container does not release readily when its edges have been latched together in preparation for ejection and disposal. It has been found that the necessary tolerance limits required for the variations in dimensions of the implement jaws and the container, both of which are manufactured in different factories by different vendors, are rather extreme and sometimes result in an interference fit between the mounting ridges of the jaws and the pockets of the disposable containers. This makes it difficult both to install the container in the implement and to eject the container from the implement after it has been filled with picked-up wastes.
The container 60 of FIGS. 9-11 alleviates these problems by the inclusion of the corrugations 70 along the rearward face of the pockets 62. FIG. 11 shows how the corrugations 70 between the relieved sections 67 deformed from the container 60 having been installed in an implement in which the dimension between the mounting ridge and the jaw hinge is slightly less than the corresponding dimension of the container 60 as fabricated. The corrugations of the foamed plastic material are crushed and deformed to the extent necessary to permit the container 60 to be installed. The result is a sufficiently tight fit to maintain the container operable between opened and closed positions as the jaws are opened and closed, while still enabling the container when latched closed to be ejected readily from the implement.
The container 60 is provided with opposed latching tongues 76 and ears 80 with slits 82. When ready for disposal, the closed container is merely squeezed inwardly on the sides bearing the tongues 76 until they clear the ears 80 so that upon release they enter the slits 82, thus latching the container closed. Actuating the implement 10 to open the jaws 24 then releases the latched container in the manner illustrated in FIG. 4.
Although there have been described hereinabove specific arrangements of a manual collection apparatus in accordance with the invention for the purpose of illustrating the manner in which the invention may be used, it will be appreciated that the invention is not limited thereto. Accordingly, any and all modifications, variations or equivalent arrangements which may occur to those skilled in the art should be considered within the scope of the invention as defined in the appended claims. | Apparatus for facilitating the collection and disposal of solid pet wastes. It includes a long-handled reciprocable implement having a pair of jaws at the distal end and a pair of handles at the proximal end connected to open and close the jaws. A disposable container having a pair of clamshell-shaped halves adapted to releasably receive mating retaining portions of the jaws is adapted to be manipulated by the jaws so as to open and close while picking up pet waste deposits. When it is ready for disposal, the edges of the container are secured together and manipulation of the jaws releases the container for dropping into a waste repository. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. patent application Ser. No. 09/336,713, filed on Jun. 21, 1999, now abandoned.
FIELD OF THE INVENTION
The present invention is directed to a novel organometallic luminescent material, and more particularly, to a novel organometallic luminescent material having the capability of emitting pure blue light and high thermal stability, and an organic electroluminescent device (OELD) containing same.
BACKGROUND OF THE INVENTION
Conventional organometallic luminescent compounds used in organic electroluminescent devices are mostly complexes of divalent or trivalent metals such as zinc and aluminum.
For example, U.S. Pat. No. 5,456,988 describes 8-hydroxyquinoline complexes of zinc, aluminum and magnesium as organic luminescent materials; U.S. Pat. No. 5,837,390 discloses magnesium, zinc and cadmium complexes of 2-(o-hydroxyphenylbenzoxazole); Japanese Patent Laid-Open Publication No. 07-133483 reports luminescent complexes of 2-(o-hydroxyphenylbenzoxazole) with divalent metals such as magnesium and copper; and U.S. Pat. No. 5,529,853, and Japanese Patent Laid-Open Publication Nos. 06-322362, 08-143548 and 10-072580 disclose divalent or trivalent metal complexes of 10-hydroxybenzo[10]quinoline.
The above organometallic luminescent compounds containing a divalent or trivalent metal have relatively loosely-bound ligands and an extended system of conjugation. As a result, they are relatively unstable and emit green or red light but not blue light.
Therefore, there has existed a need to develop an organometallic luminescent material having an improved stability and light emission characteristics such as the capability of emitting pure blue light.
SUMMARY OF THE INVENTION
Accordingly, it is a primary object of the present invention to provide a novel organometallic luminescent material having good stability and desired emission characteristics, and an organic luminescent device containing same.
In accordance with the present invention, there is provided an organometallic luminescent complex of formula (I).
wherein,
M 1 is a monovalent or tetravalent metal selected from the group consisting of Li, Na, K, Zr, Si, Ti, Sn, Cs, Fr, Rb, Hf, Pr, Pa, Ge, Pb, Tm and Md;
R is hydrogen or C 1-10 alkyl;
B is O, S, Se or Te;
D is O or S; and
n is an integer ranging from 1 to 4.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and features of the present invention will become apparent from the following description thereof, when taken in conjunction with the accompanying drawings wherein:
FIGS. 1 a , 1 b and 1 c illustrate schematic diagrams of organic electroluminescent devices having single-layered, double-layered and multi-layered organic interlayers, respectively, FIG. 1 d , energy band diagrams of OELDs, and FIG. 1 e , chemical structures of (a) m-MTDATA, (b) NPB, (c) LiPBO, (d) BCP and (e) Alq3;
FIG. 2 shows the light emission spectrum of the organometallic luminescent material obtained in Preparation 1 of the present invention;
FIG. 3 represents thermal stabilities of the LiPBO obtained in Preparation 1 and a DPVBi powder;
FIG. 4 exhibits the electroluminous spectra of the electroluminescent device obtained in Preparation 4 of the present invention;
FIG. 5 shows CIE color coordinate of the blue OELD-B1 in a multi-layered structure;
FIG. 6 demonstrates variations of the current density (A/m 2 ) and luminance (cd/m 2 ) of the electroluminescent devices obtained in Preparation 6 of the present invention as function of applied voltage(V); and
FIG. 7 depicts changes in the luminous efficiencies (cd/A) with luminance (cd/A) of the OELD-B1 (filled circle), OELD-B2 (open rectangle) and OELD-B3 (open triangle) obtained in Preparation 6.
DETAILED DESCRIPTION OF THE INVENTION
The organometallic luminescent materials of the present invention include benzoxazole- or benzthiazole-metal complexes of formula (I).
Among the organometallic luminescent materials of the present invention, preferred are those listed in Table I.
TABLE I
Compound No.
M 1
B
D
N
R
γ max (nm)
color
1
Li
O
O
1
H
450
blue
2
Na
—
O
1
H
455
blue
Compound 1,2-(2-hydroxyphenyl)benzoxazol-lithium (LiPBO) can be applied as a stable blue emission layer in an organic electroluminescent device (OELD) because it has a high glass transition temperature of more than 200° C.
The organometallic luminescent compound of the present invention may be prepared by reacting an organic compound that can serve as a ligand with an appropriate metal compound in a suitable solvent.
Exemplary solvents which can be used in the present invention include water, ethanol, methanol and propanol.
Representative metal compounds that can be used to prepare the organometallic luminescent compounds of the present invention are LiOH, NaOH, KOH, NaCl, KCl, LiCl, ZrCl 4 , SnCl 4 , TiCl 4 , SiCl 4 , BeCl 2 , MgCl 2 , AlCl 3 , CaCl 2 and ZnCl 2 .
Representative organic compounds which can be used as ligands in the present invention include 2-(2-hydroxy-phenyl) benzoxazole and 2-(2-hydroxy-phenyl)benzthiazole.
The reaction of the organic and metal compounds to prepare the organometallic luminescent compound of the present invention may be carried out in stoichiometric amounts, which depend on n, at a temperature ranging from 25 to 100° C. for 1 to 24 hours.
The organometallic complex of the present invention can be used as a luminescent doping material as well. For example, when it is doped in an amount of about 2% in a blue light emitting luminescent layer, the emitting light changes from blue to light blue or green. Accordingly, an efficient electroluminescent device capable of emitting a tuned color can be prepared.
The organic luminescent device of the present invention comprises an organic interlayer which may be in the form of a single layer, in the form of a double layer containing a hole transporting layer (HTL) or an electron transporting layer (ETL) in addition to the light emitting luminescent layer, or in the form of a multi layer containing still additionally a hole injecting layer (HIL) or a hole blocking layer (HBL). The organometallic luminescent material of the present invention can be used alone, or in combination with a polymer or an inorganic material. Further, it may be doped in a polymer to give a fluorescent thin layer.
An example of the electroluminescent device of the present invention contains a single organic layer as shown in FIG. 1 a . The device consists of (i) a glass substrate, (ii) a transparent ITO (indium tin oxides) anode electrode layer, (iii) an organic luminescent layer containing the organometallic luminescent material of the present invention, and (iv) a metal cathode electrode layer. Another example of the inventive device has an additional hole transporting layer (iii-1) as shown in FIG. 1 b , or a multi-layered structure shown in FIG. 1C, wherein (iii-2) denotes an additional electron transporting layer. The electroluminescent device of the present invention may be operated with either direct or alternative current, while the direct current is preferred.
The organic luminescent layer of the present invention may be formed by a conventional method including a wet process such as spin coating, and a dry process such as a vapor deposition, vacuum thermal deposition, sputtering and electron beam deposition method.
The novel organometallic luminescent compound of the present invention is capable of emitting blue light, and in particular, the inventive complexes containing monovalent metals are stable even at a high temperature and emit bright blue light.
The present invention is further described and illustrated in Examples, which are however, not intended to limit the scope of the present invention.
Preparation 1: 2-(2-Hydroxyphenyl)benzoxazole-lithium (LiPBO)
2-(2-hydroxyphenyl) benzoxazole and lithium oxide were added to 250 ml of ethanol in a molar ratio of 1:1 and the mixture was refluxed at 78° C. for 4 hours. The reaction mixture was filtered and the solvent and moisture were removed under a reduced pressure to give the titled compound of formula (I-1) (compound 1).
The compound thus obtained was analyzed by ICP-AES and EA, and the results are as follows:
Calculated=>C: 71.95, H: 3.68, N: 6.44, O: 14.73, Li: 3.20
Found=>C: 71.82, H: 3.95, N: 6.34, O: 13.94, Li: 3.95
EXAMPLE 1
Photoluminescence Spectrum and Thermal Stability of LiPBO
The light emission spectrum of the LiPBO complex thus obtained was measured and shown in FIG. 2 . The photoluminescence spectrum of the purified LiPBO film shows a maximum peak at 450 nm.
Also, the thermal stability of the purified LiPBO was examined by using differential scanning calorimeter (DSC). A second DSC run was performed to verify the scan is reproducible after heating and cooling. For comparison, 4,4-bis(2,2-diphenylvinyl)biphenyl (DPVBi), which is known to be one of the best organic blue emitters, was also examined by DSC. The thermal relaxation behaviors of the LiPBO and a DPVBi powder are shown in FIG. 3 . The glass transition temperature of the LiPBO and DPVBi were ca. 205° C. and 385° C., respectively.
Preparation 2: 2-(2-Hydroxyphenyl)-benzoxazole-sodium (NaPBO)
2-(2-hydroxyphenyl)benzoxazole and NaOH were added to 250 ml of ethanol in a molar ratio of 1:1 and the mixture was refluxed at 78° C. for 4 hours. The reaction mixture was filtered and the solvent and moisture were removed under a reduced pressure to obtain the titled compound of formula (I-2) (compound 2).
The maximum wavelength and emitted color of the complex thus obtained were 455 nm and blue, respectively (Table I).
The compound thus obtained was analyzed by ICP-AES and EA, and the results are as follows:
Calculated=>C: 66.96, H: 3.43, N: 6.00, O: 13.73, Na: 9.88
Found=>C: 66.41, H: 3.20, N: 6.24, O: 14.04, Na: 10.11
Preparation 3: Tetra[2-(2-hydroxyphenyl)benzoxazolato]zirconium (ZrPBO)
Preparation 1 was repeated except that zirconium chloride (ZrCl4) was used instead of lithium to give the titled compound. The compound thus obtained was analyzed by ICP-AES and EA, and the results are as follows:
Calculated=>C: 67.01, H: 3.44, N: 6.00, O: 13.75, Zr: 9.80
Found=>C: 66.79, H: 3.63, N: 5.97, O: 13.69, Zr: 9.92
Preparation 4: Double-Layered OELD
Indium-tin-oxide (ITO) was coated on a glass substrate to form a transparent anode layer. The coated substrate was subjected to photolithography and the patterned ITO glass was cleaned with a solution containing a non-phosphorous detergent, acetone and ethanol.
An equal weight mixture of polyetherimide of formula (II) and triphenyldiamine of formula (III) was dissolved in chloroform to a concentration of 0.5 wt. %, and the resulting mixture was spin-coated on the ITO glass to form a hole transporting layer;
wherein m is an integer of two or higher.
On the hole transporting layer, 2-(2-hydroxyphenyl) benzoxazole-lithium (LiPBO) complex obtained in Preparation 1 was vapor deposited to a thickness of 20 nm to form an organic luminescent layer, and then, aluminum was vapor deposited to a thickness of 500 nm to form a cathode layer on the organic luminescent layer. Subsequently, the device was packaged to obtain an organic electroluminescent device (OELD) having a double-layered structure as shown in FIG. 1 b.
EXAMPLE 2
EL Spectrum of OELD
FIG. 4 exhibits electroluminous spectra of the OELD obtained in Preparation 4 observed at various applied voltages of 8, 9, 10, 11, 12 and 13V. The main peak appears at 456 nm and shoulder peaks are observed at 430 and 487 nm. The emitted light was blue.
Preparation 5: Double-Layered OELD
Preparation 4 was repeated except that ZrPBO with a thickness of 50 nm was used as a luminescent material and Li:Al (Li content 0.15%) was used as a cathode layer to obtain an OELD having a double layer structure. The current injection started at ca. 3.5V. 24,300 cd/m 2 was achieved at 11V and the current density was 4,831 A/m 2 . The luminous efficiency was 5.03 cd/A.
Preparation 6: Multi-Layered OELD
Preparation 3 was repeated except that 4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB) and bathocuproine (BCP) were used in forming hole injecting layer (HIL), hole transporting layer (HTL) and hole blocking layer (HBL), respectively, to prepare three types (OELD-B1, OELD-B2 and OELD-B3) each having a multi-layered structure.
OELD-B1 comprises a glass plate and layers of indium-tin oxide (ITO), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (m-MTDATA) (200 Å), N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1-biphenyl)-4,4′-diamine (NPB or α-NPD) (75 Å), LiPBO (200 Å), bathocuproine (BCP) (100 Å), and Li:Al (1500 Å). OELD-B2 is composed of a glass plate and layers of ITO, m-MTDATA (200 Å), NPB (100 Å), LiPBO (200 Å), tris(8-quinolinolato)aluminum (Alq3) (75 Å), and Li:Al (1500 Å). Further, OELD-B3 had the layer structure of glass/ITO/m-MTDATA (200 Å)/NPB (100Å)/LiPBO (200 Å)/BCP (50 Å)/Alq3 (50 Å)/Li:Al (1500 Å).
Energy band diagrams of the OELDs and chemical structures of the organic materials: (a) m-MTDATA, (b) NPB, (c) LiPBO, (d) BCP, and (e) Alq3 are shown in FIGS. 1 d and 1 e , respectively.
The luminescence characteristics of the OELD-B1, OELD-B2 and OELD-B3 are shown in FIGS. 6 and 7.
EXAMPLE 3
CIE Color Coordinate of the OELD
The color purity of OELD-B1 was measured with the calibrated candela meter (Minolta CS1000) and shown in FIG. 5 . As shown in FIG. 5, the CIE color coordinate of the blue OELD is x=0.15 and y=0.08 at above 10,000 cd/m 2 , which is the nearest value to the NTSC standard value of X=0.14 and y=0.08. In FIG. 5, open circles denote the NTSC standard blue, green and red values.
EXAMPLE 4
Luminescence of OELD
FIG. 6 illustrates variations of the current density (A/m 2 ) and luminance (cd/m 2 ) of OELD-B1, OELD-B2 and OELD-B3 obtained in Preparation 6 as function of the applied voltage (V). For both OELD-B1 and OELD-B3, the current injection starts at ca. 3.5V. The maximum luminances of three OELDs are ca. 10,000 cd/m 2 or over, and in particular, ca. 14,600 cd/m 2 , and 500 cd/m 2 can be achieved with OELD-B3 at 11V.
EXAMPLE 5
Efficiency of OELD
FIG. 7 depicts changes in the luminous efficiencies (cd/A) with luminance (cd/m 2 ) of OELD-B1, OELD-B2 and OELD-B3, respectively. The luminous efficiency is steady at 1.2 lm/W at a current density of 200 A/m 2 and beyond.
As can be seen from the above results, the organometallic luminescent material of the present invention exhibits blue, green or red light emission. Therefore, an electroluminescent device containing the same is capable of exhibiting a full range of colors in the visible region with a high efficiency.
While the embodiments of the subject invention have been described and illustrated, it is obvious that various changes and modifications can be made therein without departing from the spirit of the present invention which should be limited only by the scope of the appended claims. | An organometallic luminescent material comprising the compound of formula (I) of the present invention can emit pure blue light and have high thermal stability:
wherein,
M 1 is a monovalent or tetravalent metal selected from the group consisting of Li, Na, K, Zr, Si, Ti, Sn, Cs, Fr, Rb, Hf, Pr, Pa, Ge, Pb, Tm and Md;
R is hydrogen or C 1-10 alkyl;
B is O, S, Se or Te;
D is O or S; and
n is an integer ranging from 1 to 4. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 12/926,302, filed Nov. 9, 2010, which claims benefit to Taiwanese Application No. 99101774, filed Jan. 20, 2010, the entire contents which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a medical composition for inhibiting the growth of cancer stem cells, which is capable of inhibiting the growth of cancer stem cells in addition to common cancer cells.
2. Description of Related Art
Cancer has always been one of ten leading causes of death but has increased in its perniciousness to become the first cause of death for 27 years. The main factor causing cancer is that cells become abnormal and keep dividing to form more cells, resulting in cancer.
Western medicine therapy for treatment of cancer, such as surgery, radiation therapy, chemotherapy, hormone therapy and biopharmaceutical therapy, is notorious for the distressing side-effects on patients. In view of those difficulties, more and more people opt for the less-radical Chinese medicine therapy. However, for both Chinese and Western medicine therapy, the commercial anticancer drugs can inhibit only growth of cancer cells, i.e., not cancer stem cells.
Cancer stem cells present in tumors are not large in amount, but they are highly resistant to drugs and can generate more cancer cells through cell division resulting in tumors. The aforementioned fact is a thorny problem in treating cancer. The Western chemotherapeutic drugs nowadays can kill only common cancer cells, and cannot efficiently inhibit growth of cancer stem cells. That is, a great amount of standard cancer treatment known in biomedicine has no influence on cancer stem cells. Thereby, to efficiently inhibit growth of cancer stem cells is inevitably advantageous to cancer treatment.
In general, Chinese herbal medicine is considered more moderate and more acceptable than Western chemical forms on the market. Although some clinical treatment results suggest that parts of medical compositions for treating cancer cells are indeed capable of controlling cancer, the efficiency of these medical compositions in inhibiting cancer cells as well as cancer stem cells has not been confirmed.
Accordingly, to develop a medical composition that has the confirmed efficiency in inhibiting cancer cells, particularly the growth of precursor cells (i.e. cancer stem cells), is helpful to cancer treatment.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a medical composition capable of inhibiting growth of cancer stem cells. Also, the medical composition according to the present invention can inhibit growth of common cancer cells.
To achieve the object, the present invention provides a medical composition for inhibiting the growth of cancer stem cells including: an extract provided by mixing Coptis chinensis, Scutellaria baicalensis, Phellodendron amourense, Gardenia jasminoides, Radix Glycyrrhizae , and Atractylodes japonica with a water-containing solution or an alcohol-containing solution, followed by heating and extraction.
In the medical composition, Coptis chinensis ranges from 3 to 5 weight parts, Scutellaria baicalensis ranges from 3 to 5 weight parts, Phellodendron amourense ranges from 3 to 5 weight parts, Gardenia jasminoides ranges from 3 to 5 weight parts, Radix Glycyrrhizae ranges from 3 to 5 weight parts, and Atractylodes japonica ranges from 3 to 5 weight parts.
In addition, the present invention further provides a medical composition for inhibiting the growth of cancer stem cells including: an extract provided by mixing Coptis chinensis, Rhizoma cimicifugae, Angelica sinensis , Rhizome of rehmannia , and Cortex Moutan Radicis with a water-containing solution or an alcohol-containing solution, followed by heating and extraction.
In the medical composition, Coptis chinensis ranges from 3 to 5 weight parts, Rhizoma cimicifugae ranges from 3 to 5 weight parts, Angelica sinensis ranges from 3 to 5 weight parts, Rhizome of rehamnnia ranges from 3 to 5 weight parts, and Cortex Moutan Radicis ranges from 3 to 5 weight parts.
The above-mentioned medical compositions are prepared by heating and extraction with a water-containing or alcohol-containing solution. In the case of using an alcohol-containing solution, preferably, the alcohol-containing solution contains alcohol in 20-40%. In addition, during extraction, the solution containing the Chinese herb materials may be heated up to 70° C. or more. Preferably, the solution containing the Chinese herb materials is heated up to 70° C. or more and subjected to extraction for at least 60 minutes. Accordingly, the medical composition according to the present invention can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a statistical chart for showing the cell survival rates of lung cancer cells after treatment with various dosages of the medical composition according to Example 1 of the present invention;
FIG. 2 is a statistical chart for showing the cell survival rates of lung cancer cells and normal cells after treatment with the medical composition according to Example 1 of the present invention;
FIG. 3 is a chart for showing the correlation between treatment time and the lung cancer cell survival rate after treatment with the dose for 50% inhibition (ID50) of the medical composition according to Example 1;
FIG. 4 is a statistical chart for showing the percentage of lung cancer cells in each cycle stage after treatment with the medical composition according to Example 1 of the present invention;
FIG. 5 is a statistical chart for showing the percentage of lung cancer cells in the G0 stage after treatment with the medical composition according to Example 1 of the present invention;
FIG. 6 is a statistical chart for showing the fold change of cancer stem cells after treatment with the medical composition according to Example 1 of the present invention;
FIG. 7 is a statistical chart for showing the cell survival rates of lung cancer cells after treatment with various dosages of the medical composition according to Example 2 of the present invention;
FIG. 8 is a statistical chart for showing the cell survival rates of lung cancer cells and normal cells after treatment with the medical composition according to Example 2 of the present invention;
FIG. 9 is a chart for showing the correlation between treatment time and the lung cancer cell survival rate after treatment with the dose for 50% inhibition (ID50) of the medical composition according to Example 2;
FIG. 10 is a statistical chart for showing the percentage of lung cancer cells in each cycle stage after treatment with the medical composition according to Example 2 of the present invention;
FIG. 11 is a statistical chart for showing the percentage of lung cancer cells in the G0 stage after treatment with the medical composition according to Example 2 of the present invention; and
FIG. 12 is a statistical chart for showing the fold change of cancer stem cells after treatment with the medical composition according to Example 2 of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the following examples according to the present invention, A549 cancer cell survival is characterized after treatment with the medical compositions according to the present invention. Then, the arresting stage of cell cycle by use of these medical compositions according to the present invention is identified by flow cytometric analysis. In addition, the cell apoptosis resulted from the medical compositions according to the present invention is studied through cell staining. Moreover, the efficiency of the medical compositions according to the present invention killing cancer stem cells is evaluated by double fluorescence staining and flow cyometric analyses.
Example 1
Coptis chinensis (10 g), Scutellaria baicalensis (10 g), Phellodendron amourense (10 g), Gardenia jasminoides (10 g), Radix Glycyrrhizae (10 g), and Atractylodes japonica (10 g) are cut into slices and mixed with water to perform heating and extraction to obtain an extract. Herein, the heating is performed for 90 minutes at 70° C. Accordingly, the resulting extract is the medical composition according to the present example.
Test Example 1
Cell Survival Rate Test
A549 lung cancer cell survival rate is characterized through MTT assay after treatment with 5 μl, 10 μl and 50 μl of the medical composition according to Example 1 for 72 hours, respectively. The results are shown in FIG. 1 . Herein, the horizontal axis represents a control group and various dosages of medical compositions, and the vertical axis represents the absorption of cells at 570 nm, which depends on the cell survival rate.
FIG. 1 shows that the increased dosage of the medical composition causes the reduction of A549 cancer cell survival rate after treatment for 72 hours. In addition, it can be inferred from FIG. 1 that the dose for 50% inhibition (ID50) of the medical composition according to Example 1 on A549 cells is 20 μl.
Test Example 2
Cell Survival Rate Test
After A549 lung cancer cells and MRC-5 normal cells are treated with 20 μl of the medical composition according to Example 1 for 72 hours, respectively, the cell survival rates thereof are characterized by MTT assay. The results are shown in FIGS. 2 and 3 . FIG. 2 is a statistical chart showing the survival rates of the lung cancer cells and the normal cells after treatment with the medical composition according to Example 1. FIG. 3 is a chart showing the correlation between treatment time and the lung cancer cell survival rate after treatment with the dose for 50% inhibition (ID50) of the medical composition according to Example 1.
FIG. 2 suggests that the A549 lung cancer cell survival rate is significantly reduced with no decrease of the MRC-5 cell survival rate after treatment with the dose for 50% inhibition (ID50) of the medical composition according to Example 1 for 72 hours. Thereby, the medical composition according to Example 1 can significantly inhibit the growth of cancer cells but not the growth of normal cells.
FIG. 3 shows that the survival rate of A549 lung cancer cells is significantly reduced after treatment with ID50 of the medical composition according to Example 1 for 24, 48 and 72 hours in comparison with the A549 lung cancer cells with no treatment with the medical composition according to Example 1. Meanwhile, the variation of the cell survival rate increases with the increase of time.
Test Example 3
Arresting Stage of Cell Cycle Test
A549 lung cancer cells are PI stained after treatment with 20 μl (ID50) of the medical composition according to Example 1 for 72 hours. Subsequently, the DNA content of the lung cancer cells is detected by flow cytometric analysis to determine cell cycle distribution of lung cancer cells. The quantitative statistical results are shown in FIG. 4 . Herein, the G0/G1, S and G2/M on the horizontal axis represent various cell cycle stages, respectively, and the vertical axis represents the percentage of cells in each cycle stage.
FIG. 4 suggests that the cell percentage in the G0/G1 stage significantly increases in the lung cancer cells treated with the medical composition according to Example 1 for 24, 48 and 72 hours, in comparison with the lung cancer cells without treatment with the medical composition according to Example 1. Thereby, it is confirmed that the medical composition according to Example 1 causes A549 lung cancer cells to be arrested in the G0/G1 stage.
Test Example 4
Arresting Stage of Cell Cycle Test
A549 lung cancer cells are double stained with PI and Ki67 antibody and observed by flow cytometric analysis to determine cell percentage of lung cancer cells in G0 stage after treatment with 20 μl (ID50) of the medical composition according to Example 1 for 72 hours.
FIG. 5 suggests that the cell percentage in the G0 stage significantly increased in the lung cancer cells treated with the medical composition according to Example 1, in comparison with the lung cancer cells without treatment with the medical composition according to Example 1. Thereby, it is confirmed that more A549 cells can leave the cell cycle and stay in the quiescent G0 stage after treatment with the medical composition according to Example 1.
Test Example 5
Cancer Stem Cell Ratio Test
A549 lung cancer cells are stained with Hoechst33342 in the presence or absence of reserpine after treatment with 20 μl (ID50) of the medical composition according to Example 1 for 72 hours. The ratio of side population (SP) cells (i.e. cancer stem cells) is evaluated by flow cytometric analysis. Reserpine is used to inhibit ABCG2-mediated Hoechst33342 dye efflux. Accordingly, SP cancer stem cells in which ABCG2 is highly expressed can be identified by comparing the presence/absence of reserpine.
The quantitative statistical results are shown in FIG. 6 . Herein, the horizontal axis represents a fold change, i.e. the ratio of the measured value in the presence of reserpine to that in its absence. FIG. 6 suggests that the fold change can be reduced to about 0.1 after treatment with the medical composition according to Example 1. That is, the SP cancer stem cell mass is lower and the ratio of the cancer stem cells is significantly reduced. Thereby, it is confirmed that the medical composition according to Example 1 can inhibit the growth of cancer stem cells.
EXAMPLE 2
Coptis chinensis (10 g), Rhizoma cumicifugae (10 g), Angelica sinensis (10 g), Rhizome of rehmannia (10 g) and Cortex Moutan Radicis (10 g) are cut into slices and mixed with water to perform heating and extraction to obtain an extract. Herein, the heating is performed for 90 minutes at 70° C. Accordingly, the resulting extract is the medical composition according to the present example.
Test Example 6
Cell Survival Rate Test
The test method according to the present test example is the same as that of Test Example 1, except that the medical composition according to Example 1 is replaced by that according to Example 2. The results are shown in FIG. 7 .
FIG. 7 shows that the increased dosage of the medical composition causes the reduction of A549 cancer cell survival rate after treatment for 72 hours. In addition, it can be inferred from FIG. 7 that the dose for 50% inhibition (ID50) of the medical composition according to Example 2 on A549 cells is 11 μl.
Test Example 7
Cell Survival Rate Test
The test method according to the present test example is the same as that of Test Example 2, except that 20 μl of the medical composition according to Example 1 is replaced by 11 μl of the medical composition according to Example 2. The results are shown in FIGS. 8 and 9 .
FIG. 8 suggests that the A549 lung cancer cell survival rate is significantly reduced with no decrease of the MRC-5 cell survival rate after treatment with the dose for 50% inhibition (ID50) of the medical composition according to Example 2 for 72 hours.
FIG. 9 shows that the survival rate of A549 lung cancer cells is significantly reduced after treatment with ID50 of the medical composition according to Example 2 for 24, 48 and 72 hours in comparison with the A549 lung cancer cells with no treatment with the medical composition according to Example 2. Meanwhile, the variation of the, cell survival rate increases with the increase of time.
Test Example 8
Arresting Stage of Cell Cycle Test
The test method according to the present test example is the same as that of Test Example 3, except that 20 μl of the medical composition according to Example 1 is replaced by 11 μl of the medical composition according to Example 2, The quantitative statistical results are shown in FIG. 10 .
FIG. 10 suggests that the cell percentage in the G0/G1 stage significantly increases regarding the lung cancer cells treated with the medical composition according to Example 2 far 24, 48 and 72 hours, in comparison with the lung cancer cells of the control group without treatment with the medical composition according to Example 2. Thereby, it is confirmed that the medical composition according to Example 2 causes A549 lung cancer cells to be arrested in the G0/G1 stage.
Test Example 9
Arresting Stage of Cell Cycle Test
The test method according to the present test example is the same as that of Test Example 4, except that 20 μl of the medical composition according to Example 1 is replaced by 11 μl of the medical composition according to Example 2. The quantitative statistical results are shown in FIG. 11 .
FIG. 11 suggests that the cell percentage in the G0 stage significantly increases regarding the lung cancer cells treated with the medical composition according to Example 2, in comparison with the lung cancer cells without treatment with the medical composition according to Example 2. Thereby, it is confirmed that more A549 cells can leave the cell cycle and stay in the quiescent G0 stage after treatment with the medical composition according to Example 2.
Test Example 10
Cancer Stem Cell Ratio Test
The test method according to the present test example is the same as that of Test Example 5, except that 20 μl of the medical composition according to Example 1 is replaced by 11 μl of the medical composition according to Example 2. The quantitative statistical results are shown in FIG. 12 .
FIG. 12 suggests that the fold change can be reduced to about 0.2 after treatment with the medical composition according to Example 2. That is, the SP cancer stem cell mass is lower and the ratio of the cancer stem cells is significantly reduced. Thereby, it is confirmed that the medical composition according to Example 2 can inhibit the growth of cancer stem cells.
From the results of Test Examples 1 to 10, it can be confirmed that the medical composition according to the present invention can inhibit the growth of cancer cells as well as cancer stem cells.
Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the scope of the invention as hereinafter claimed. | A medical composition for inhibiting the growth of cancer stem cells is disclosed. The medical composition is prepared by mixing herbal medicines with water or alcohol, followed by heating and extraction to obtain a filtrate. One of the medical compositions according to the present invention includes: Coptis chinensis, Scutellaria baicalensis, Phellodendron amourense, Gardenia jasminoides, Radix Glycyrrhizae, and Atractylodes japonica. | 0 |
FIELD OF THE INVENTION
The invention relates to the general field of perpendicular magnetic writers with particular emphasis on delivering more flux to the ABS (air bearing surface).
BACKGROUND OF THE INVENTION
Tapered write gaps have been previously used to enhance field and field gradient, as shown in FIG. 1 . It is based on the fundamental principle of increasing the choke area around the neck region so that the sides of ABS 11 are not quite parallel but, instead, converge at an angle θ thereby providing gradual flux concentration to bring additional field to the ABS. Because of the slope of the main pole, the area A 2 behind the ABS is larger than the area A 1 at the ABS. So a larger ratio of A 2 to A 1 corresponds to more flux concentration at the ABS. Other elements shown in FIG. 1 include trailing shield 12 , write gap 13 , and main pole 14 .
As track widths narrow, still further enhancements are needed to this flux concentration approach. While steeper tapered write gap angles can increase A 2 /A 1 , the main drawbacks are the processing difficulty and too high a sensitivity of the ABS area A 1 to the ABS lapping position ‘aa’. If the taper angle θ is too large, a small displacement of ABS line ‘aa’, caused by the ABS lapping process, will result in a large change in both the ABS area and the physical width of the main pole. Therefore, methods for flux concentration are required that are not overly sensitive to changes in the angle at which the write gap lies relative to the ABS.
A routine search of the prior art was performed with the following references of interest being found:
In U.S. Pat. No. 6,621,659, Shukh et al. say “it is common to taper the pole from the larger width in the paddle region to a narrower width in the pole tip region at the ABS.” However, the form of the taper is different from that disclosed by the present invention. U.S. Pat. No. 7,151,647 (Sasaki et al—Headway) shows a yoke portion having a wide portion, a narrow portion, and a sloping flare portion and U.S. Patent Application 2006/0044677 (Li et al—Headway) teaches a plated bevel pole design where the top is wider than the bottom.
U.S. Pat. No. 7,193,815 (Stoev et al) shows an upper section of the write shield wider than the lower section. U.S. Pat. No. 7,116,517 (He et al) teaches a T-shaped pole tip. U.S. Pat. No. 7,133,253 (Seagle et al) discloses a tapered pole tip while U.S. Pat. No. 6,680,815 (Sasaki) shows a tapered write gap as part of their FIG. 9
SUMMARY OF THE INVENTION
It has been an object of at least one embodiment of the present invention to provide a perpendicular write pole that provides increased magnetic flux at the ABS.
Another object of at least one embodiment of the present invention has been to provide a process for manufacturing said write pole.
Still another object of at least one embodiment of the present invention has been to achieve the above objects without increasing the degree of taper of the pole at the ABS.
A further object of at least one embodiment of the present invention has been to render performance of the completed device insensitive to small variations of the precise location of the ABS relative to other parts of the structure.
These objects have been achieved by increasing the amount of write flux that originates above the write gap without changing the pole taper at the ABS. In a first embodiment, this is achieved by increasing the taper of the section above the write gap. In a second embodiment, this section is extended so that it overlaps the write gap laterally. In a third embodiment, a part of this section is brought closer to the ABS while keeping the main parts of the write pole and the trailing shield well separated, magnetically speaking.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a tapered write pole of the prior art.
FIG. 2 shows a cross sectional view of the 1 st embodiment.
FIG. 3 shows a 3D view of the 1 st embodiment.
FIG. 4 shows a cross sectional view of the 2 nd embodiment.
FIG. 5 shows a 3D view of the 2 nd embodiment.
FIG. 6 shows a cross sectional view of the 3 rd embodiment.
FIGS. 7-8 show process steps to make the 1 st and 2nd embodiments respectively.
FIG. 9 shows the starting point for manufacturing the 3 rd embodiment.
FIGS. 10 and 11 show additional steps in the manufacture of the 3 rd embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
We describe below three embodiments of the invention, presented as processes for manufacturing the invention while also serving to describe the invented structure:
It should be noted that the descriptions that follow below, along with their drawings, are written as though the bodies described there, including in some cases cantilever-like projections, have no external support. In reality, these bodies are embedded in one or more layers of insulating material (typically Al 2 O 3 ) which provide whatever mechanical support that is needed without influencing the performance of the device being portrayed. In the interests of simplifying both the descriptions and the figures, these supporting layers are not necessarily shown or mentioned.
FIG. 2 shows the first of the new configurations disclosed in the present invention to enhance flux concentration ratio A 2 /A 1 while still keeping the taper angle of the write gap unchanged. Compared to the prior art shown in FIG. 1 , main pole 14 taper is now formed from two layers, 14 and 25 .
To form layer 14 , a first trench, with sidewalls that slope at an angle θ to the vertical, is formed in a layer of insulation (not shown) to a first depth. This trench is now just filled (overfill followed by CMP) with a layer of material suitable for the main pole followed by a non-magnetic layer (for the write gap). The (filled) first trench is then covered with a second layer of insulation (also not shown). A second trench, whose floor is aligned with the roof of the first trench, is now formed in the second insulation layer, said second trench having sidewalls that slope at an angle greater than θ. The second trench is then just filled with the same material as the first trench, thereby forming layer 25 and completing formation of element 14 as seen in FIG. 7 .
This is followed by an angle-lapping step to form the appropriately sloped surface onto which non-magnetic write gap layer 13 is then deposited (as well as being simultaneously deposited onto the top surface of lower pole 14 ). The process concludes with the deposition and shaping of trailing shield 12 .
Thus top part 25 of layer 14 has a larger taper angle than bottom part 11 , which increases A 2 relative to A 1 without increasing the sensitivity of the ABS to the lapping angle. This is because, after tapered write gap 13 is formed, top layer 25 will be recessed from ABS 11 so that the larger taper angle will not change A 1 when ABS line ‘aa’ is moved.
FIG. 3 shows a 3D view of the structure after tapered write gap 13 has been formed.
FIG. 4 (cross sectional view) and FIG. 5 (3D view of FIG. 4 ) show the 2 nd embodiment of the invention. It differs from the 1 st embodiment in that newly added top layer 45 is not simply an extension of bottom layer 14 with a larger taper angle. Instead, layer 45 does not need to be tapered (although using a tapered shape here would still be within the scope of the invention) In FIGS. 4 and 5 we show element 45 as having a rectangular cross-section (our preferred shape) but as long as there is a net increase in the A 2 /A 1 ratio, the objects of the invention will have been met. In general, element 45 will be wider than the top of write gap 13 enabling the achievement of a larger A 2 /A 1 .
Process-wise the main departure from the first embodiment is that the second trench, also aligned with the first trench and also formed in the second insulation layer, extends outwards from the mouth of the first trench (typically up to about 0.2 to 0.5 microns in each direction) and has straight, as opposed to sloping, sides. As for the first embodiment, the second trench is then just filled with the same material as before, thereby completing formation of element 14 as illustrated in FIG. 8 .
The 3 rd embodiment takes a different approach from the previous two embodiments. Instead of changing the A 2 /A 1 ratio, a non-uniform write gap is formed. This is illustrated FIG. 6 which shows that extra non-magnetic layer 63 has been inserted between write pole 14 and trailing shield 12 . Thus, the write gap is narrower at the ABS and wider away from it. This reduces flux leakage from the main pole to the write shield. Consequently, for a given A 2 /A 1 , this larger separation of the main pole from the trailing shield results in more flux being delivered at the ABS, while the field gradient is unchanged since the write gap at the ABS is unchanged. FIG. 9 shows how non-magnetic layer 13 (the write gap layer) is made up of two connected parts, both of which lie on the upper surface of element 14 —a sloping part (on the left of the figure) and a level part (on the right).
The starting point for forming a write pole built according to the teachings of the third embodiment is similar to the point where, in the first two embodiments, layer 14 has been angle-lapped to provide a suitably tilted surface for layer 13 . After deposition of non-magnetic layer 13 , as seen in FIG. 10 , the non-uniform write gap can be formed by depositing 2 nd write gap layer 93 which is then patterned so that it terminates at a distance (typically between about 0.05 and 0.2 microns from the ABS. The process ends with the deposition and patterning pf layer 12 to form the trailing shield, as shown in FIG. 11 . | A structure and a process for a perpendicular write pole that provides increased magnetic flux at the ABS is disclosed. This is accomplished by increasing the amount of write flux that originates above the write gap, without changing the pole taper at the ABS. Three embodiment of the invention are discussed. | 6 |
FIELD OF THE INVENTION
The present invention relates to an electrically controlled jacquard apparatus; in particular a jacquard apparatus which is capable of selectively controlling individual warp yarns.
BACKGROUND OF THE INVENTION
Maximum pattern flexibility can be achieved on a loom if each individual warp yarn can be independently moved to a selected shed position.
Difficulties arise in independently controlling individual warp yarn in warp sheets having a high density of yarns; eg. density of warp yarns in excess of 15 warp ends per cm. The greater the warp yarn density, the greater the difficulty.
The difficulty arises due to the large number of warp yarns and the limited space available for the jacquard apparatus.
SUMMARY OF THE INVENTION
It is a general object of the present invention to provide a jacquard apparatus capable of controlling individual warp yarns in a warp sheet having a density in excess of 15 warp ends per cm.
According to one aspect of the present invention there is provided a jacquard mechanism for controlling shed selection of warp yarns, the mechanism including at least one selector body adapted for connection to a heald and mounted for movement between upper and lower shed positions, a plurality of elongate support members arranged side by side in a parallel relationship, the selector body being slidably mounted relative to said support members for longitudinal movement therealong, at least one of said plurality of support members being static and at least one other of the plurality of support members being mounted for longitudinal reciprocal movement, the selector body and support members including co-operable latch means operable between latch and unlatch positions causing selective engagement therebetween.
Preferably said plurality of elongate support members comprises a static support member and a pair of reciprocally mounted support members, the support members of said pair being reciprocated out of phase.
Preferably the selector body is elongate and is polygonal in cross-section, preferably triangular. In the case of a triangular cross-section, the selector body slidingly engages the support members at the apices of the cross-section.
Preferably the jacquard mechanism includes a plurality of selector bodies and associated support members, the selector bodies being arranged to be slidingly received on common support members to which other selector bodies are slidably connected.
Preferably the cross-sectional shape of the selector bodies and location of the support members is chosen to define a tessellated assembly.
Preferably the density of selector bodies is in the region of 41,600 per square meter.
Preferably each selector body is connected to an individual heald for controlling the shed position of an individual warp end.
The co-operable latch means preferably comprises a movable latch member mounted on the selector body or support member and a static latch formation on the support member or selector body respectively.
Various aspects of the present invention are hereinafter described, with reference to the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of a selector for controlling movement of an individual warp yarn, the selector being shown at top shed position;
FIG. 2 is a plan view of a plurality of selectors arranged in a jacquard apparatus;
FIG. 3 is the same plan view as FIG. 2 highlighted to show the arrangement of the selectors into hexagonal assemblies;
FIG. 4 is a detailed side view of a selector according to one embodiment of the present invention and as shown in FIG. 3;
FIG. 5 is a broken away side view of a selector according to another embodiment of the present invention;
FIG. 6 is a sectional view taken along line VI--VI in FIG. 5;
FIGS. 7a, 7b are schematic illustrations of a drive mechanism for driving the support members;
FIG. 8 is a schematic illustration similar to FIG. 1 of an alternative embodiment according to the present invention; and
FIG. 9 is a plan view of the embodiment shown in FIG. 8.
FIGS. 10, 11, 12 show alternative latch arrangements incorporated in the support members.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring initially to FIG. 1, there is shown a selector 10 located between three guide elongate support members in the form of pins 11, 12 and 13. The pins 11, 12 and 13 may be made from any suitable non-deformable material which is relatively rigid; a metal such as steel, or a suitable plastics material may be used.
The selector 10 has a body 15 which is generally of elongate form and is generally triangular in cross-section.
The selector body 15 is arranged such that it is slidably mounted in a longitudinal direction on the pins 11, 12 and 13. In this respect, a longitudinally extending groove 55 is provided at each apex of the triangular cross-section which slidably engages a respective pin 11, 12 or 13.
One of the pins is arranged to be stationary whilst the other two pins are arranged to reciprocate longitudinally between upper and lower positions out of phase by 180°. In the illustrated example, pin 11 is stationary, and pins 12, 13 reciprocate.
The selector body 15 houses three movable latches 18, 19 and 20 for respective latching engagement with pins 11, 12 and 13. The latches 18, 19 and 20 are moved between retracted and extended positions by electronically controlled motive means (not shown in FIG. 1) housed within body 15. The motive means may be in the form of an electrostrictive or piezo-electric strip.
A single motive means is preferably provided for each latch 18, 19 and 20.
The pins 11, 12 and 13 are each provided with latch formations for cooperation with latches 18, 19 and 20. Preferably the latch formations comprise the upper end face 22 of the respective pins. The end face 22 may be recessed, for example of conical shape, to define a peripheral knife edge for engagement with latches 18, 19 and 20. Alternatively the latch formation on each pin may be spaced from the end of the pin and be defined by a peripheral groove.
The selector body 15 is attached at one end to a cord 25 which in turn is connected to a heald 26; the heald 26 being biased toward a bottom shed position by a spring 29.
The pins 11, 12 and 13 pass through a support board 30 and in the bottom shed position, the selector body 15 rests upon board 30.
The selector body 15 is moved to an upper shed position (as seen in FIG. 1) by actuating an appropriate latch 19 or 20 to move to an extended position to engage the appropriate pin 12 or 13 which is about to move toward its upper position.
In FIG. 1, pin 12 is shown at its uppermost position and pin 13 is shown at its lowermost position. The body 15 is held at its upper shed position by latch 18 engaging the upper face 22 of pin 11. In order to move the body 15 to the position shown from its bottom shed position and using pin 12, the following sequence occurs:
Prior to pin 12 rising to its uppermost position, latch 19 is moved to its extend position to engage the upper face 22 on pin 12 and the body 15 is thereby raised. The lowermost position of face 22 on pins 12 and 13 is located below the height of latches 19 and 20 when the body 15 is at its bottom shed position. Accordingly actuation of a latch 19 or 20 to move it to its extended position may occur at any time during the period of time taken for the associated pin to fall below the latch as it moves to its lowermost position and then rise to the height of the latch as it begins its upward stroke towards its uppermost position.
The uppermost position of face 22 of pins 12 and 13 is located above the face 22 on pin 11.
Accordingly as the body 15 is raised by pin 12, latch 18 is raised above face 22 on pin 11 as the pins 12 or 13 approaches the end of its upward stroke.
Latch 18 may therefore be actuated to move to its extended position at any time during the time period taken for the pin 12 (or 13) to raise latch 18 above the face 22 on pin 11 and then subsequently lower the latch 18 to the height of face 22 on pin 11.
As the body 15 is lowered with its latch 18 extended, latch 18 engages face 22 on pin 11 and holds the body 15 at its upper shed position as shown in FIG. 1. Disengagement between latch 19 and its associated pin 12 is automatically achieved as pin 12 continues on its downward stroke. Latch 19 may be moved to its retracted position at any time before pin 12 rises to the height of latch 19 on its next upward stroke.
When it is desired to move body 15 to its lower shed position, latch 19 or 20 is extended to engage either pin 12 or 13 as it travels on its upward stroke toward its uppermost position. End face 22 of the rising pin contacts the extended latch and raises the body 15. This causes the latch 18 to lift off face 22 on pin 11. Latch 18 is then retracted before it is lowered to the height of face 22 on pin 11 so that body 15 can continue its downward movement to its lower shed position.
When the body engages board 30, the latch 19 or 20 is automatically disengaged from the associate pin 12 or 13 as the pin continues on the downward stroke to its lowermost position.
In FIG. 2 there is illustrated a plan view of a jacquard apparatus including a plurality of selector bodies 15. The bodies 15 are of triangular cross-section and are arranged in a tessellated manner. In this way, a high number of selector bodies 15 may be accommodated in a limited amount of space.
In the embodiment illustrated in FIG. 2, each pin 11, 12 or 13 is about 8 mm in diameter and their axes are space apart by about 17 mm. Thus, in an area of about 8850 sq mm there are 68 selector bodies. With such an arrangement it is possible in an area of about 0.6 M 2 to accommodate 25000 selector bodies 15 and associated pins 11, 12 and 13; this equates to approximately 41,000 selectors per square meter.
The pins 11, 12, 13 are located at the apices of the triangular bodies 15 and the bodies 15 are arranged in groups of six to define a series of hexagonal assemblies 50 (shown schematically in FIG. 3). A static pin 11 is located at the center of each hexagonal assembly 50 and so each of the six bodies 15 surrounding that pin 11 may be latched thereon in order to be maintained at its upper shed position. Complete hexagonal assemblies 50 are not formed at the periphery of the tessellated assembly.
Similarly, internally of the tessellated assembly, each pin 12 and each pin 13 is surrounded by six selector bodies 15. Accordingly, during any weaving cycle, each selector body 15 may be independently latched on to an associated pin 11, 12 or 13 so as to be independently moved between upper and lower shed positions or retained at these positions.
As more clearly seen in FIG. 4, each selector body 15 preferably comprises a lower body portion 51 which is spaced from and secured to an upper body portion 52 by a series of struts 54. The upper and lower body portions 51, 52 are preferably moulded from a suitable plastics material and are each of triangular cross-section.
A groove 55 is located at the apex of each body portion 51, 52 for sliding engagement with associated pins 11, 12 and 13. The interconnecting struts may be formed from a suitable plastics material or metal.
Each latch 18, 19 and 20 is mounted on an upper end of a deflectable elongate support 60. The support 60 is mounted at its lower end on the lower body portion 15. An electrostrictive or piezo-electric strip 62 is associated with the support 60 to cause the upper end of the support 60 to be deflected outwardly and so move the latch mounted thereon to its extended position. The elongate support 60 may be resilient so as to bias the latch carried by the support 60 to its retracted position.
In FIGS. 5 and 6 an alternative selector body 115 is illustrated; parts similar to those in the embodiment of FIG. 4 have been designated by similar reference numerals.
The selector body 115 includes a unitary elongate body 116 including recessed grooves 117 located at the bottom of grooves 55 for accommodating an electrostictive or piezo-electric strip 62. A movable latch 120 is associated with each strip 62; each latch 120 being pivotally mounted in an associated slot 121 formed in the body 117 via a pivot 123.
Each latch 120 is connected to one end of the associated strip 62 so as to be movable between a retracted, non-latching position (as indicated by latch 120a) and an extended, latching, position (as indicated by latch 120b).
As illustrated, each strip 62 engages its associated latch 120 at the terminal end of the latch 120 remote from pivot 123. It is envisaged that the strip 62 could engage the latch 120 at a position closer to the pivot 123, this provides the advantage of amplifying the displacement of the terminal end of the latch 123 in relation to the displacement of the end of the strip 62.
In the embodiments disclosed in relation to FIGS. 1 to 6, the selector body is provided with a movable latch for co-operation with a static latch formation on the support members 11, 12 and 13.
Alternatively, it is envisaged that the movable latch may be provided on the support members for co-operation with static latch formations on the selector body. An embodiment in which the movable latches are mounted on the support members 11, 12, 13 is illustrated in FIGS. 8 and 9. In FIG. 8, the pins 11, 12 and 13 are shown broken away in order to give a clear view of the selector body 15 within each groove 55 a recess 70 is provided which defines a static latch formation.
Each pin 11, 12 and 13 is provided with a movable latch assembly 72 which is co-operable with each respective static latch.
Each movable latch assembly 72 preferably comprises a latch member (not shown in FIG. 8) which is moved between extended and retracted positions by motive means, preferably in the form of an electrostrictive or piezo-electric strip 62.
In the retracted position, each latch assembly lies within the periphery of the pin on which it is mounted so as to provide no obstruction to sliding movement of the body 15 along the pins 11, 12 and 13.
These alternative constructions of latch assemblies 80, 90 and 100 for mounting on pins 11, 12 and 13 are shown in respective FIGS. 10, 11 and 12.
In FIG. 10, each latch assembly 80 includes an elongate latch member 81 which extends longitudinally of the pin 11. The lower end of the latch member 81 is pivotally attached to the pin 11 so that the upper end 82 of the latch member 81 is movable between a retracted position (not shown) and an extended position as shown. The upper end 82 defines a latch formation for engagement with the selector body. The pivotal connection between the pin 11 and the lower end of the latch member 81 is preferably formed as shown by the provision of a recessed seat 84 in the pin 11 and a rounded end 85 of the member 81.
Such an arrangement not only permits pivotal movement but also enables loads carried by the latch member 81 to be transmitted to the pin 11 via the abutment between rounded end 85 and recessed seat 84.
The latch member 81 is preferably moved between its extended and retracted position by means of an electrostrictive or piezo-electric strip 82.
In the embodiment shown in FIG. 11 the latch member 91 is mounted on the lower end of an electrostrictive or piezo-electric strip 92. The strip 92 is secured to the pin 11 at its upper end 94 and is arranged to move the latch member 91 between an extended position (as seen on the left-hand side of FIG. 11 ) and a retracted position (as seen on the right-hand side of FIG. 11 ). The upper end 93 of the latch member 91 defines a latch formation for engagement with the selector body.
When engaged with the selector body, forces applied to the latch member 91 are transmitted to the pin 11 via the strip 92 and so places the strip 92 in tension. Preferably, at least in this embodiment, the strip 92 is reinforced with fibres such as carbon fibres in order to improve its load bearing capabilities when in tension.
In the embodiment shown in FIG. 12, the latch member 101 is pivotally mounted on the pin 11 via a pivot pin 103.
The latch member 101 has an upper end 104 which defines a latch formation for engagement with the selector body and is arranged so that on movement about its pivot axis the upper end 104 is moved between an extended position (as shown) and a retracted position (not shown). An electrostrictive or piezo-electric strip 105 is provided for moving the latch member between its extended and retracted positions. The latch member 101 preferably includes an abutment face 106 which abuts against the pin 11 when the latch member is in its extended position. In this way, loads applied to the latch member when in engagement with the selector body are transmitted directly to the pin 11 and so the strip 105 is isolated from such loads.
For all embodiments 80, 90 and 100, the respective latch members are preferably moulded from a suitable hard wearing plastics material.
In addition, for the embodiments of 80 and 100, the amount of displacement of the upper end of the latch member when moving between its retracted and extended positions in relation to the amount of displacement of the electrostrictive or piezo-electric strip may be varied by altering the distance of the upper end of the latch from its pivotal connection with the pin and/or altering the distance of the point of attachment of the strip from the pivotal connection.
An arrangement for mounting and driving the pins 11, 12 and 13 is illustrated in FIGS. 7c and 7b.
A pair of spaced fixed boards 30a, 31a are provided between which the stationary pins 11 are fixed.
One end of pins 12 are mounted in a movable board 32a and one end of pins 13 are mounted in a movable board 33a.
The boards 32a and 33a are reciprocated between upper and lower limits of reciprocal movement by appropriate drive means (not shown) such as cam operated levers; those limits between shown in FIGS. 7a, 7b.
Accordingly the boards 30c, 31a serve to maintain regular spacing between pins 11, 12 and 13.
The length of pins 12 and 13 are chosen such that throughout their reciprocal movement they extend continuously between boards 30a, 31a.
The selector bodies 15 are located between the boards 30a, 31a and the position of latch assemblies 72 on respective pins 11, 12 and 13 is chosen so that these assemblies function to move the selector bodies 15 between upper and lower shed positions in between boards 30a, 31a. | An electrically controlled jacquard apparatus capable of selectively controlling individual warp yarns. Each warp yarn is controlled by a selector body which is engaged by at least two and preferably three parallel support members and is adapted to be reciprocated by sliding longitudinally of the support members. One of the support members is static and the other two support members are reciprocated longitudinally out-of-phase with each other. The selector body is selectively latched to the three members so as to be moved in either direction or to be supported at a static position. | 3 |
PRIORITY
[0001] The present application is related to and claims the benefit under 35 U.S.C. §119(a) of a Korean patent application No. 10-2013-0105774 filed in the Korean Intellectual Property Office on Sep. 3, 2013, the entire disclosure of which is hereby incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to a method of providing notification in an electronic device and the electronic device thereof.
BACKGROUND
[0003] As mobile communication technology develops, electronic devices are provided in various forms such as a smart phone, a wearable device, and a tablet personal computer (PC) and may transmit and receive various data through a communication system between electronic devices. The electronic device may provide various functions such as a phone function, a message function, and an alarm function.
[0004] The electronic device may provide an event that has occurred in an electronic device to a user through various output methods and transmit and receive information about an event to and from another electronic device with various communication methods.
[0005] In the conventional art, when a user uses a plurality of electronic devices for providing notification, by providing the same notification information through each electronic device, unnecessary notification may be repeatedly provided, and thus in each electronic device, power consumption may increase. Further, as notification information checked through the electronic device is repeatedly provided through another device, inconvenience in which the user should repeatedly check the same notification information may occur.
SUMMARY
[0006] A method in an electronic device is provided. The method includes establishing a wireless communication between the electronic device and an external device, detecting an event to be notified in the electronic device, obtaining a status of the electronic device, and determining whether to transmit an notification on the event to an external device, based on the status of the electronic device.
[0007] In some embodiments, the electronic device is configured to transmit the notification to the external device when a screen of the electronic device is not available to display a notification.
[0008] In some embodiments, the electronic device is in a power saving mode.
[0009] In some embodiments, the screen of the electronic device is being occupied by a software program.
[0010] In some embodiments, the method further includes obtaining a status of the external device.
[0011] In some embodiments, the method further includes determining whether to present the notification on a screen of the electronic device, based on the status of the external object.
[0012] In some embodiments, the electronic device is configured to display the notification when the external device is not available to display a notification.
[0013] In some embodiments, the method further includes determining whether the event to be notified has a priority over the status of the electronic device.
[0014] In some embodiments, the method further includes determining which one of the electronic device and the external device being positioned within visibility of a user, displaying the notification on the determined device.
[0015] In some embodiments, the method further includes measuring a distance between the electronic device and the external device, transmitting the notification when the distance is less than a threshold distance.
[0016] In some embodiments, the method further includes when the notification is transmitted to the external device, determining whether the notification on the external device is read, storing a status of reading the notification in the electronic device.
[0017] An electronic device is provided. The electronic device includes a transceiver configured to establish a wireless communication between the electronic device and an external device, a processor configured to detect an event to be notified in the electronic device, obtain a status of the electronic device, and determine whether to transmit an notification on the event to an external device, based on the status of the electronic device.
[0018] In some embodiments, the electronic device is configured to transmit the notification to the external device when a screen of the electronic device is not available to display a notification.
[0019] In some embodiments, the electronic device is in a power saving mode.
[0020] In some embodiments, the screen of the electronic device is being occupied by a software program.
[0021] In some embodiments, the processor is further configured to obtain a status of the external device, and determine whether to present the notification on a screen of the electronic device, based on the status of the external object.
[0022] In some embodiments, the electronic device is configured to display the notification when the external device is not available to display a notification.
[0023] In some embodiments, the processor is further configured to determine whether the event to be notified has a priority over the status of the electronic device.
[0024] In some embodiments, the processor is further configured to determine which one of the electronic device and the external device being positioned within visibility of a user, display the notification on the determined device.
[0025] In some embodiments, the processor is further configured to measure a distance between the electronic device and the external device.
[0026] In some embodiments, the processor is further configured to transmit the notification when the distance is less than a threshold distance.
[0027] In some embodiments, the processor is further configured to, when the notification is transmitted to the external device, determine whether the notification on the external device is read,
[0028] In some embodiments, the processor is further configured to cause a status of reading the notification to be stored in the electronic device.
[0029] Before undertaking the DETAILED DESCRIPTION below, it may be advantageous to set forth definitions of certain words and phrases used throughout this patent document: the terms “include” and “comprise,” as well as derivatives thereof, mean inclusion without limitation; the term “or,” is inclusive, meaning and/or; the phrases “associated with” and “associated therewith,” as well as derivatives thereof, may mean to include, be included within, interconnect with, contain, be contained within, connect to or with, couple to or with, be communicable with, cooperate with, interleave, juxtapose, be proximate to, be bound to or with, have, have a property of, or the like; and the term “controller” means any device, system or part thereof that controls at least one operation, such a device may be implemented in hardware, firmware or software, or some combination of at least two of the same. It should be noted that the functionality associated with any particular controller may be centralized or distributed, whether locally or remotely. Definitions for certain words and phrases are provided throughout this patent document, those of ordinary skill in the art should understand that in many, if not most instances, such definitions apply to prior, as well as future uses of such defined words and phrases.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] For a more complete understanding of the present disclosure and its advantages, reference is now made to the following description taken in conjunction with the accompanying drawings, in which like reference numerals represent like parts:
[0031] FIG. 1 is a block diagram illustrating an electronic device according to various embodiments of the present invention;
[0032] FIG. 2 is a block diagram illustrating a notification control module of an electronic device according to various embodiments of the present invention;
[0033] FIGS. 3A and 3B are diagrams illustrating the operations of controlling a notification information output in an electronic device according to various embodiments of the present invention;
[0034] FIGS. 4A to 4E are diagrams illustrating the operations of controlling a notification information output in an electronic device according to various embodiments of the present invention;
[0035] FIGS. 5A and 5D are diagrams illustrating the operations of controlling a notification information output in an electronic device according to various embodiments of the present invention;
[0036] FIG. 6 is a diagram illustrating the operations of processing notification information in an electronic device according to various embodiments of the present invention;
[0037] FIG. 7 is a flowchart illustrating the operation of processing notification information in an electronic device according to various embodiments of the present invention;
[0038] FIG. 8 is a flowchart illustrating the operation of providing notification information in an electronic device according to various embodiments of the present invention; and
[0039] FIG. 9 is a block diagram of an electronic device according to various embodiments of the present invention.
DETAILED DESCRIPTION
[0040] FIGS. 1 through 9 , discussed below, and the various embodiments used to describe the principles of the present disclosure in this patent document are by way of illustration only and should not be construed in any way to limit the scope of the disclosure. Those skilled in the art will understand that the principles of the present disclosure may be implemented in any suitably arranged electronic devices. Hereinafter, in various embodiments of the present invention, a method of outputting notification of various data received in an electronic device or an event that has occurred in an electronic device and the electronic device thereof are described with reference to the accompanying drawings.
[0041] In various embodiments according to a method of providing notification and an electronic device thereof, it can be determined whether at least one another electronic device connected to the electronic device can be used and at least one electronic device that provides notification information according to a designated reference can be determined. Further, in various embodiments according to a method of providing notification and an electronic device thereof, when an event to provide notification occurs in an electronic device in which at least one function is executing, information on whether to output notification or whether the output notification has been checked can be managed.
[0042] While the present invention may be embodied in many different forms, specific embodiments of the present invention are shown in drawings and are described herein in detail, with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated. The same reference numbers are used throughout the drawings to refer to the same or like parts. Detailed descriptions of well-known functions and structures incorporated herein may be omitted to avoid obscuring the subject matter of the present invention.
[0043] An expression of “comprising” and “can comprise” used in the present invention indicates existence of a corresponding function, operation, element and does not limit at least one additional function, operation, and element. In addition, in the present invention, a term “comprise” or “have”, will be understood to imply the inclusion of a characteristic, a numeral, a step, an operation, a element, a component, or a combination thereof described in the specification but not the exclusion of at least one another characteristic, numeral, step, operation, element, component, or combination thereof.
[0044] An electronic device according to the present invention may be a device including a communication function. For example, the electronic device may include a smart phone, a tablet personal computer (tablet PC), a mobile phone, an audiovisual phone, an e-book reader, a desktop PC, a laptop PC, a netbook computer, a personal digital assistant (PDA), a portable multimedia player (PMP), an MP3 player, a mobile medical device, a camera, and a wearable device (e.g., at least one of a head-mounted-device (HMD) such as electronic glasses, electronic clothes, an electronic bracelet, an electronic necklace, electronic accessories, and a smart watch).
[0045] According to an embodiment, the electronic device can be a smart home appliance having a communication function. The smart home appliance can include at least one of, for example, a television, a digital video disk (DVD) player, an audio device, a refrigerator, an air-conditioner, a cleaner, an oven, a microwave oven, a washing machine, an air cleaner, a set-top box, a television box (e.g., Samsung HomeSync™, Apple TV™, or Google TV™), game consoles, an electronic dictionary, an electronic key, a camcorder, and an electronic frame.
[0046] According to an embodiment, the electronic device can include at least one of various medical devices (e.g., a magnetic resonance angiography (MRA), a magnetic resonance imaging (MRI), a computed tomography (CT), a camera, and an ultrasonic wave device), a navigation device, a global positioning system (GPS) receiver, an event data recorder (EDR), a flight data recorder (FDR), a vehicle infotainment device, a ship electronic equipment (e.g., a navigation device and a gyro compass for a ship), avionics, and a security device.
[0047] According to an embodiment, the electronic device can include at least one of a portion of furniture or a building/structure having a communication function, an electronic board, an electronic signature receiving device, a projector, and various measuring devices (e.g., water supply, electricity, gas, or electric wave). The electronic device according to the present invention can be at least one combination of the foregoing various devices. Further, it will become apparent to a person of common skill in the art that the electronic device according to the present invention is not limited to the foregoing devices. Hereinafter, an electronic device according to various embodiments will be described with reference to the accompanying drawings. A term ‘user’ used in various embodiments can include a person who uses an electronic device or a device (e.g., artificial intelligence electronic device) using an electronic device.
[0048] FIG. 1 is a block diagram illustrating an electronic device 101 according to various embodiments of the present invention.
[0049] Referring to FIG. 1 , the electronic device 101 can include a notification control module 120 , a bus 110 , a processor 160 , a memory 130 , an input and output interface 140 , a display 150 , and a communication interface 170 .
[0050] The notification control module 120 can refer to a database stored at the memory 130 of the electronic device 101 or a database of each application. When the notification control module 120 detects that an event to provide notification to the electronic device 101 has occurred, the notification control module 120 can determine whether the electronic device 101 is to output the notification or another electronic device (e.g., an electronic device 102 or an electronic device 104 ) connected to the electronic device 101 is to output the notification. Further, the notification control module 120 can acquire information about whether notification information related to notification output through the electronic device 101 or another electronic device has been checked by a user of the electronic device 101 and update a database stored at, for example, the memory 130 or a database of each application. When a check history of the notification information does not exist, the notification control module 120 can process to re-output notification corresponding to the notification information through the electronic device 101 or another electronic device.
[0051] The bus 110 can be a circuit that connects the foregoing elements and that transfers communication (e.g., a control message) between the foregoing elements.
[0052] The processor 160 can receive an instruction from the foregoing another elements (e.g., the memory 130 , the input and output interface 140 , the display 150 , and the communication interface 170 ) through, for example, the bus 110 , decode the received instruction, and execute a calculation or a data processing according to the decoded instruction.
[0053] The memory 130 can store an instruction or data received from the processor 160 or other elements (e.g., the input and output interface 140 , the display 150 , and the communication interface 170 ) or generated by the processor 160 or other elements. The memory 130 can include programming modules such as a kernel 131 , middleware 132 , an application programming interface (API) 133 , or an application 134 . The foregoing each programming module can be formed with software, firmware, hardware, or at least two combinations thereof.
[0054] The kernel 131 can control or manage system resources (e.g., the bus 110 , the processor 160 , or the memory 130 ) used for executing an operation or a function embodied in the remaining programming modules, for example, the middleware 132 , the API 133 , or the application 134 . Further, the kernel 131 can provide an interface that accesses to an individual element of the electronic device 101 in the middleware 132 , the API 133 , or the application 134 to control or manage the individual element.
[0055] The middleware 132 can function as an intermediary that enables the API 133 or the application 134 to communicate with the kernel 131 to transmit and receive data. Further, the middleware 132 can perform load balancing of a work request using a method of aligning a priority that can use a system resource (e.g., the bus 110 , the processor 160 , or the memory 130 ) of the electronic device 101 in, for example, at least one application of the (plurality of) applications 134 in relation to work requests received from the (plurality of) applications 134 .
[0056] The API 133 is an interface in which the application 134 can control a function in which the kernel 131 or the middleware 132 provides and can include at least one interface or function for, for example, file control, window control, image processing, or character control.
[0057] The input and output interface 140 receives an input of an instruction or data from, for example, the user to transfer the instruction or the data to the processor 160 or the memory 130 through the bus 110 . The display 150 can display an image or data to the user.
[0058] The communication interface 170 can connect communication between the electronic device 101 and another electronic device 102 or electronic device 104 , or a server 164 . The communication interface 170 can support a predetermined short range communication protocol (e.g., wireless fidelity (Wifi), Bluetooth (BT), near field communication (NFC), or communication of a predetermined network (e.g., Internet, a local area network (LAN), a wire area network (WAN), a telecommunication network, a cellular network, a satellite network, or plain old telephone service (POTS)) 162 . The electronic devices 102 and 104 each can be the same (e.g., the same type) device as the electronic device 101 or can be a device different (e.g., different type) from the electronic device 101 .
[0059] The electronic device 101 can be connected to another electronic device 102 through network communication. Hereinafter, when describing various embodiments, as in another electronic device 102 or the second electronic device 102 (e.g., when the electronic device 101 is represented with a first electronic device 101 ), another electronic device connected to the electronic device 101 can be represented with the electronic device 102 shown in FIG. 1 . In FIG. 1 , the electronic device 102 and the electronic device 104 are divided to describe a method connected to the electronic device 101 , and unless a communication method such as short range wireless communication (not shown) or the network 162 is distinguished, the electronic device 102 or the electronic device 104 can be represented with another electronic device connected to the electronic device 101 . Therefore, unless it is specially separately described, the electronic device 102 described in various embodiments and embodiments thereof can be applied to the electronic device 104 connected through the network 162 . The server 164 displayed in FIG. 1 can be applied with a similar method.
[0060] FIG. 2 is a block diagram illustrating the notification control module 120 of the electronic device 101 according to various embodiments of the present invention.
[0061] Referring to FIG. 2 , the notification control module 120 can include at least one of a determining module 210 , a check module 220 , an acquiring module 230 , and a providing module 240 .
[0062] Hereinafter, various embodiments of each module will be described.
[0063] The determining module 210 can determine notification information to provide to the user. According to an embodiment, the determining module 210 can determine notification information about some event of events acquired in the electronic device 101 as notification information to provide to the user. For example, the electronic device 101 can determine whether the user checks notification information related to at least one event. The electronic device 101 can determine notification information related to an event in which the user does not check as notification information to provide. The event can include, for example, a phone reception event, a message reception event, an alarm event, or a social network service (SNS) event.
[0064] According to an embodiment, the determining module 210 can determine whether to output notification of an event (e.g., data) received in the electronic device 101 through the input and output interface 140 or the display 150 . When the electronic device 101 determines notification information to provide through the determining module 210 , the electronic device 101 can detect at least one another electronic device (e.g., the electronic device 102 and the electronic device 104 ) that can be connected to the electronic device 101 through the check module 220 .
[0065] According to an embodiment, the check module 220 can acquire information about another electronic device having a history at least one time connected to the electronic device 101 and search for at least one another electronic device that can connect communication through the communication interface 170 of the electronic device 101 with another method.
[0066] The acquiring module 230 can acquire status information related to at least one of the electronic device 101 or at least one another electronic device (e.g., the electronic device 102 , the electronic device 104 , and the server 164 ) communicating with the electronic device 101 . According to an embodiment, status information can include information that determines whether the user uses each of the electronic device 101 or another electronic device. For example, the acquiring module 230 can acquire information about whether the electronic device 101 or another electronic device is in an enabling status or a disabling status. According to an embodiment, when the electronic device 101 is in an enabling status, it can be determined that the user uses the electronic device 101 . For example, it can be determined whether each of the electronic device 101 or another electronic device is in an enabling status or a disenabling status through an operation status of a display functionally connected to each of the electronic device 101 or another electronic device. For example, when a display functionally connected to the electronic device 101 is turned on, it can be determined that the electronic device 101 is in an enabling status. Further, for example, status information of the electronic device 101 or another electronic device can include status information about the user. The status information on the user can include information detected through at least one of sensors such as a touch sensor, a grip sensor, a motion sensor (e.g., an acceleration sensor, an gyro sensor), an image sensor, a proximity detection sensor, a microphone, a living body detection sensor (fingerprint detection sensor, vein detection sensor, temperature sensor), and an image sensor (e.g., a sight line recognition sensor) functionally connected to the electronic device 101 or another electronic device. Further, the acquiring module 230 can acquire information about a communication state with at least one another electronic device connected to the electronic device 101 or at least one communication method that can be connected to another electronic device 102 as the status information about the electronic device 101 or another electronic device.
[0067] For example, when a motion sensor functionally connected to the electronic device 101 detects a motion of the electronic device 101 , it can be determined that the user uses the electronic device 101 . Further, for example, when a touch sensor functionally connected to the electronic device 101 detects a user input, it can be determined that the user uses the electronic device 101 . Further, for example, the user's sight line can be detected through an image sensor that can recognize a sight line functionally connected to the electronic device 101 . When the user's sight line is detected in the electronic device 101 , it can be determined that the user uses the electronic device 101 . Further, for example, the electronic device 101 is a wearable device, and when it is detected that the user wears the electronic device 101 through a grip sensor and a proximity detection sensor functionally connected to the electronic device 101 , it can be determined that the user uses the electronic device 101 .
[0068] According to an embodiment, the status information can include attribute information of an application executing in the electronic device 101 or another electronic device. For example, attribute information of an application can include information about whether to provide notification information while executing an application. According to an embodiment, the status information can include power source status information or load information of the electronic device 101 or another electronic device.
[0069] According to an embodiment, the status information can include attribute information of notification information. For example, attribute information of notification information can include priority information about notification information. For example, attribute information of notification information can include information on whether an event occurs and time information consumed to provide notification information related to the event. For example, attribute information of notification information related to a phone event can be designated as an event that should be provided in real time. According to an embodiment, the status information can include designated information. For example, an electronic device to provide notification information can be designated according to a designated time or a designated location. For example, at a work time, it can be set to receive notification information through another electronic device connected to an electronic device, and at a time other than a work time, it can be set to receive notification information through an electronic device. Further, for example, in a vehicle, it can be set to receive notification information through another electronic device connected to an electronic device, and at a home, it can be set to receive notification information through an electronic device. According to an embodiment, the status information can include distance information or communication information between the electronic device 101 and another electronic device.
[0070] According to an embodiment, the acquiring module 230 can acquire at least one information of the foregoing status information or a combination thereof.
[0071] The providing module 240 can determine at least one device to provide notification information related to an event that has occurred in the electronic device 101 of the electronic device 101 or other electronic devices communicating with the electronic device 101 based on the status information acquired through the acquiring module 230 in an embodiment. The providing module 240 can control to provide notification information through the electronic device 101 or another electronic device based on the determined result. For example, when it is determined that the user is using the electronic device 101 based on the status information acquired in the acquiring module 230 , the providing module 240 can provide notification information through the electronic device 101 . When it is determined that the user does not use the electronic device 101 , the providing module 240 can transmit notification information to another electronic device so that another electronic device connected to the electronic device 101 provides notification information.
[0072] When the status information acquired in the electronic device 101 is attribute information of an application, for example, when it is determined that an application executing in the electronic device 101 has a priority lower than that of notification information to provide based on the status information acquired in the acquiring module 230 , the providing module 240 can provide notification information through the electronic device 101 . Further, when it is determined that an application executing in the electronic device 101 has a priority higher than that of notification information to provide, the providing module 240 can transmit notification information to another electronic device so that another electronic device connected to the electronic device 101 provides notification information.
[0073] When the status information acquired in the electronic device 101 is load information of the electronic device 101 , for example, when a load of the electronic device 101 is lower than a designated reference (e.g., 90% of a total load that can process), the providing module 240 can provide notification information through the electronic device 101 . Further, when a load of the electronic device 101 is higher than a designated reference, the providing module 240 can transmit notification information to another electronic device so that another electronic device connected to the electronic device 101 provides notification information. When the status information acquired in the electronic device 101 is power information of the electronic device 101 , for example, when a battery residual quantity of the electronic device 101 is higher than a designated reference (e.g., 10% of a total battery capacity or 150 mAh), the providing module 240 can provide notification information through the electronic device 101 . Further, when a battery residual quantity of the electronic device 101 is lower than a designated reference, the providing module 240 can transmit notification information to another electronic device so that another electronic device connected to the electronic device 101 provides notification information.
[0074] For example, in the status information acquired in the electronic device 101 , when notification information (e.g., incoming call notification information) should be provided in real time based on attribute information of notification information, the providing module 240 can control to provide notification information through a device in which the user uses among the electronic device 101 or another electronic device connected to the electronic device 101 . When it is unnecessary to provide notification information (e.g., weather information notification information) in real time based on attribute information of notification information, the providing module 240 can control to provide notification information through a device having a small load or a large battery capacity among the electronic device 101 or another electronic device. According to an embodiment, a designated reference of various information related to the electronic device 101 can be variously changed according to the user's setting, a designer's setting, or product information about the electronic device 101 .
[0075] According to an embodiment, when it is determined that the providing module 240 transmits notification information to at least one another electronic device, the electronic device 101 can receive additionally or alternatively the status information from each of at least one another electronic device connected to the electronic device 101 , determine a device (e.g., the electronic device 102 ) in which a display (e.g., a touch screen) is in an on state and/or in an unlock state among at least one another electronic device using the received status information, and transmit notification that has occurred to the determined device.
[0076] FIGS. 3A and 3B are diagrams illustrating the operation of controlling a notification information output in an electronic device according to various embodiments of the present invention.
[0077] Hereinafter, various embodiments of the present invention will be described with reference to FIG. 3A .
[0078] Referring to FIG. 3A , for example, the electronic device 101 can be represented with a first electronic device 301 , and the electronic device 102 can be represented with a second electronic device 302 . According to an embodiment described with reference to FIG. 3A , the first electronic device 301 can be represented with a smart phone, and the second electronic device 302 can be represented with a wearable smart watch. The first electronic device 301 and the second electronic device 302 are not limited to a smart phone or a wearable watch and can be electronic devices of various forms that can apply to various embodiments of the present invention.
[0079] The first electronic device 301 can check that an event to provide notification has occurred and output notification information. In a method of outputting notification information that has occurred, the first electronic device 301 can control the first electronic device 301 that detects that notification has occurred to output notification information or control the second electronic device 302 connected to the first electronic device 301 to output notification information.
[0080] According to an embodiment, the first electronic device 301 can detect an event to provide notification. The event to provide notification can include calling information, Short Message Service (SMS) information, missed call information, and alarm information of a notification function in which the first electronic device 301 receives.
[0081] At a time point that detects an event to provide notification, when the first electronic device 301 is in a disabling status (e.g., a sleep mode), the first electronic device 301 can transmit notification information that has occurred in the first electronic device 301 so that another electronic device (e.g., the second electronic device 302 ) connected to the first electronic device 301 outputs the notification information. In order for the first electronic device 301 to transmit notification information that has occurred to another electronic device (e.g., the second electronic device 302 ), the first electronic device 301 can check, for example, at least one another electronic device connected to the first electronic device 301 . According to an embodiment, in order for the first electronic device 301 to transmit notification information that has occurred to another electronic device (e.g., the second electronic device 302 ), the first electronic device 301 can check at least one another electronic device having a history of at least one time connection with short range wireless communication or communication using the network 162 . According to an embodiment, in order for the first electronic device 301 to transmit notification information that has occurred to another electronic device (e.g., the second electronic device 302 ), the first electronic device 301 can determine at least one another electronic device that can connect with short range wireless communication or communication using the network 162 . The first electronic device 301 can be connected to at least one determined another electronic device. For example, when a second electronic device is included in at least one determined another electronic device, the first electronic device 301 can receive status information related to the connected second electronic device 302 . The status information related to the second electronic device 302 can include at least one of information (e.g., enabling information of the second electronic device 302 ) about whether the user uses the second electronic device 302 , attribute information of an application executing in the second electronic device 302 , battery residual quantity information (e.g., power information) or load information of the second electronic device 302 , communication information or distance information between the second electronic device 302 and the electronic device, and the status information (e.g., at least one sensor information acquired by a sensor functionally connected to the second electronic device 302 ) of the user of the second electronic device 302 .
[0082] The first electronic device 301 can determine at least one device to output notification based on a designated priority according to the received status information of the second electronic device 302 or an importance level designated to an element included in the status information. According to an embodiment, the first electronic device 301 can include at least one processor. When the first electronic device 301 includes a plurality of processors, the plurality of processors can include an application processor (AP) or a communication processor (CP). The AP or the CP can be independently formed as each processor or can be included in one processor. The AP can be an application of the first electronic device 301 or a processor that controls the operation of at least one partial device (or a module) constituting the first electronic device 301 , and the CP can be a processor that transmits and receives information to and from the second electronic device 302 through short range wireless communication or communication using the network 162 . When the first electronic device 301 detects information about an event to provide notification received from an external device (e.g., the server 164 ) through the CP, the first electronic device 301 can determine an operation status of the AP that controls operation of outputting notification. When it is determined that the AP is in a disabling status (e.g., a sleep mode), the first electronic device 301 can control to output notification information through at least one another electronic device (e.g., the second electronic device 302 ) connected to the first electronic device 301 instead of outputting notification information through the first electronic device 301 . Here, in an embodiment of a sleep mode, when a current amount or a power amount in which the device consumes is a designated numerical value (e.g., 20 mW or less), and it can be determined that a current consumed amount or a power consumed amount of the same level is maintained. In this case, the first electronic device 301 can transmit notification information to at least one other electronic device, for example, so as to output alarm information from at least one other electronic device through the CP instead of controlling operations of the AP. According to an embodiment, the first electronic device 301 can detect an event to provide notification and check a connection status of another electronic device (e.g., the second electronic device 302 ) designated to a top priority according to the status information of the first electronic device 301 or information stored at a database. The first electronic device 301 can check that the second electronic device 302 is connected and transmit notification information to the second electronic device 302 .
[0083] According to various embodiments, the first electronic device 301 can have authority that can control operations of the second electronic device 302 . In this case, the first electronic device 301 can transmit notification information including an instruction that controls the second electronic device 302 to output notification of the first electronic device 301 to the second electronic device 302 . The second electronic device 302 can receive notification information from the first electronic device 301 and output notification according to notification information. According to an embodiment, the first electronic device 301 can receive a calling request from ‘Joseph’. When the AP of the first electronic device 301 is in a disabling status at a calling request reception time point with reference to the status information or a database, the first electronic device 301 can determine at least one device for outputting received calling information among other electronic devices including the second electronic device 302 that can output calling request information received from ‘Joseph’. For example, the first electronic device 301 can transmit phone connection request information received from ‘Joseph’ to the second electronic device 302 determined to output notification information. The second electronic device 302 can output calling request information as illustrated in FIG. 3A , according to the received information, and when a communication connection icon is selected in the second electronic device, a user of the second electronic device can perform a phone connection with ‘Joseph’.
[0084] According to an embodiment, the first electronic device 301 can receive a text (character) message from ‘Joseph’. When the AP of the first electronic device 301 is in a disabling status at a text message reception time point with reference to the status information or a database, the first electronic device 301 can determine at least one device for outputting message information among other electronic devices including the second electronic device 302 that can output text message information received from ‘Joseph’. The first electronic device 301 can transmit text message information received from ‘Joseph’ to the second electronic device 302 determined to output notification information. The second electronic device 302 can output text message information (FIG. 3 A(b)) according to received information, and the user of the second electronic device can check a text message in the second electronic device 302 through a designated operation (e.g., selection of a message check icon output to the display 150 of the second electronic device 302 ).
[0085] According to an embodiment, the first electronic device 301 can detect missed call information according to a phone connection received from ‘Joseph’. When the AP of the first electronic device 301 is in a disabling status at a time point that detects missed call information with reference to the status information or a database, the first electronic device 301 can determine at least one device for providing missed call information among other electronic devices including the second electronic device 302 that can output missed call information received from ‘Joseph’. The first electronic device 301 can transmit missed call information received from ‘Joseph’ to the second electronic device 302 determined to output notification information. The second electronic device 302 can output missed call information as illustrated in (c) of FIG. 3A , according to received information and can request a phone connection from the second electronic device 302 to the electronic device of ‘Joseph’ through the communication interface 170 of the first electronic device 301 with a designated operation (e.g., selection of a calling request icon output to the display 150 of the second electronic device 302 ). According to various embodiments, an event to provide notification that controls the first electronic device 301 to output from the second electronic device 302 is not limited to embodiments described in FIG. 3A , and various embodiments of similar methods can be applied thereto.
[0086] Hereinafter, various embodiments of the present invention will be described with reference to FIG. 3B .
[0087] Referring to FIG. 3B , for example, the electronic device 101 can be represented with a first electronic device 311 , the electronic device 102 can be represented with a second electronic device 312 , and the same electronic device as the electronic device 104 or the electronic device 102 or an electronic device similar to the electronic device 104 or the electronic device 102 can be represented with a third electronic device 314 . Hereinafter, when describing an embodiment of the present invention, the second electronic device 312 can be applied to the electronic device 104 and the third electronic device 314 can be applied to the same electronic device as the electronic device 102 or an electronic device similar to the electronic device 102 . In an embodiment described with reference to FIG. 3B , for example, the first electronic device 311 can be represented with a smart phone, the second electronic device 312 can be represented with a smart television, and the third electronic device 314 can be represented with a wearable smart watch. The first electronic device 311 can check that an event to provide notification has occurred and can output notification information. In a method of outputting notification information that has occurred, the first electronic device 311 , having detected notification occurrence can output notification information and the second electronic device 312 connected to the first electronic device 311 can output notification information.
[0088] According to an embodiment, the first electronic device 311 can detect an event to provide notification. When the first electronic device 311 detects an event to provide notification, the first electronic device 311 can determine whether the first electronic device 311 or the AP functionally connected to the first electronic device 311 is in a disabling status. According to an embodiment, when the first electronic device 311 or the AP is in a disabling status, for example, the display 150 of the first electronic device 311 can be in an off state or the AP can be in a sleep mode status. When the first electronic device 311 is in a disabling status, the first electronic device 311 (e.g., the providing module 240 ) can determine so that another electronic device (e.g., the second electronic device 312 or the third electronic device 314 connected to the first electronic device 311 ) outputs notification information that has occurred in the first electronic device 311 . In order to transmit notification information that has occurred, the first electronic device 311 can check the first electronic device 311 and another electronic device connected to, for example, the communication interface 170 . Further, in order to transmit notification information that has occurred, the first electronic device 311 can check at least one another electronic device having a history connected at least one time by the communication interface 170 . Further, in order to transmit notification information that has occurred, the first electronic device 311 can check another electronic device that can be connected through the communication interface 170 .
[0089] The first electronic device 311 can be connected to the checked at least one another electronic device, and for example, when the second electronic device 312 and the third electronic device 314 is included in at least one another electronic device, the first electronic device 311 can receive the status information of another electronic device including the connected second electronic device 312 and third electronic device 314 . The status information of the second electronic device 312 or the third electronic device 314 can include information (e.g., enabling information of the second electronic device 312 or the third electronic device 314 ) about whether the user uses the second electronic device 312 or the third electronic device 314 , information about an operation (e.g., an application) being performed, importance level information of an operation (e.g., an application) being performed, battery residual quantity information (or power information), communication state information between the second electronic device 312 or the third electronic device 314 and an external electronic device (e.g., a first electronic device), and user information (e.g., at least one sensing information in which the second electronic device 312 or the third electronic device 314 acquires) of the second electronic device 312 or the third electronic device 314 . According to an embodiment, sensing information can be information about a state of each electronic device acquired through at least one sensor included in the second electronic device 312 or the third electronic device 314 . The first electronic device 311 can determine a priority according to an importance level designated to elements included in the received status information of the second electronic device 312 or the third electronic device 314 and can determine at least one another electronic device to output notification with reference to the status information and a designated priority.
[0090] According to an embodiment, the first electronic device 311 can check a connecting method of the second electronic device 312 or the third electronic device 314 connected by the communication interface 170 and can determine signal information of a connected communication method. According to an embodiment, the first electronic device 311 can determine a communication environment through signal information of a communication method of transmitting and receiving information to and from the second electronic device 312 or the third electronic device 314 and determine another electronic device to transmit notification with reference to a designated priority of an element such as stability of a communication method, an information transmitting and receiving speed of the connected communication method, or a distance that can transmit and receive according to communication signal intensity. The first electronic device 311 can determine the third electronic device 314 faster than that of the second electronic device 312 in an information transmitting and receiving speed of a connected communication method as another electronic device to transmit notification according to a designated condition and transmit output information of notification that has occurred in the first electronic device 311 to the third electronic device 314 . The third electronic device 314 can output information about notification that has occurred in the first electronic device 311 according to received information.
[0091] According to an embodiment, when determining another electronic device to transmit notification, the first electronic device 311 can determine an electronic device having low real time dependence of an application executing in at least one another electronic device as a device to transmit notification. For example, the first electronic device 311 can determine an application that should execute without stopping such as a moving picture photographing application or a game application as an application having high real time dependence. Further, for example, the first electronic device 311 can determine an application that can execute after stopping such as Internet as an application having low real time dependence. According to an embodiment, the first electronic device 311 can check real time dependence of an application in which another electronic device including the second electronic device 312 and the third electronic device 314 is executing. When outputting notification information to an electronic device executing, for example, some application, real time dependence can be numerical value information of damage (e.g., data damage) that can cause when executing the application. According to an embodiment, the first electronic device 311 can use a real time dependence numerical value as information for determining an electronic device to provide notification. According to an embodiment, the first electronic device 311 can store information (e.g., real time dependence information of an application) about at least one application included in the second electronic device 312 or the third electronic device 314 at a database through the status information in which the second electronic device 312 or the third electronic device 314 receives, and the database can check information about a priority (e.g., a priority determined based on real time dependence) of an application stored at each electronic device. According to an embodiment, the first electronic device 311 can compare real time dependence information about a media data reproduction operation executing in the second electronic device 312 and real time dependence information of a recording operation of media data performing in the third electronic device 314 and can determine the second electronic device 312 executing an application having low real time dependence to output notification information. The first electronic device 311 can transmit output information of notification information that has occurred to the second electronic device 312 . The second electronic device 312 can output notification information that has occurred in the first electronic device 311 according to the received information.
[0092] FIGS. 4A to 4E are diagrams illustrating the operations of controlling a notification information output in an electronic device according to various embodiments of the present invention.
[0093] Referring to FIGS. 4A to 4E , for example, the electronic device 101 can be represented with a first electronic device 401 , and the electronic device 102 can be a second electronic device 402 . According to an embodiment, the first electronic device 401 can be represented with a smart phone, and the second electronic device 402 can be represented with a wearable smart watch.
[0094] Hereinafter, various embodiments of the present invention will be described with reference to FIG. 4A .
[0095] Referring to FIG. 4A , while executing at least one application, the first electronic device 401 can detect that an event to provide notification has occurred. The first electronic device 401 can determine whether to output notification information with reference to attribute information (e.g., real time dependence information) of at least one executing application. When it is determined that the first electronic device 401 does not output notification information, the first electronic device 401 can determine the second electronic device 402 as an electronic device to output notification information and transmit output information of the detected notification information to the determined second electronic device 402 .
[0096] When the first electronic device 401 detects an event to provide notification, the first electronic device 401 can determine whether the first electronic device 401 is to output notification information. According to an embodiment, when the first electronic device 401 detects an event to provide notification information, the first electronic device 401 can acquire the status information of the first electronic device 401 . When the first electronic device 401 executes at least one application at a time point that detects an event to provide notification, the first electronic device 401 can determine whether at least one executing application is an application designated to display notification. According to an embodiment, while recording media data, the first electronic device 401 can receive a calling request from ‘Joseph’. When a calling request event occurs while media data recording with reference to, for example, a database of an executing media data recording application or a database for processing an event to provide notification that has occurred in the first electronic device 401 , the first electronic device 401 can determine whether the first electronic device 401 is set to output notification about a calling request. When the first electronic device 401 is set to not display notification of a calling request event that has occurred while media data recording, the first electronic device 401 can control another electronic device to output information about a calling request that has occurred. The first electronic device 401 can check at least one another electronic device that can connect through the communication interface 170 . The first electronic device 401 can receive the status information from at least one connected another electronic device and select at least one another electronic device to transmit notification information with reference to the status information. According to an embodiment, the first electronic device 401 in a wearing the status and that is not in a maximum power saving mode or a sleep mode (e.g., a disabling status) can be designated to have a high priority to be determined as a device to provide notification at a database. When the first electronic device 401 checks that the second electronic device 402 is in a wearing status and is not in a sleep mode status through the status information received from the second electronic device 402 , the first electronic device 401 can transmit notification information about a calling request received from ‘Joseph’ to the second electronic device 402 based on database information, and the second electronic device 402 can output notification according to received information.
[0097] According to another embodiment, the first electronic device 401 can detect an alarm event output while executing a navigation application. The first electronic device 401 can determine whether the first electronic device 401 is set to output notification about an alarm event output while executing a navigation application with reference to a database of the executing navigation application or a database for processing an event to provide notification that has occurred in the first electronic device 401 . When the first electronic device 401 is set to not display notification about an alarm event output that has occurred while executing a navigation application, the first electronic device 401 can control another electronic device to output information about an alarm event that has occurred. The first electronic device 401 can check at least one another electronic device that can connect through the communication interface 170 . The first electronic device 401 can receive the status information from at least one connected another electronic device and select at least one another electronic device to transmit notification information with reference to the status information. According to an embodiment, a wearing electronic device that is not in a state such as a maximum power saving mode or a sleep mode can be designated to have a high priority to be determined as an electronic device to provide notification at a database of the first electronic device 401 . When the first electronic device 401 checks that the second electronic device 402 is in a wearing status and is not in a sleep mode status through the status information received from the second electronic device 402 , the first electronic device 401 can transmit notification information of an alarm event that has occurred to the second electronic device 402 based on database information, and the second electronic device 402 can output alarm according to received information.
[0098] According to various embodiments, the first electronic device 401 can determine whether the first electronic device 401 is to output information about an event to provide notification that has occurred according to a checked time. According to an embodiment, the first electronic device 401 can receive a calling request from ‘Joseph’ while recording media data. When a calling request event occurs while media data recording with reference to a database of executing media data recording or a database for processing an event to provide notification that has occurred in the first electronic device 401 , the first electronic device 401 can determine whether the first electronic device 401 is set to output notification about the calling request. When the first electronic device 401 is set (designated) not to display notification about a calling request event that has occurred in the first electronic device 401 from a time point ‘11:00’ to a time point ‘14:30’, the first electronic device 401 can control another electronic device to output information about a calling request event that has occurred from a time point ‘11:00’ to a time point ‘14:30’. When a calling request event has occurred in the first electronic device 401 from a time point ‘11:00’ to a time point ‘14:30’, the first electronic device 401 can check at least one another electronic device that can output notification about the calling request event instead of the first electronic device 401 . The first electronic device 401 can receive the status information from at least one connected another electronic device and select at least one another electronic device to transmit notification information with reference to the status information. According to various embodiments, when the first electronic device 401 determines at least one another electronic device to output notification about an event that has occurred, the first electronic device 401 can determine at least one another electronic device to output notification through information (designated information) about a designated range of at least one information of various status information such as location information of the first electronic device 401 , illumination amount information of the first electronic device 401 or an area in which the first electronic device is located, and moving speed information of the first electronic device instead of limiting to designated time information.
[0099] Hereinafter, various embodiments of the present invention will be described with reference to FIGS. 4B and 4C .
[0100] Referring to FIGS. 4B and 4C , the first electronic device 401 can detect that an event to provide notification has occurred while performing at least one operation. The first electronic device 401 can determine whether to output notification with reference to at least one executing application, and when it is determined that the first electronic device 401 does not output notification, the first electronic device 401 can determine the second electronic device 402 as an electronic device to output notification and transmit output information of detected notification to the determined second electronic device 402 . When the second electronic device 402 does not check an output result of notification information according to output information of notification transmitted to the second electronic device 402 , the first electronic device 401 can check importance level information about an event to provide notification that has occurred at a database, and when operation is not designated to output notification in real time, the first electronic device 401 can retransmit notification information to the second electronic device 402 or can transmit notification information to another electronic device.
[0101] According to an embodiment, the first electronic device 401 can detect message data reception while executing a navigation application. The first electronic device 401 can determine whether the first electronic device 401 is set to output notification of message data reception while executing a navigation application with reference to a database of an executing navigation application or a database for processing an event to provide notification that has occurred in the first electronic device 401 . When the first electronic device 401 is set not to display notification of message reception that has occurred while executing a navigation application, the first electronic device 401 can control another electronic device to output information about message reception that has occurred. The first electronic device 401 can check at least one another electronic device that can connect through the communication interface 170 . The first electronic device 401 can receive the status information from at least one connected another electronic device and select at least one another electronic device to transmit notification information with reference to the status information. According to another embodiment, when the first electronic device 401 does not check whether the second electronic device 402 outputs notification of message data, having transmitted to the second electronic device 402 or when it is determined that the second electronic device 402 does not output notification about message data, the first electronic device 401 can retransmit notification about message data to the second electronic device 402 and transmit notification information to another electronic device so that another electronic device connected to the first electronic device 401 outputs notification.
[0102] According to another embodiment, when the first electronic device 401 outputs information about message data reception determined as a priority (e.g., a priority determined based on real time dependence) lower than that of a navigation application and that has occurred while executing an application having high real time dependence such as a navigation application, if a connected another electronic device that can output notification information instead of the first electronic device 401 is not checked, the first electronic device 401 can hold the operation of outputting notification of received message data. When the first electronic device 401 checks and connects at least one another electronic device that can connect, for example, the second electronic device 402 while operating a navigation application or when the first electronic device 401 checks that the first electronic device 401 is connected to the second electronic device 402 , the first electronic device 401 can transmit holding notification information about message data reception to the second electronic device 402 .
[0103] Further, according to an embodiment, when outputting information about message data reception determined as having a lower priority (e.g., a priority determined based on real time dependence) than that of a navigation application and that has occurred while executing an application having a high priority (e.g., a priority determined based on real time dependence) such as a navigation application, if a connected another electronic device that can output notification information instead of the first electronic device 401 is not checked or if it is not checked that transmitted notification information about message data reception is output, the first electronic device 401 can control to terminate the navigation application and control the first electronic device 401 to output notification information about message data reception.
[0104] According to various embodiments, when the first electronic device 401 outputs information about a calling request determined as having a higher priority (e.g., a priority determined based on real time dependence) than that of a navigation application and that has occurred while executing an application having high real time dependence such as a navigation application, if a connected another electronic device that can output notification information instead of the first electronic device 401 is not checked or if it is not checked that transmitted notification information about message data reception is output, the first electronic device 401 can control the first electronic device 401 to output notification information about message data reception.
[0105] The foregoing various embodiments can be performed according to information set or stored at a database stored at the first electronic device 401 and/or a database of each application or control information set at a control module that controls an output of the notification.
[0106] Hereinafter, various embodiments of the present invention will be described with reference to FIGS. 4D and 4E .
[0107] Referring to FIGS. 4D and 4E , while executing at least one operation (e.g., application), the first electronic device 401 can detect that an event to provide notification has occurred. The first electronic device 401 can determine whether to output notification with reference to at least one operation being performed, and when it is determined that the first electronic device 401 does not output notification, the first electronic device 401 can determine the second electronic device 402 as an electronic device to output notification, and the first electronic device 401 can transmit output information of the detected notification to the determined second electronic device 402 .
[0108] According to an embodiment, the first electronic device 401 can receive a calling request from ‘Joseph’ while performing a large capacity data processing such as an on-line system updating operation. The first electronic device 401 can determine whether the first electronic device 401 is set to output notification of calling request reception while performing an on-line system updating operation with reference to a database for processing an event to provide notification that has occurred in the first electronic device 401 . When the first electronic device 401 is set not to display notification of a calling request that has occurred while an on-line system updating operation, the first electronic device 401 can control another electronic device to output information about a calling request that has occurred. The first electronic device 401 can determine the second electronic device 402 having a few data load in at least one connected another electronic device to output information about a calling request that has occurred in the first electronic device 401 and transmit notification information about a calling request to the second electronic device 402 . The first electronic device 401 can enable the first electronic device 401 to perform operations such as a sound or a vibration together with the operation of transmitting notification information about a calling request to the second electronic device 402 , enable the display 150 of the first electronic device 401 to output information about notification information transmission, and to perform a combined operation of at least two operations of a sound, a vibration, and the operation of outputting to the display.
[0109] FIGS. 5A and 5D are diagrams illustrating the operation of controlling a notification information output in an electronic device according to various embodiments of the present invention.
[0110] Hereinafter, various embodiments of the present invention will be described with reference to FIG. 5A .
[0111] Referring to FIG. 5A , for example, the electronic device 101 can be represented with a first electronic device 501 , and the electronic device 102 can be represented with a second electronic device 502 . According to an embodiment, the first electronic device 501 can be represented with a smart phone, and the second electronic device 502 can be represented with a wearable smart watch.
[0112] Referring to FIG. 5A , when the first electronic device 501 detects an event to provide notification, the first electronic device 501 can acquire the status information of the first electronic device 501 and the status information of the connected second electronic device 502 and determine at least one electronic device that outputs information about an event to provide notification that has occurred in the first electronic device 501 according to a state of the first electronic device 501 and the second electronic device 502 .
[0113] According to an embodiment, the first electronic device 501 can receive a calling request from ‘Joseph’, which is an event to provide notification and acquire the status information of the first electronic device 501 . The first electronic device 501 can receive a calling request from ‘Joseph’ through the CP and determine (or check) that the AP is in a sleep mode status. The first electronic device 501 can determine not to output notification of a calling request that has occurred, when the AP is in a sleep mode but determine the second electronic device 502 to output notification. The first electronic device 501 can acquire the status information from the connected second electronic device 502 . The first electronic device 501 can check that the second electronic device 502 is in a wearing status from the acquired status information of the second electronic device 502 and transmit notification information about a calling request to the second electronic device 502 so that the wearing second electronic device 502 outputs information about a calling request that has occurred in the first electronic device 501 . Further, the first electronic device 501 or the second electronic device 502 can determine a distance between the first electronic device 501 and the second electronic device 502 through at least one device that can determine a proximity status, such as a proximity detection sensor or a communication module (e.g., an NFC module, a Wifi module, and a Bluetooth (BT) module). When it is determined that the second electronic device 502 is located within a designated distance from the first electronic device 501 , the first electronic device 501 can determine so that the second electronic device 502 outputs notification. According to an embodiment, when the first electronic device 501 receives a calling request according to information stored at a database, the first electronic device 501 can check a status of the AP. When the AP of the first electronic device 501 is in a sleep mode, the first electronic device 501 can acquire the status information about at least one connected another electronic device. When it is determined (or checked) that the wearable second electronic device 502 is in a wearing status through the acquired status information and in a state tagged with the first electronic device 501 (a state in which the first electronic device 501 and the second electronic device 502 are located within a designated distance range) through an NFC communication module, the first electronic device 501 can determine the second electronic device 502 to output notification of the received calling request and transmit notification information about a calling request to the second electronic device 502 .
[0114] According to another embodiment, when the first electronic device 501 receives message data while performing an audio dedicated communication operation, the first electronic device 501 can determine another electronic device to output notification information about message information in which the first electronic device 501 receives according to information stored at a database. The first electronic device 501 can acquire the status information about at least one connected another electronic device. The first electronic device 501 can detect that the wearable second electronic device 502 is in a wearable status through the acquired status information and detect Bluetooth communication signal intensity of the first electronic device 501 in the second electronic device 502 through Bluetooth communication, and when Bluetooth communication signal intensity is in a designated range (when a distance range between the first electronic device 501 and the second electronic device 502 determined as communication signal intensity is within a designated distance range), the first electronic device 501 can determine the second electronic device 502 to output notification of the received message data and transmit notification information about message data to the second electronic device 502 .
[0115] Referring to FIG. 5B , when the first electronic device 501 receives a calling request in a standby mode status or while performing operations such as Internet surfing in which a priority (e.g., a priority determined based on real time dependence) is not high, the first electronic device 501 can determine the first electronic device 501 to output notification of a calling request with reference to information stored at, for example, a database. Connected another electronic device can be a second electronic device 502 , and the second electronic device 502 can receive the status information. The first electronic device 501 can check that the wearable second electronic device 502 is not in a wearing status and/or is in a sleep mode status through the status information of the second electronic device 502 . When the connected second electronic device 502 is not in a wearing status and/or operates in a sleep mode status, the first electronic device 501 may not process the second electronic device 502 to output notification information about a calling request in which the first electronic device 501 receives but process the first electronic device 501 to output notification information.
[0116] Hereinafter, various embodiments of the present invention will be described with reference to FIGS. 5C and 5D .
[0117] Referring to FIGS. 5C and 5D , when the electronic device 101 detects occurrence of an event to provide notification, when determining whether the electronic device 101 is to output corresponding notification, the electronic device 101 can determine the electronic device 101 to output notification through information that is set at, for example, a database stored at the electronic device 101 or a database of an application performing in the electronic device 101 at a time point in which an event to provide notification has occurred. When determining whether to display notification of the operation that has occurred, the electronic device 101 can refer to the status information of the electronic device 101 .
[0118] Referring to FIG. 5D , for example, when the electronic device 101 detects an event to provide notification in the electronic device 101 , in a method of determining whether the electronic device 101 is to output corresponding notification, the electronic device 101 can refer to at least one information of a state, a location and/or a motion of the electronic device 101 determined through information measured through at least one sensor in which the electronic device 101 includes.
[0119] According to an embodiment, the electronic device 101 can acquire information about a coordinate (two-dimension or three-dimension) that determines a motion of the electronic device 101 in which the electronic device 101 locates through a gyro sensor at a time point that detects an event to provide notification, and when the acquired coordinate is included in a range of a motion that determines the electronic device 101 to output notification stored at a database of the electronic device 101 , the electronic device 101 can output notification.
[0120] According to another embodiment, the electronic device 101 can acquire information about a space coordinate (e.g., a GPS coordinate) at which the electronic device 101 locates at a time point that detects an event to provide notification through a GPS functionally connected to the electronic device, and when information about the acquired coordinate is included in a range of a coordinate that determines the electronic device 101 to output notification stored at a database of the electronic device 101 , the electronic device 101 can output notification.
[0121] According to another embodiment, the electronic device 101 can acquire information about a speed in which the electronic device 101 moves at a time point that detects an event to provide notification through an acceleration sensor, and when information about the acquired speed is included in a range of a speed that determines the electronic device 101 to output notification stored at a database of the electronic device 101 , the electronic device 101 can output notification.
[0122] Referring to FIG. 5D , when the electronic device 101 detects an event to provide notification in a state of performing at least one function, in a method of determining whether the electronic device 101 is to output corresponding notification, the electronic device 101 can refer to at least one information of a state, a location and/or a motion of the electronic device 101 determined through information measured through at least one sensor in which the electronic device 101 includes.
[0123] According to an embodiment, the electronic device 101 can detect occurrence of an event to provide notification while controlling a document displayed in the display 150 of the electronic device 101 through a pupil detection sensor (e.g., an image sensor). When the electronic device 101 detects a pupil through a pupil detection sensor, the electronic device 101 determines that the user controls the electronic device 101 and the electronic device 101 can display notification of an event that has occurred in the electronic device 101 through the electronic device 101 .
[0124] The electronic device 101 can compare information acquired by at least one sensor of various sensors in which the electronic device 101 includes and information stored at a database and determine whether the electronic device 101 or at least one another electronic device is to output notification of an event to provide notification that has occurred in the electronic device 101 without limiting to the foregoing embodiment. Further, the foregoing various embodiments can be performed according to information set or stored at a database stored at the electronic device 101 and/or a database of each application, or control information set at a control module that controls an output of the notification.
[0125] FIG. 6 is a diagram illustrating the operation of processing notification information in an electronic device according to various embodiments of the present invention.
[0126] Referring to FIG. 6 , for example, the electronic device 101 can be represented with a first electronic device 601 and the electronic device 102 can be represented with a second electronic device 602 . According to an embodiment, the first electronic device 601 can be represented with a smart phone, and the second electronic device 602 can be represented with a wearable smart watch.
[0127] When the first electronic device 601 detects that an event to provide notification occurs, the first electronic device 601 can process the first electronic device 601 or at least one another electronic device to output notification information about an event that has occurred. The first electronic device 601 can process the first electronic device 601 or the second electronic device 602 to output notification about an event that has occurred and acquire information about an event notification output from the second electronic device 602 . The first electronic device 601 can determine whether an event that has occurred in the first electronic device 601 has been checked through information about an event notification output received in the second electronic device 602 . The first electronic device 601 can synchronize information on whether an event that has occurred has been checked with recorded information of an event occurred at the first electronic device 601 or a database of an application connected to an event. When it is determined that an event that has occurred is not check in the first electronic device 601 or at least one another electronic device (e.g., the second electronic device 602 ) that transmits notification information so as to output notification about an event, the first electronic device 601 can output or re-output notification about a corresponding event or can transmit notification information about an event to the second electronic device 602 so that the connected second electronic device 602 outputs or re-outputs.
[0128] According to an embodiment, in order to enable the second electronic device 602 to display notification information about a received ‘character #01’ and ‘character #03’, the first electronic device 601 can transmit notification information about the ‘character #01’ and notification information about the ‘character #03’ to the second electronic device 602 . The first electronic device 601 can store information about the ‘character #01’ and the ‘character #03’ transmitted to the second electronic device 602 (notification information transmitted to the second electronic device 602 ) and information 611 , 615 , 621 , and 625 (information about notification check) about a state in which the ‘character #01’ and the ‘character #03’ are not checked at a database 620 of the first electronic device 601 and/or a database 630 of a character application connected to ‘character #01’ data ‘character #03’ data.
[0129] According to an embodiment, the first electronic device 601 can check whether the first electronic device 601 has been transmitted notification information (e.g., the ‘character #01’ and the ‘character #03’) to another electronic device (e.g., the second electronic device 602 ). When the first electronic device 601 does not transmit notification information, the first electronic device 601 can determine whether the user of the first electronic device 601 checks notification information. If the user of the first electronic device 601 does not check notification information, the first electronic device 601 can designate the notification information as non-transmission notification at the database 620 of the first electronic device 601 or a character application database 630 . Additionally or alternatively, the first electronic device 601 can transmit notification information designated as non-transmission notification to another electronic device (e.g., the second electronic device 602 ).
[0130] For example, when the first electronic device 601 does not transmit a ‘character #01’ and a ‘character #02 to the second electronic device 602 , the first electronic device 601 can check that the user of the first electronic device 601 does not check the ‘character #01’ and the ‘character #02’ based on information 611 on whether the ‘character #01’ and the ‘character #02’ are checked. In this case, the first electronic device 601 can transmit the ‘character #01’ and the ‘character #02’ to the second electronic device 602 communicating with the first electronic device 601 .
[0131] The second electronic device 602 can output notification information about the ‘character #01’ in which the first electronic device 601 receives and notification information about the ‘character #03’ and store information on whether the ‘character #01’ has been checked and information on whether the ‘character #03’ has been checked at a database 620 of the second electronic device 602 and/or a database (not shown) of a character application of the second electronic device 602 . The second electronic device 602 can transmit information of the database 620 in which information 621 on whether the ‘character #01’ has been checked and information 625 on whether the ‘character #03’ has been checked is stored to the first electronic device 601 . When the second electronic device 602 is not connected to the first electronic device 601 through the communication interface 170 , the second electronic device 602 can hold transmission of the information 621 of the database 620 on whether the ‘character #01 has been checked and the information 625 on whether the ‘character #03’ has been checked, and at a time point at which the second electronic device 602 is connected to the first electronic device 601 , the second electronic device 602 can transmit the information 621 of the database 620 on whether the ‘character #01 has been checked and the information 625 on whether the ‘character #03’ has been checked to the first electronic device 601 . Alternatively, the second electronic device 602 can include and transmit the information 621 on whether the ‘character #01 has been checked and the information 625 on whether the ‘character #03’ has been checked in the status information transmitting to the first electronic device 601 .
[0132] The first electronic device 601 can combine the information 621 on whether the ‘character #01 has been checked and the information 625 on whether the ‘character #03’ has been checked received from the second electronic device 602 to the database 620 of the first electronic device 601 and update the information 621 on whether the ‘character #01 has been checked and the information 625 on whether the ‘character #03’ has been checked at a database 630 of a character application connected to the ‘character #01 and the ‘character #03’.
[0133] According to an embodiment, the first electronic device 601 can update information in which the ‘character #01’ transmitted to the second electronic device has been checked by the user of the second electronic device 602 at the database 620 of the first electronic device 601 . Further, the first electronic device 601 can transmit the information to the second electronic device 602 , and the second electronic device 602 can update the information at the database 620 of the second electronic device 602 .
[0134] According to an embodiment, the first electronic device 601 can detect information about an event that is not checked with reference to the database 620 and a database 630 or 640 in which each application includes. When the first electronic device 601 checks information 615 about the ‘character #03’ of the database 620 of FIG. 6 , the first electronic device 601 can determine that the ‘character #03’ has been output from the second electronic device 602 and that the ‘character #03’ is in a state that is not checked. Additionally or alternatively, according to an embodiment, the first electronic device 601 can output notification about the ‘character #03’ with reference to the database 620 or the status information received in the second electronic device 602 . When the ‘character #03’ has been checked in the first electronic device 601 by the user of the first electronic device 601 , the first electronic device 601 can update information in which the ‘character #03’ has been checked by the user of the first electronic device 601 at the database 620 of the first electronic device 601 . Further, in order to update the information at the database 620 of the second electronic device 602 , the first electronic device 601 can transmit the information to the second electronic device 602 .
[0135] According to a embodiment, in order to enable the second electronic device 602 to output the ‘character #03’, the first electronic device 601 can retransmit notification information about the ‘character #03’ to the second electronic device 602 . Further, according to an embodiment, in order to enable a third electronic device (e.g., the third electronic device 314 ) (not shown), which is another external device to output the ‘character #03’, the first electronic device 601 can transmit notification information about the ‘character #03’ to the third electronic device. Alternatively, the first electronic device 601 may not retransmit the transmitted notification information about the ‘character #03’ to the second electronic device 602 and can await until the second electronic device 602 checks the transmitted notification information. When the first electronic device 601 receives information on whether the ‘character #03’ has been checked or when the ‘character #03’ is not checked for a designated time or more, the first electronic device 101 can update information on whether the ‘character #03’ has been checked at the database 620 of the first electronic device 601 and the database 630 of a character application.
[0136] According to a embodiment, the first electronic device 601 can output notification about a ‘weather #02’ event that has occurred and record information about a check status checked in the first electronic device 601 at the database 620 together with information 613 about ‘weather #02’, and update the information at a database 640 of a weather application. Alternatively, according to an embodiment, notification (e.g., weather #02) checked in the first electronic device 601 can be deleted from the database 620 or the database 640 of a weather application. The first electronic device 601 can determine an event that has been output one time or more but that was not checked according to the database 620 or a database of each application and process to re-output the event that was not checked.
[0137] According to various embodiments, the electronic device (e.g., the electronic device 101 ) that provides notification can include a determining module (e.g., a determining module 210 ) for determining notification information, an acquiring module (e.g., an acquiring module 230 ) for acquiring the status information about at least one of the electronic device or at least one of external device communicating with the electronic device, and a providing module (e.g., a providing module 240 ) for providing the notification information through at least one of the electronic device or the at least one of external device based on the status information.
[0138] According to various embodiments, the acquiring module can acquire information corresponding to designated information based on an attribute of the notification information as the status information.
[0139] According to various embodiments, the providing module can provide the notification information through a device in which the user presently uses based on the status information about the user of the electronic device acquired as the status information.
[0140] According to various embodiments, when an application executing in the electronic device has a priority higher than that of the notification information, the providing module can transmit the notification information to the at least one external device.
[0141] According to various embodiments, the determining module can determine information in which the user of the electronic device is not checked through the electronic device as the notification information.
[0142] According to various embodiments, the determining module can determine information in which the electronic device does not transmit to the at least one external device as the notification information.
[0143] According to various embodiments, the acquiring module can acquire the notification information having a first priority and information about an application having a second priority executing in the electronic device.
[0144] According to various embodiments, the providing module can provide the notification information through the electronic device based on that the first priority is higher than the second priority and can provide the notification information through the at least one external device based on that the first priority is lower than the second priority.
[0145] According to various embodiments, the providing module can provide the notification information through an enabled device of the electronic device and the at least one external device.
[0146] According to various embodiments, the providing module can provide the notification information through a device that acquires user information corresponding to information set to be related to the user of the electronic device. For example, when the electronic device acquires the user's touch input and when the at least one external device does not acquire the user's touch input, the providing module can provide the notification information through the electronic device.
[0147] According to various embodiments, when power source information or load information acquired as the status information corresponds to a range designated to the electronic device, the providing module can provide the notification information through a device corresponding to the status information.
[0148] According to various embodiments, when the electronic device or the at least one external device is located at a first location, the providing module can provide the notification information through the electronic device, and when the electronic device or the at least one external device is located at a second location, the providing module can provide the notification information through the at least one external device.
[0149] According to various embodiments, when time information acquired as the status information is a first time, the providing module can provide the notification information through the electronic device, and when time information acquired as the status information is a second time, the providing module can provide the notification information through the at least one external device.
[0150] According to various embodiments, when communication information or distance information between the electronic device and the at least one external device belongs to a range designated to the electronic device, the providing module can transmit the notification information to the at least one external device.
[0151] According to various embodiments, the electronic device includes a first processor for processing an application and a second processor for controlling communication with the electronic device, and when the first processor executes the application, the providing module can transmit the notification information to the at least one external device through the second processor.
[0152] According to various embodiments, the electronic device can acquire check information on whether the user of the electronic device and the at least one external device checks the notification information or transmitting information on whether the electronic device has transmitted the notification information to the at least one external device and store the check information or the transmitting information at a database functionally connected to the electronic device.
[0153] According to various embodiments, when the check information or the transmitting information is changed, the electronic device can update the database.
[0154] According to various embodiments, the acquiring module can be set to acquire at least one of wearing information, sight line information, gesture information, and authentication information of the user of at least one of the electronic device and at least one external device as the status information.
[0155] According to various embodiments, the acquiring module can control to acquire the status information about whether at least one of the electronic device and at least one external device is using.
[0156] According to various embodiments, the determining module can control to determine notification information based on whether the user check input is acquired among at least one notification information related to the electronic device.
[0157] According to various embodiments, the acquiring module can acquire user input information acquired in the electronic device as the status information, and the providing module can control to provide notification information through at least one of the electronic device or at least one external electronic device based on user input information.
[0158] According to various embodiments, when the electronic device acquires user input information, the providing module provides notification information through the electronic device, and when the electronic device does not acquire user input information, the providing module can control to provide notification information through at least one external device. According to various embodiments, the acquiring module can be set to include sensor information detected by a sensor functionally connected to at least one of the electronic device or at least external device in user input information or the status information.
[0159] According to various embodiments, the providing module can provide the notification information through an enabled device of the electronic device and the at least one external device.
[0160] According to various embodiments, the acquiring module can be set to acquire enabling the status information of a display functionally connected to each of the electronic device and at least one external device as the status information.
[0161] According to various embodiments, the acquiring module acquires enabling the status information of the electronic device as the status information, and the providing module can control to provide notification information through at least one of the electronic device or at least one external electronic device based on the enabling status information. According to various embodiments, when the electronic device is in an enabling status, the providing module can control to provide notification information through the electronic device, and when the electronic device is in a disabling status, the providing module can control to provide notification information through at least one external device.
[0162] According to various embodiments, the acquiring module acquires attribute information of an application executing in the electronic device as the status information, and the providing module can control to provide notification information through at least one of the electronic device or at least one external electronic device based on attribute information of an application.
[0163] According to various embodiments, the determining module, the acquiring module, and the providing module are connected to a first processor that processes transmission and reception of information, the determining module determines notification information through the first processor, the acquiring module determines whether a second processor that controls operations of the electronic device through the first processor is in a state that can provide notification information, and the providing module can control to transmit notification information to a second electronic device through the first processor, if a second processor is not in a state that can provide notification information.
[0164] According to various embodiments, the electronic device includes a first processor and a second processor, and when the first processor determines notification information and the second processor executes an application, the providing module can control at least one external device to provide notification information through the first processor based on an attribute of the application.
[0165] According to various embodiments, the providing module can control to provide notification information through at least one of methods of outputting with a sound designated in the electronic device or at least one external device electronic device, displaying in at least one display unit, or vibrating the electronic device or at least one external device with a designated method.
[0166] According to various embodiments, when providing notification information with at least one external device, the acquiring module receives feedback information from at least one external device, having provided notification information, and the providing module can determine that notification information provided from at least one external device is not checked through the feedback information and provide notification information to retransmit the notification information to at least one external device. According to various embodiments, the acquiring module can control to acquire feedback information that records whether notification information provided to at least one external electronic device has been checked.
[0167] According to various embodiments, the determining module can determine that provided notification is not checked, and the providing module can control to provide again notification information.
[0168] According to various embodiments, the determining module can determine that provided notification is not checked, the acquiring module can acquire the status information of at least one external device, and the providing module can control the external device to provide notification information or to transmit notification information to at least one external device according to whether notification information determined as the status information can be provided.
[0169] According to various embodiments, the acquiring module can control to include at least one of enabling information of the electronic device or at least one external device, performing operation information, importance level information of a performing operation, battery residual quantity information, communication state information with a connected device, at least one acquired sensing information, information about a priority of an application or a function that can operate, and information on whether provided notification has been checked in the status information. According to various embodiments, the acquiring module can control to include distance information between an electronic device and at least one external electronic device acquired with at least one connected communication method in communication state information.
[0170] According to another embodiment, the electronic device can be an application for performing operation of determining notification information, operation of acquiring the status information related to at least one of the electronic device and at least one external device, and operation of controlling to provide notification information through at least one of the electronic device and at least one external device based on the status information, or a computer readable recording medium on which the application is recorded.
[0171] According to another embodiment, the first electronic device includes a touch screen that outputs notification information, a memory that stores the notification information in the first electronic device, and a notification processing module that processes the notification information; and at least one processor that executes the notification processing module, and the notification processing module can control to detect notification occurrence and to acquire the first status information on the first electronic device and control to output the notification or to transmit the notification information to the second electronic device according to whether notification determined as the first status information is output.
[0172] According to various embodiments, at step of transmitting notification information, the notification processing module receives the second status information of the connected second electronic device, and when the received the second status information represents a state that can output, the notification processing module can control to transmit notification information to the second electronic device. According to various embodiments, at step of transmitting notification information, the notification processing module can control the notification information to process an output of the notification of the second electronic device.
[0173] According to various embodiments, at step of transmitting notification information, the notification processing module receives each state information from the second electronic device and a third electronic device connected to the electronic device, and when the received state information of each of the second electronic device and the third electronic device represents a state that can output, the notification processing module can control to transmit the notification information to the second electronic device and/or the third electronic device.
[0174] According to various embodiments, when transmitting the notification information to the second electronic device, the notification processing module can control to receive feedback information from the second electronic device, to determine that the notification information in which the second electronic device outputs is not checked through the feedback information, and to retransmit the notification information to the second electronic device. According to various embodiments, after the notification processing module outputs the notification information from the second electronic device, the notification processing module can control to determine information that records whether the output notification information has been checked as the feedback information. According to various embodiments, the notification processing module can control the second electronic device to determine whether the notification information has been checked with operation of controlling at least one application connected to the notification information.
[0175] According to various embodiments, the notification processing module can control the second electronic device to determine whether the notification information has been checked with a load of the notification information.
[0176] According to various embodiments, the notification processing module can control to determine notification of at least one of a received calling request, a received message, and notification of an alarm operation as the notification.
[0177] According to various embodiments, the notification processing module can determine that the output notification is not checked when outputting the notification and control to re-output the notification.
[0178] According to various embodiments, the notification processing module can control to determine that the output notification is not checked when outputting the notification, to acquire the second status information of the electronic device, and to re-output the notification or to retransmit the notification information to the second electronic device according to whether notification determined as the second status information can be output.
[0179] According to various embodiments, the notification processing module can control to include at least one of enabling information, performing operation information, importance level information of the performing operation, and battery residual quantity information of the first electronic device, communication state information with the second electronic device, at least one acquired sensing information, information about a priority of an application or a function that can operate, and information on whether output notification has been checked as the status information of the first electronic device and can control to include at least one of enabling information, performing operation information, importance level information of the performing operation, and battery residual quantity information of the second electronic device, communication state information with the first electronic device, at least one acquired sensing information, information about a priority of an application or a function that can operate, and information on whether output notification has been checked as the status information of the second electronic device.
[0180] According to various embodiments, the notification processing module can detect at least one of information that detects a pupil of the user and information that detects a touch and control to determine the detected information as sensing information. According to various embodiments, the notification processing module can further include distance information between the first electronic device and the second electronic device acquired with at least one communication method and control to determine the first status information or the second status information.
[0181] According to another embodiment, an electronic device can include a touch screen that outputs notification information, a memory that stores the notification information in the electronic device, a notification processing module that processes the notification information, and at least one processor that executes the notification processing module, and in the notification processing module, a first processor that processes transmission and reception of information receives notification information, and the first processor determines whether a second processor that controls operation of the electronic device is in a state that can control an output of the notification information, and when the second processor is not in a state that can control an output of the notification information, the first processor can control to transmit the notification information to the second electronic device.
[0182] FIG. 7 is a flowchart illustrating the operation of processing notification information in an electronic device according various embodiments.
[0183] Referring to FIG. 7 , the electronic device 101 can detect an event to provide notification, acquire the status information of the electronic device 101 and another electronic device, and determine at least one electronic device to output notification information through a database of the electronic device 101 and the acquired status information, and an output notification or a transmit notification information to the determined electronic device.
[0184] The electronic device 101 can detect that an event to provide notification occurs, such as an alarm function necessary to notify to the user and a phone connection and message data received through the communication interface 170 ( 701 ). The electronic device 101 can detect an event to provide notification in a sleep mode the status and detect an event to provide notification in a state in which at least one operation or function is performing.
[0185] The electronic device 101 can acquire the status information about the electronic device 101 or at least one connected another electronic device ( 703 ). The status information that the electronic device 101 or at least one another electronic device acquires can include at least one of information on whether the electronic device 101 is in an enabling status or a disabling status (can be determined by whether the AP or the CP is in an enabling status), a performing operation or function when the electronic device 101 is in an enabling status, the status information of the user and/or each device information measured through at least one sensor in which the electronic device 101 includes among sensors such as a touch sensor, a grip sensor, a motion sensor (e.g., an acceleration sensor, a gyro sensor), an image sensor, a proximity detection sensor, a microphone, and a living body detection sensor (a fingerprint detection sensor, a vein detection sensor, and a temperature sensor), information about a communication state with at least one another electronic device connected to the electronic device 101 or at least one communication method that can be connected to another electronic device 602 , distance information between two devices checked through signal strength of a communication method in which the electronic device 101 and the another electronic device 602 are connected, information about a priority of an application and/or a function that can operate in the electronic device 101 , and information on whether output notification has been checked.
[0186] The electronic device 101 can determine at least one electronic device to output notification about an event that has occurred through the acquired status information and information stored at a database ( 705 ).
[0187] According to an embodiment, when the electronic device 101 detects that an event to provide notification occurs in a sleep mode status, the electronic device 101 can determine another electronic device to output notification according to information stored at a database and the acquired status information. According to an embodiment, when the electronic device 101 is in an enabling status, the electronic device 101 can determine a priority of a performing function and an event to provide notification with reference to a database, and when it is determined that a priority of a function performing in the electronic device 101 is high, the electronic device 101 can determine another electronic device to output notification through information stored at a database and the acquired status information. According to another embodiment, when it is determined that a wearable device (or an electronic device) connected to the electronic device 101 is in a wearing status or when it is determined that a wearing device is located within a designated distance from the electronic device 101 , the electronic device 101 can determine the wearable device in which the user is wearing to output notification about an event to provide notification that has occurred in the electronic device 101 .
[0188] The electronic device 101 detects an event to provide notification and when it is determined that the first electronic device 101 outputs notification information, the electronic device 101 can output corresponding notification ( 707 ). According to an embodiment, when it is determined that the electronic device 101 outputs received message data, the electronic device 101 can output the received message data with a method of generally outputting a received message. When the electronic device 101 outputs message data and checks a corresponding message, the electronic device 101 can store information about check at a database or a database of a message (character) application connected to message data.
[0189] According to another embodiment, the electronic device 101 detects an event to provide notification and when it is determined that another electronic device connected to the first electronic device 101 outputs notification information, the electronic device 101 can transmit output information of corresponding notification to the determined another electronic device. According to an embodiment, when the electronic device 101 receives an e-mail while reproducing media data, the electronic device 101 can determine another electronic device to output notification about e-mail reception through a database and the acquired status information. The electronic device 101 can transmit information that processes to output notification about e-mail reception to the determined another electronic device. The electronic device 101 can receive information about whether an e-mail corresponding to notification output from another electronic device, having transmitted notification information has been checked.
[0190] When the electronic device 101 performs operation 707 , an embodiment of FIG. 7 can be terminated.
[0191] FIG. 8 is a flowchart illustrating the operation of providing notification information in an electronic device according to various embodiments.
[0192] Referring to FIG. 8 , the electronic device 101 can detect an event to provide notification and control notification information so that the electronic device 101 or an external electronic device outputs notification. Here, the external electronic device can be the above-described another electronic device (e.g., an electronic device 602 , an electronic device 104 , or a server 164 ) and can be represented with the above-described various methods of an external device, the second electronic device 602 , and the third electronic device 104 .
[0193] The electronic device 101 can detect that an event to provide notification occurs in operation 801 . Here, an event to provide notification can be a receiving operation through the communication interface 170 such as phone connection and message data in the electronic device 101 and can be operation necessary to notify to the user, such as an alarm function.
[0194] The electronic device 101 can determine whether the electronic device is in an enable state in operation 803 . According to an embodiment, the electronic device 101 can include at least one processor, and the processor 160 can include an application processor (AP) or a communication processor (CP). The AP or the CP can be independently formed as each processor and be included in one processor. The AP can be a processor that controls operation of an application of the electronic device 101 or at least one partial device constituting the electronic device 101 , and the CP can be a processor that transmits and receives information to and from an external electronic device through short range wireless communication or communication using the network 162 . When the AP is in an enabling status, the electronic device 101 can perform operation 805 , and when the AP is in a disabling status, the electronic device 101 can perform operation 807 .
[0195] The AP can be in an enabling status and the electronic device 101 can determine whether the electronic device 101 satisfies a condition that can output notification through the AP in operation 805 . According to an embodiment, when the electronic device 101 performs at least one application and function, the electronic device 101 can detect occurrence of an event to provide notification. The electronic device 101 can determine whether to process the electronic device 101 or an external electronic device to output notification of operation that has occurred through a priority and/or importance level information between a performing application or function and an event to provide notification through information of a database and status information. When it is determined that the electronic device 101 outputs notification of operation that has occurred, the electronic device 101 can perform operation 811 , and when it is determined that the external electronic device outputs notification of operation that has occurred, the electronic device 101 can perform operation 807 .
[0196] The electronic device 101 can acquire status information of at least one external electronic device from at least one connected external electronic device. The electronic device 101 can determine whether an external electronic device is in a state that can output information about notification that has occurred through information of a database and the acquired status information in operation 807 . According to an embodiment, it can be determined whether the electronic device can output information about notification that has occurred in the electronic device 101 through at least one of information such as information on whether the external electronic device is wearing, when the external electronic device is a wearable electronic device, a priority and/or importance level information between operations that output information about notification that has occurred when there is an application or a function in which the external electronic device is performing, and a distance measured between the electronic device 101 and the external electronic device. When an external electronic device can output information about notification that has occurred in the electronic device 101 , the electronic device 101 can perform operation 809 , and when the external electronic device may not output information about notification that has occurred in the electronic device 101 , the electronic device 101 can perform operation 811 .
[0197] The electronic device 101 can transmit notification information to the external electronic device determined to output information about notification that has occurred in operation 809 . The external electronic device can output notification (or notification information) according to received notification information. The external electronic device can store information about whether the external electronic device has checked output notification and transmit the information to the electronic device 101 .
[0198] When the electronic device 101 performs operation 809 , an embodiment of FIG. 8 can be terminated. The electronic device 101 can output information about notification that has occurred ( 811 ). The electronic device 101 can store information about whether the electronic device 101 has checked output notification, and when a history that checks information corresponding to output notification is not detected in the electronic device 101 or connected another electronic device, the electronic device 101 can re-output output notification or can transmit or retransmit output notification to another electronic device.
[0199] When the electronic device 101 performs operation 811 , an external embodiment of FIG. 8 can be terminated.
[0200] According to various embodiments, a method of operating an electronic device can include operation of determining notification information, the operation of acquiring the status information related to at least one of the electronic device or at least one external device communicating with the electronic device, and operation of controlling to provide the notification information through at least one of the electronic device and at least one external device based on the status information.
[0201] According to various embodiments, the operation of determining can include operation in which the user of the electronic device determines information that is not checked through the electronic device as the notification information.
[0202] According to various embodiments, the operation of determining can include operation of determining information that is not transmit from the electronic device to the at least one external device as the notification information.
[0203] According to various embodiments, the operation of acquiring can include operation of acquiring the notification information having a first priority and information about an application having a second priority executing in the electronic device.
[0204] According to various embodiments, the operation of providing can include operation of providing the notification information through the electronic device based on that the first priority is higher than the second priority and providing the notification information through the at least one external device based on that the first priority is lower than the second priority.
[0205] According to various embodiments, the operation of providing can include operation of providing the notification information through a device that acquires user information corresponding to information set to be related to the user of the electronic device.
[0206] According to various embodiments, the operation of providing can include operation of providing the notification information through a device corresponding to the status information, when power source information or load information acquired as the status information corresponds to a range designated to the electronic device.
[0207] According to various embodiments, the operation of providing can include operation of providing the notification information through the electronic device, when the electronic device or the at least one external device is located at a first location and providing the notification information through the at least one external device, when the electronic device or the at least one external device is located at a second location.
[0208] According to various embodiments, the operation of providing can include operation of providing the notification information through the electronic device, when time information acquired as the status information is a first time and providing the notification information through the at least one external device, when time information acquired as the status information is a second time.
[0209] According to various embodiments, the operation of providing can include operation of transmitting the notification information to the at least one external device, when communication information or distance information between the electronic device and the at least one external device belongs to a range designated to the electronic device.
[0210] According to various embodiments, the electronic device can acquire check information on whether the user of the electronic device and the at least one external device has checked the notification information or transmitting information on whether the electronic device has transmitted the notification information to the at least one external device, and the check information or the transmitting information can be stored at a database functionally connected to the electronic device.
[0211] According to various embodiments, the operation of storing can include updating the database, when the check information or the transmitting information is changed.
[0212] According to various embodiments, the status information can include information on whether at least one of an electronic device or at least one external device is using.
[0213] According to various embodiments, the operation of determining can include operation of determining notification information based on whether a user check input has been acquired among at least one notification information related to the electronic device.
[0214] According to various embodiments, the operation of determining can include operation of acquiring user check information of each of at least one notification information from at least one external device.
[0215] According to various embodiments, the status information can include at least one information of power information and load information of at least one of an electronic device or at least one external device, status information of the user, and information designated at the electronic device.
[0216] According to various embodiments, the status information can include user input information acquired in the electronic device, and operation of controlling can include operation of controlling to provide notification information through at least one device of an electronic device or at least one external electronic device based on user input information. According to various embodiments, user input information can include information detected by a sensor functionally connected to at least one of an electronic device or at least one external device.
[0217] According to various embodiments, the operation of controlling can include operation of controlling to provide notification information through the electronic device, when the electronic device acquires user input information and to provide notification information through at least one external device, when the electronic device does not acquire user input information.
[0218] According to various embodiments, the operation of providing can include operation of providing the notification information through an enabled device of the electronic device and the at least one external device. According to various embodiments, the operation of controlling can include operation of controlling to provide notification information through the electronic device, when the electronic device is in an enabling status and to provide notification information through at least one external device, when the electronic device is in a disabling status.
[0219] According to various embodiments, the status information can include attribute information of an application performing in the electronic device, and operation of controlling can include operation of controlling to provide notification information through at least one device of an electronic device or at least one external electronic device based on attribute information of an application.
[0220] According to various embodiments, the electronic device can include a first processor for processing an application and a second processor for controlling communication of the electronic device, and operation of providing can include operation of transmitting the notification information to the at least one external device through the second processor, when the first processor executes the application.
[0221] According to various embodiments, the operation of providing can use at least one of methods of outputting with a sound designated in an electronic device or at least one external device, displaying with an image and/or a text in at least one display unit, and vibrating an electronic device or at least one external device with a designating method.
[0222] According to various embodiments, the electronic device includes a first processor and a second processor, and operation of determining can include operation of determining notification information in the first processor and operation of executing an application in the second processor.
[0223] According to various embodiments, the operation of controlling can include operation of controlling at least one external device to provide notification information through the first processor based on an attribute of an application.
[0224] According to various embodiments, the operation of providing notification information to at least one external device can further include operation of receiving feedback information from at least one external device that provides notification information, operation of determining notification information provided in at least one external device as information that is not checked through feedback information, and operation of retransmitting notification information to at least one external device. According to various embodiments, feedback information can be information that records whether provided notification information has been checked after at least one external electronic device provides notification information.
[0225] According to various embodiments, the operation of providing notification information can further include operation of determining that provided notification is not checked and operation of providing again notification information.
[0226] According to various embodiments, the operation of providing notification can further include operation of determining that notification is not checked, the operation of acquiring the status information of at least one external device, and operation in which the electronic device provides notification information or operation of transmitting notification information to at least one external device according to whether notification information determined as the status information can be provided.
[0227] According to various embodiments, the status information can include at least one of enabling information of the electronic device or at least one external device, performing operation information, importance level information of a performing operation, battery residual quantity information, communication state information with a connected device, acquired at least one sensing information, information about a priority of an application or a function that can operate, and information about whether provided notification has been checked. According to various embodiments, communication state information can further include distance information between an electronic device and at least one external device acquired with at least one connected communication method.
[0228] According to various embodiments, the status information can include at least one information of distance information or communication information between the electronic device and at least one external device.
[0229] According to another embodiment, a method of operating a first electronic device can include step of detecting notification occurrence, step of acquiring the first status information of the first electronic device, and the step of outputting the notification or transmitting the notification information to a second electronic device according to whether notification determined as the first status information is output.
[0230] According to various embodiments, the step of transmitting the notification information can include the step of receiving the second status information of the connected second electronic device and step of transmitting the notification information to the second electronic device when the received second status information represents a state that can be output. According to various embodiments, the step of transmitting the notification information can include control information that processes an output of the notification of the second electronic device in the notification information.
[0231] According to various embodiments, the step of transmitting the notification information can include the step of receiving the status information of each thereof from the second electronic device and a third electronic device connected to the electronic device and step of transmitting the notification information to the second electronic device and/or the third electronic device, when the received the status information of each of the second electronic device and third electronic device represents a state that can output.
[0232] According to various embodiments, the step of transmitting the notification information to the second electronic device can further include step of receiving feedback information from the second electronic device, the step of determining that the notification information in which the electronic device outputs is not checked through the feedback information, and the step of retransmitting the notification information to the second electronic device. According to various embodiments, the feedback information can be information that records whether the output notification information has been checked after the second electronic device outputs the notification information. According to various embodiments, whether the notification information has been checked can be determined with operation in which the second electronic device controls at least one application connected to the notification information. According to various embodiments, the notification can be determined as notification of at least one of a received calling request, a received message, and notification of an alarm operation.
[0233] According to various embodiments, the step of outputting notification can further include the step of determining that the output notification is not checked and step of re-outputting the notification.
[0234] According to various embodiments, the step of outputting notification can further include step of determining that the output notification is not checked, step of acquiring the second the status information of the electronic device, and the step of re-outputting the notification or retransmitting the notification information to the second electronic device according to whether notification determined as the second the status information can be output.
[0235] According to various embodiments, the first the status information of the first electronic device can include at least one of enabling information of the first electronic device, performing operation information, importance level information of the performing operation, battery residual quantity information, communication state information with a second electronic device, at least one acquired sensing information, information about a priority of an application or a function that can operate, and information on whether output notification has been checked, and the second the status information of the second electronic device can include at least one of enabling information of the second electronic device, performing operation information, importance level information of the performing operation, battery residual quantity information, communication state information with the first electronic device, at least one acquired sensing information, information about a priority of an application or a function that can operate, and information on whether output notification has been checked. According to various embodiments, each sensing information can detect at least one of information that detects the user's pupil and information that detects a touch. According to various embodiments, each communication status information can further include distance information between the first electronic device and the second electronic device that acquires with at least one communication method.
[0236] According to another embodiment, a method of operating an electronic device can include step in which a first processor that processes transmission and reception of information receives notification information, step of determining whether a second processor that controls operation of the electronic device is in a state that can output the notification information, and step in which the first processor transmits the notification information to a second electronic device, when the second processor is not in a state that can control an output of the notification information.
[0237] FIG. 9 is a block diagram illustrating hardware 900 according to various embodiments. The hardware 900 can form, for example, the entire or a portion of the electronic device 101 of FIG. 1 . Referring to FIG. 9 , the hardware 900 can include at least one processor 910 , a subscriber identification module (SIM) card 914 , a memory 920 , a communication module 930 , a sensor module 940 , a user input module 950 , a display module 960 , an interface 970 , an audio codec 980 , a camera module 991 , a power management module 995 , a battery 996 , an indicator 997 , and a motor 998 .
[0238] The processor 910 (e.g., the processor 160 ) can include at least one application processor (AP) 911 or at least one communication processor (CP) 913 . The processor 910 can be, for example, the processor 160 of FIG. 1 . As shown in FIG. 9 , the AP 911 and the CP 913 are included within the processor 910 , but the AP 911 and the CP 913 can be included within different IC packages, respectively. In an embodiment, the AP 911 and the CP 913 can be included within one IC package.
[0239] The AP 911 can drive an operation system or an applied application to control a plurality of hardware or software elements connected to the AP 911 and perform various data processing and calculation including multimedia data. The AP 911 can be embodied, for example, with a system on chip (SoC). According to an embodiment, the processor 910 can further include a graphic processing unit (GPU) (not shown).
[0240] The CP 913 can perform a function of managing a data link in communication between an electronic device (e.g., the electronic device 101 ) including the hardware 900 and another electronic device connected by a network and a function of converting a communication protocol. The CP 913 can be embodied, for example, with a SoC. According to an embodiment, the CP 913 can perform at least a portion of a multimedia control function. The CP 913 can perform identification and authentication of a terminal within a communication network using, for example, a subscriber identification module (e.g., the SIM card 914 ). Further, the CP 913 can provide services such as audio dedicated communication, audiovisual communication, a text message, or packet data to the user.
[0241] Further, the CP 913 can control data transmission and reception of the communication module 930 . In FIG. 9 , elements of the CP 913 , the power management module 995 , or the memory 920 are elements separate from the AP 911 , but according to an embodiment, the AP 911 can include at least a portion (e.g., the CP 913 ) of the foregoing elements.
[0242] According to an embodiment, the AP 911 or the CP 913 can load and process an instruction or data received from at least one of a non-volatile memory and another element connected to each thereof in a volatile memory. Further, the AP 911 or the CP 913 can be received from at least one of other elements or can store data generated by at least one of other elements at a non-volatile memory.
[0243] The SIM card 914 can be a card that embodies a subscriber identification module and be inserted into a slot formed in a specific location of an electronic device. The SIM card 914 can include intrinsic identification information (e.g., integrated circuit card identifier (ICCID) or subscriber information (e.g., international mobile subscriber identity (IMSI).
[0244] The memory 920 can include a built-in memory 922 or a removable memory 924 . The memory 920 can be, for example, the memory 130 of FIG. 1 . The built-in memory 922 can include at least one of, for example, a volatile memory (e.g., a dynamic RAM (DRAM), a static RAM (SRAM), a synchronous dynamic RAM (SDRAM)), or a non-volatile memory (e.g., a one time programmable ROM (OTPROM), a programmable ROM (PROM), an erasable and programmable ROM (EPROM), an electrically erasable and programmable ROM (EEPROM), a mask ROM, a flash ROM, a NAND flash memory, and a NOR flash memory). According to an embodiment, the built-in memory 922 can have a form of a Solid State Drive (SSD). The removable memory 924 can further include a flash drive, for example, a compact flash (CF), secure digital (SD), micro secure digital (Micro-SD), mini secure digital (Mini-SD), extreme digital (xD), or a memory stick.
[0245] The communication module 930 can include a wireless communication module 931 or a radio frequency (RF) module 934 . The communication module 930 can be, for example, the communication interface 170 of FIG. 1 . The wireless communication module 931 can include, for example, WiFi 933 , Bluetooth (BT) 935 , GPS 937 , or near field communication (NFC) 939 . For example, the wireless communication module 931 can provide a wireless communication function using a radio frequency. Additionally or alternatively, the wireless communication module 931 can include a network interface (e.g., a LAN card) or a modem for connecting the hardware 900 to a network (e.g., Internet, a local area network (LAN), a wire area network (WAN), a telecommunication network, a cellular network, a satellite network, or a plain old telephone service (POTS).
[0246] The RF module 934 can perform transmission and reception of data, for example, transmission and reception of an RF signal or a called electronic signal. Although not shown, the RF module 934 can include, for example, a transceiver, a power amp module (PAM), a frequency filter, or a low noise amplifier (LNA). Further, the RF module 934 can further include a component, for example, a conductor or a leading wire for transmitting and receiving electromagnetic waves on free space in wireless communication.
[0247] The sensor module 940 can include at least one of, for example, a gesture sensor 940 A, a gyro sensor 940 B, an atmospheric pressure sensor 940 C, a magnetic sensor 940 D, an acceleration sensor 940 E, a grip sensor 940 F, a proximity sensor 940 G, a red, green, and blue (RGB) sensor 940 H, a living body sensor 940 I, a temperature/humidity sensor 940 J, an illumination sensor 940 K, and a ultra violet (UV) sensor 940 M. The sensor module 940 can measure a physical quantity or detect an operation status of an electronic device and convert measured or detected information to an electric signal. Additionally or alternatively, the sensor module 940 can include, for example, an E-nose sensor (not shown), an electromyography sensor (EMG sensor) (not shown), an electroencephalogram sensor (EEG sensor) (not shown), an electrocardiogram sensor (ECG sensor) (not shown), or a fingerprint sensor. The sensor module 940 can further include a control circuit that controls at least one sensor belonging to the inside.
[0248] The user input module 950 can include a touch panel 952 , a (digital) pen sensor 954 , a key 956 , or an ultrasonic wave input device 958 . The user input module 950 can be, for example, the input and output interface 140 of FIG. 1 . The touch panel 952 can recognize a touch input with at least one method of for example, a capacitive, resistive, infrared ray, or ultrasonic wave method. Further, the touch panel 952 can further include a controller (not shown). When the touch panel 952 is a capacitive type touch panel, the touch panel 952 can perform a direct touch or proximity recognition. The touch panel 952 layer can further include a tactile layer. In this case, the touch panel 952 can provide a haptic reaction to the user.
[0249] The (digital) pen sensor 954 can be embodied using the same method as and a method similar to, for example, reception of a touch input of the user or a separate recognition sheet. As the key 956 , for example, a keypad or a touch key can be used. The ultrasonic wave input device 958 is a device that can check data by detecting a sound wave with a microphone (e.g., a microphone 988 ) in a terminal through a pen that generates an ultrasonic wave signal and can perform wireless recognition. According to an embodiment, the hardware 900 can receive a user input from an external device (e.g., a network, a computer, or a server) connected to the communication module 930 using the communication module 930 .
[0250] The display module 960 can include a panel 962 or a hologram 964 . The display module 960 can be, for example, the display module 150 of FIG. 1 . The panel 962 can be, for example, a liquid-crystal display (LCD) or an active-matrix organic light-emitting diode (AM-OLED). The panel 962 can be embodied with, for example, a flexible, transparent, or wearable method. The panel 962 can be formed with one module and the touch panel 952 . The hologram 964 can show a stereoscopic image in the air using interference of light. According to an embodiment, the display module 960 can further include a control circuit that controls the panel 962 or the hologram 964 .
[0251] The interface 970 can include, for example, a high-definition multimedia interface (HDMI) 972 , a universal serial bus (USB) 974 , a projector 976 , or a D-subminiature (D-SUB) 978 . Additionally or alternatively, the interface 970 can include, for example, secure digital (SD)/multi-media card (MMC)(not shown) or infrared data association (IrDA) (not shown).
[0252] The audio codec 980 can convert a sound and an electronic signal in two-ways. The audio codec 980 can convert sound information input or output through, for example, a speaker 982 , a receiver 984 , an earphone 986 , or a microphone 988 .
[0253] The camera module 991 is a device that can photograph an image and a moving picture and can include at least one image sensor (e.g., a front surface lens or a rear surface lens), an image signal processor (ISP) (not shown), or a flash LED (not shown) according to an embodiment.
[0254] The power management module 995 can manage power of the hardware 900 . Although not shown, the power management module 995 can include, for example, a power management integrated circuit (PMIC), a charger integrated circuit (charge IC), or a battery fuel gauge.
[0255] The PMIC can be mounted within, for example, an integrated circuit or a SoC semiconductor. A charging method can be classified into a wired method and a wireless method. The charge IC can charge a battery and prevent an overvoltage or an overcurrent from being injected from a charging device. According to an embodiment, the charge IC can include a charge IC for at least one of a wired charge method or a wireless charge method. A wireless charge method can include, for example, a magnetic resonance method, a magnetic induction method, or an electromagnetic wave method and can add an additional circuit, for example, a circuit such as a coil loop, a resonant circuit, and a rectifier for wireless charge.
[0256] The battery gauge can measure, for example, a residual quantity of the battery 996 and a voltage, a current, or a temperature while charging. The battery 996 can generate electricity to supply power and can be, for example, a rechargeable battery.
[0257] The indicator 997 can display a specific the status, for example, a booting the status, a message the status, or a charge the status of the hardware 900 or a portion thereof (e.g., the AP 911 ). The motor 998 can convert an electrical signal to a mechanical vibration. A main control unit (MCU) (not shown) can control the sensor module 940 .
[0258] Although not shown, the hardware 900 can include a processing device (e.g., GPU) for supporting a mobile TV. The processing device for supporting the mobile TV can process media data according to a specification of, for example, digital multimedia broadcasting (DMB), digital video broadcasting (DVB), or media flow. Each of the foregoing elements of hardware according to the present invention can be formed with at least one component, and a name of corresponding element can be changed according to a kind of an electronic device. Hardware according to the present invention can include at least one of the foregoing elements and can be formed in a form in which some elements are omitted or hardware can further include additional another element. Further, some of elements of hardware according to the present invention are coupled to form an entity, thereby equally performing a function of corresponding elements before coupling.
[0259] According to an embodiment, a method of operating the electronic device 101 can include the operation of detecting notification, the operation of acquiring communication connection information with another electronic device, the operation of acquiring situation information of another electronic device, and the operation of transferring notification to another electronic device based on communication connection information or situation information.
[0260] According to various embodiments, operation of transferring notification can include operation of acquiring situation information of an electronic device and operation of transferring notification based on situation information of an electronic device and situation information of another electronic device.
[0261] According to various embodiments, the operation of transferring notification can further include operation of checking an operation the status of an electronic device or another electronic device and operation of transferring notification to another electronic device based on an operation the status.
[0262] According to various embodiments, the electronic device includes a first processor and a second processor, and operation of transferring notification can further include the operation of selecting at least one of a first processor or a second processor based on an operation the status, the operation of processing notification in the first processor or the second processor based on the selection, and the operation of transferring notification to another electronic device.
[0263] According to various embodiments, the operation of checking can include the operation of checking an application that provides in an electronic device or another electronic device. According to various embodiments, the operation of checking can include operation of determining a load of data while operating in an electronic device or another electronic device. According to various embodiments, the operation of checking can include operation of checking a power source the status (e.g., a battery the status) of an electronic device or another electronic device. According to various embodiments, the operation of transferring can include operation of transferring a kind (e.g., call, text message, and alarm) of notification.
[0264] According to various embodiments, the operation of acquiring situation information can include operation of detecting a wearing status of another electronic device. According to various embodiments, the operation of acquiring situation information can include operation of detecting a motion of another electronic device. According to various embodiments, the operation of acquiring situation information can include operation of detecting at least one of the user's pupil or touch in another electronic device. According to various embodiments, the operation of acquiring situation information can include operation of acquiring distance information between an electronic device and another electronic device.
[0265] In a method and device for providing notification according to various embodiments, at least one electronic device of a plurality of electronic devices that can provide notification can be selected, notification can be provided through the selected electronic device and thus power consumption can be reduced.
[0266] Further, in a method and device for providing notification according to various embodiments, it can be determined whether the user checks notification and notification in which the user does not check can be provided and thus use convenience can be provided.
[0267] A method in an electronic device, the method comprising: determining notification information; acquiring state information of at least one of the electronic device and at least one external device communicating with the electronic device; and providing the notification information through at least one of the electronic device and the at least one external device based on the state information.
[0268] Wherein the determining of notification information comprises determining, by a user of the electronic device, information that is not checked through the electronic device as the notification information.
[0269] Wherein the determining of notification information comprises determining information that is not transmitted from the electronic device to the at least one external device as the notification information.
[0270] Wherein the acquiring of state information comprises acquiring the notification information having a first priority and information about an application having a second priority executing in the electronic device. And the providing of the notification information comprises: providing the notification information through the electronic device based on that the first priority is higher than the second priority; and providing the notification information through the at least one external device based on that the first priority is lower than the second priority.
[0271] Wherein the providing of the notification information comprises providing the notification information through an enabled device of the electronic device and the at least one external device.
[0272] Wherein the providing of the notification information comprises providing the notification information through a device that acquires user information corresponding to information set to be related to the user of the electronic device.
[0273] Wherein the providing of the notification information comprises providing the notification information through a device corresponding to the state information, when power source information or load information acquired as the state information corresponds to a range designated to the electronic device.
[0274] Wherein the providing of the notification information comprises: providing the notification information through the electronic device, when the electronic device or the at least one external device is located at a first location; and providing the notification information through the at least one external device when the electronic device or the at least one external device is located at a second location.
[0275] Wherein the providing of the notification information comprises: providing the notification information through the electronic device, when time information acquired as the state information is a first time; and providing the notification information through the at least one external device, when time information acquired as the state information is a second time.
[0276] Wherein the providing of the notification information comprises transmitting the notification information to the at least one external device, when communication information or distance information between the electronic device and the at least one external device belongs to a range designated to the electronic device.
[0277] Wherein the electronic device comprises a first processor that processes an application and a second processor that controls communication of the electronic device, and the providing of the notification information comprises transmitting the notification information to the at least one external device through the second processor, when the first processor executes the application. And further comprising: acquiring check information on whether a user of the electronic device and the at least one external device checks the notification information or transmitting information on whether the electronic device transmits the notification information to the at least one external device; and storing the check information or the transmitting information at a database functionally connected to the electronic device. And the storing of the check information comprises updating the database, when the check information or the transmitting information is changed.
[0278] A term “module” used for the present invention can indicate a unit including a combination of one or two or more of, for example, hardware, software, or firmware. The “module” can be interchangeably used with a term of, for example, a unit, logic, a logical block, a component, or a circuit. The “module” can become a minimum unit or a portion of an integrally formed component. The “module” can become a minimum unit or a portion that performs at least one function. The “module” can be mechanically or electronically embodied. For example, a “module” according to the present invention can include at least one of an application-specific integrated circuit (ASIC) chip, field-programmable gate arrays (FPGAs), and a programmable-logic device that performs some operations that are known or to be developed in the future.
[0279] According to various embodiments, at least a portion of a device (e.g., modules or functions) or a method (e.g., operations) according to the present invention can be embodied with an instruction stored at computer-readable storage media in a form of, for example, a programming module. When the instruction is executed by at least one processor (e.g., the processor 810 ), the at least one processor can perform a function corresponding to the instruction. The computer-readable storage media can be, for example, the memory 860 . At least a portion of the programming module can be implemented (e.g., executed) by, for example, the processor 810 . At least a portion of the programming module can include, for example, a module, an application, a routine, and sets of instructions and/or a process for performing at least one function.
[0280] An electronic device, comprising: a determining module that determines notification information in the electronic device; an acquiring module that acquires state information of at least one of the electronic device and at least one external device that communicates with the electronic device; and a providing module that provides the notification information through at least one of the electronic device and the at least one external device based on the state information.
[0281] Wherein the acquiring module acquires information corresponding to designated information as the state information based on an attribute of the notification information.
[0282] Wherein the providing module provides the notification information through a device in which a user presently uses based on state information of the user of the electronic device acquired as the state information.
[0283] Wherein the providing module provides the notification information through an enabled device of the electronic device and the at least one external device.
[0284] Wherein the providing module transmits the notification information to the at least one external device, when an application executing in the electronic device has a priority higher than that of the notification information.
[0285] A computer readable recording medium on which an application or a program for performing operation of determining notification information in an electronic device; operation of acquiring state information of at least one of the electronic device and at least one external device that communicates with the electronic device; and operation of providing the notification information through at least one of the electronic device and the at least one external device based on the state information is recorded.
[0286] A programming module according to the present invention can include at least at least one of the foregoing elements or can further include elements in which some elements are omitted or additional other elements. A programming module according to the present invention or operations performed by another element can be executed with a sequential, parallel, repetitional, or heuristic method. Further, some operations can be executed in another order or are omitted, or other operations can be added thereto.
[0287] The computer readable recording media can include magnetic media such as a hard disk, a floppy disk, and a magnetic tape, optical media such as a compact disc read-only memory (CD-ROM) or a digital versatile disc (DVD), magnetic-optical media such as a floptical disk, and a hardware device specially formed to store and perform an application instruction (e.g., a programming module) such as a read-only memory (ROM), a read access memory (RAM), and a flash memory. Further, the application instruction can include a high-level language code that can be executed by a computer using an interpreter as well as a machine language code made by a compiler. The foregoing hardware device can be formed to operate as at least one software module to perform operation of the present invention and vice versa.
[0288] While the present invention has been particularly shown and described with reference to embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims. | A method of providing notification information in an electronic device includes establishing a wireless communication between the electronic device and an external device, detecting an event to be notified in the electronic device, obtaining a status of the electronic device, and determining whether to transmit an notification on the event to an external device, based on the status of the electronic device. An electronic device includes a transceiver configured to establish a wireless communication between the electronic device and an external device, and a processor configured to detect an event to be notified in the electronic device, obtain a status of the electronic device, and determine whether to transmit an notification on the event to an external device, based on the status of the electronic device. Other embodiments are also disclosed. | 7 |
FIELD TO WHICH THE INVENTION RELATES
The present invention relates to a weft yarn guide for a fluid jet loom, and especially, it pertains a weft yarn guide for an air jet loom.
BACKGROUND OF THE INVENTION
British Pat. No. 1,424,703 discloses a weft yarn guide for a jet loom which comprises: a base portion connected to a sley; a pair of guide members forked from the base portion so as to form a weft inserting opening, and; a plurality of fluid blowing holes disposed on the circumference of the pair of guide members around the weft inserting opening. In this weft yarn guide, an air flow is supplied through an air passage formed within both the base portion and the pair of guide members. When this weft yarn guide is actually used, there is a defect in that the intensities of the auxiliary air jets blown through the fluid blowing holes are not uniform therebetween, and accordingly, the weft yarn cannot be carried properly because the weft yarn is pushed upwards.
To eliminate the defect in the above-mentioned prior art apparatus, another type of weft yarn guide has been proposed, wherein fluid blowing holes are formed only on the upper surfaces of the forked guides members, so that air jets which may push up the weft yarn are omitted. However, in this weft yarn guide, no consideration is given to the design of the air passage formed within the base portion and the pair of guide members, especially at the junction of the base portion and the pair of guide members, and accordingly, air flow fed from the base portion impinges upon the upper inner wall of the air passage at the junction and causes turbulences, and as a result, the intensities of the auxiliary air jets blown through the fluid blowing holes cannot be uniform.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a weft yarn guide for a fluid jet loom, by which flow resistance to the fluid flow can be minimized and the intensities of the auxiliary fluid jets blown through the fluid blowing holes can be uniform, and accordingly, the insertion of the weft yarn can assuredly and smoothly be effected.
According to the present invention, the above mentioned object is achieved by a weft yarn guide for a fluid jet loom comprising: a base portion capable of being connected to a sley; a pair of guide members which are connected to the upper end of the base portion and which are forked to form a weft inserting opening therebetween; a base fluid passage formed within the base portion, and; a plurality of fluid blowing holes which are formed on the surface of the forked guide members, except for the lower surfaces thereof, and which are communicated with the base fluid passage. The weft yarn guide according to the present invention is characterized in that: a branching wall is projected from the upper inner wall of the base fluid passage so that fluid flow fed from the base fluid passage is branched into two flows, and; a pair of branch passages, the lower ends of which are communicated with the base fluid passage and which are communicated with the fluid blowing holes formed on the forked guide members, are formed within said guide members, so that the branched flows are blown through the fluid blowing holes.
BRIEF DESCRIPTION OF THE DRAWINGS
Disadvantages of the prior art devices and some embodiments of the present invention will now be explained in detail with reference to the accompanying drawings, wherein:
FIG. 1 is an elevational view of a conventional weft yarn guide;
FIGS. 2 and 3 are elevational and partial cross sectional views of another conventional weft yarn guide;
FIG. 4 is an elevational view of a weft yarn guide according to the present invention;
FIG. 5 is a cross sectional view taken along line V--V in FIG. 4;
FIG. 6 is an enlarged cross sectional view of a part of the guide illustrated in FIG. 4;
FIG. 7 is a cross sectional view of the guide illustrated in FIG. 4, wherein upper part is omitted, and;
FIG. 8 is an elevational view of another weft yarn guide according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Prior to the explanation concerning the embodiments of the present invention, some weft yarn guides belonging to the prior art will be explained, with reference to FIGS. 1 through 3, in order to clarify the defects of the conventional weft yarn guides.
In a conventional closed type weft yarn guide 1 for a fluid jet loom illustrated in FIG. 1, an annular body 3 is formed by an arced guide member 1a of the weft yarn guide 1 and an upright guide member 1b of the weft yarn guide 1, and the annular body has an inner circumference which faces the weft yarn inserting direction. A plurality of fluid blowing holes 2 for blowing auxiliary air jets are formed on the inner circumference. As a result, the fluid blowing holes 2 serve to blow auxiliary air jets in the weft inserting direction by utilizing air fed through an air passage 4 formed within the weft yarn guide 1. In this case, the air jets are so blown that they surround the entire outer periphery of a main air flow which is flowed from a main nozzle (not shown) in the weft inserting direction. However, in this weft yarn guide, the air flow fed from the air passage 4 is directly blown through the fluid blowing holes 2 which are formed at the lower portion adjacent to the base portion of the weft yarn guide 1, and accordingly, the intensity of the auxiliary air jets blown through these lower fluid blowing holes 2 becomes stronger than the intensity of the auxiliary air jets blown through the other fluid blowing holes 2 located on the upper surfaces of the guide members 1a and 1b. As a result, a weft yarn passing through a weft inserting opening surrounded by the guide members 1a and 1b is pushed upwards towards a slit 5 of the weft yarn guide 1, and the weft yarn cannot correctly be carried in the inserting direction. Consequently, there is a defect in this yarn guide in that the weft yarn is sometimes pushed out through the slit 5 and the weaving operation cannot be continued.
To eliminate the above-mentioned defect, an improvement has been proposed, wherein the inner diameter of the fluid blowing holes 2 located at the lower portion is made smaller than the other fluid blowing holes 2, so that the intensities of the air jets blown through all the fluid blowing holes are uniform. However, adjustment of the sizes of the fluid blowing holes in accordance with this proposal is difficult, and its application to actual devices is impossible.
Another weft yarn guide has been also proposed to eliminate the above-mentioned defect, in which guide the lower fluid blowing holes 2 (FIG. 1) which may blow auxiliary air jets with high tensity are omitted as illustrated in FIG. 2. However, in this weft yarn guide 1, air flow fed from an air passage 4 formed within the base portion directly impinges upon an inner upper wall 6 of the air passage 4, and, then, is dispersed. Accordingly, the flow speed of the air flow is reduced and the air flow generates turbulence therein, and thereafter, the air flow containing turbulence is fed to fluid blowing holes 7 located in the upper portion of the guide 1. Because of the turbulence, the flow resistance of the air flow becomes large, and the intensities of the auxiliary air jets blown through the fluid blowing holes cannot be uniform. In addition, it should be noted that, as illustrated in FIG. 3, the auxiliary air jets blown through the fluid blowing holes 7 are blown upwards forming a large angle θ of attack from the horizontal plane because the fluid flows straight due to its momentum, and that, accordingly, a similar defect to that of the guide illustrated in FIG. 1, that the weft yarn is pushed upwards, is caused.
The first embodiment of a weft yarn guide for a fluid jet loom, which is constructed as a weft yarn guide for an air jet loom, according to the present invention will now be explained in detail with reference to FIGS. 4 through 7. Reference numeral 10 in FIG. 4 generally denotes a weft yarn guide, which comprises a base portion 11 adapted to be connected to a sley (not shown), an arced guide member 12 branched from the upper end of the base portion 11 and extending towards the woven fabric (not shown), and an upright guide member 13 branched also from the upper end of the base portion 11 and extending upwards so as to face the arced guide member 12. A circular weft yarn inserting opening 14 is formed by the arced guide member 12 and the upright guide member 13, and a slit 15 is formed between the upper ends of the arced guide member 12 and the upright guide member 13, so that the picked weft yarn (not shown) can be passed outwards through the slit 15 when the weft yarn guide 10 is swung toward the woven fabric in order to beat the reeds (not shown).
A base fluid passage 16 is formed within the base portion 11, and the upper inner walls of the fluid passage 16 are so formed that there is formed a branching wall 17, which converges in the direction of the bottom of the base portion 11 and which branches the base fluid passage 16 into a branch passage 18 formed within the arced guide member 12 and a branch passage 19 formed within the upright guide member 13. The branching wall 17 has such a thickness that the branch passages 18 and 19 formed within the arced guide member 12 and the upright guide member 13, respectively, are deviated towards the outer side of the arced and upright guide members 12 and 13 respectively. In addition, the ratio of the cross sectional areas of the branch passages 18 and 19 at their lower ends 18a and 19a where they are connected to the base fluid passage 16 is determined based on the ratio of the areas of fluid blowing holes 21 and 23, as will be explained later, so that the intensities of the auxiliary air jets blown through the fluid blowing holes 21 and 23 becomes uniform.
A fluid chamber 20 is formed within the upper portion of the arced guide member 12 and is communicated with the upper end 18b of the branch passage 18, which is formed within the arced guide member 12. As illustrated in FIG. 7, the inner diameter of the fluid chamber 20 is larger than that of the branch passage 18 formed within the arced guide member 12, because the inner wall of the fluid chamber 20 bulges towards the inner wall of the arced guide member 12. A plurality of fluid blowing holes 21, six in the illustrated embodiment, are formed on the inner surface of the arced guide member 12, which surface faces the weft inserting direction, as illustrated in FIGS. 4 and 5, so that air flow fed from the base fluid passage 16 and branched into the branch passage 18 and the fluid chamber 20 formed within the arced guide member 12 is blown as auxiliary air jets through the six fluid blowing holes 21 towards the central axis of the weft inserting opening 14.
A fluid chamber 22 is formed within the upper portion of the upright guide member 13 and is communicated with the upper end 19b of the branch passage 19, which is formed within the upright guide member 13. As illustrated in FIGS. 6 and 7, the inner diameter of the fluid chamber 22 is larger than that of the branch passage 19 formed within the upright guide member 13, because the inner wall of the fluid chamber 22 bulges towards the inner wall of the upright guide member 13. A plurality of fluid blowing holes 23, four in the illustrated embodiment, are formed on the inner surface of the upright guide member 13, which surface faces the weft inserting direction, as illustrated in FIGS. 4 and 5, so that air flow fed from the base fluid passage 16 and branched into the branch passage 19 and the fluid chamber 22 formed within the upright guide member 13 is blown as auxiliary air jets through the four fluid blowing holes 23 towards the central axis of the weft inserting opening 14.
The first embodiment according to the present invention operates as follows. The air flow fed through the base fluid passage 16 is smoothly branched by the branching wall 17 into the branch passage 18 formed within the arced guide member 12 and the branch passage 19 formed within the upright guide member 13 without encountering any substantial resistance, and the branched air flows are blown through the fluid blowing holes 21 and 23. Accordingly, when the air flow is branched, the air flow speed is not reduced and turbulence is not introduced into the air flow or the effects are reduced from those caused by conventional guides. The flow resistance can be minimized.
In addition, the ratio of the cross sectional area of the branch passage 18 at its lower end 18a, which passage is formed within the arced guide member 12, to the cross sectional area of the branch passage 19 at its lower end 19a, which passage is formed within the upright guide member 13, is so selected that it corresponds to the ratio of the total area of the fluid blowing holes 21 formed on the arced guide member 12 to the total area of the fluid blowing holes 23 formed on the upright guide member 13, and accordingly, the intensities of the auxiliary air jets blown through the fluid blowing holes 21 and 23 can be uniform.
Furthermore, as illustrated in FIG. 6, since the inner surface of the upper end 19b of the branch passage 19 formed within the upright guide member 13 is separated from the fluid blowing holes 23 formed on the inner surface of the fluid chamber 22 formed within the upright guide member 13 because of the thickness of the branching wall 17, the air flow flowing from the branch passage 19 is bent to the fluid blowing holes 23, and accordingly, the angle θ of attack of the auxiliary air jets blown through the fluid blowing holes 23 is less than that generated by the above-mentioned conventional weft yarn guide. Regarding the angle of attack of the auxiliary air jets, if the thickness of the inner wall on which the fluid blowing holes 23 are formed is increased to a certain amount which does not create excessive flow resistance, the angle θ of attack of the auxiliary air jets can be further be decreased. The above discussion is also applicable to the branch passage 18 formed within the arced guide member 12 and the fluid blowing holes 21 formed on the arced guide member 12.
The present invention is not limited to the above-explained first embodiment, and various modifications or improvements can be effected to the first embodiment, for example, as described in the explanation of the second embodiment, below, within the scope of the present invention which is defined in the attached claims.
A second embodiment of the weft yarn guide according to the present invention is illustrated in FIG. 8, wherein the upright guide member 13 utilized in the first embodiment is inclined inwards, so that a weft yarn guide 26 is obtained.
According to the present invention, the flow resistance of the air flow can be minimized, and at the same time the intensities of the auxiliary air jets blown through the fluid blowing holes can be uniform, and accordingly, the insertion of the weft yarn can assuredly and smoothly be effected. Therefore, the weft yarn guide according to the present invention has a remarkable advantage when it is used in an air jet loom. | A weft yarn guide of an air jet loom comprises a base portion capable of being connected to a sley, a pair of guide members which are connected to the upper end of the base portion and which are forked to form a weft inserting opening therebetween, a base fluid passage formed within the base portion, and a plurality of fluid blowing holes formed on the upper portions of the guide members and communicated with the base fluid passage. The weft yarn guide further comprises a branching wall projected from the upper inner wall of the base fluid passage in order to branch air flow fed from the base passage into two flows, and a pair of branch passages formed within the guide members in order to communicate the base fluid passage with the fluid blowing holes, whereby the air flow is smoothly branched without causing substantial turbulence. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to recovery of oil from a subterranean reservoir through the use of a surfactant-cosurfactant system.
It has long been known that the primary recovery of oil from a subterranean formation leaves a substantial amount of the oil still in the formation. This has led to the use of what is commonly referred to as secondary recovery or water flooding wherein a fluid such as brine is injected into a well to force the oil from the pores of the reservoir toward a recovery well. However, this technique also leaves substantial amounts of oil in the reservoir, so-called residual oil, because of the capillary retention of the oil. Accordingly, post-primary surfactant systems have been employed either in place of the secondary recovery or more generally in a tertiary recovery process. One particularly suitable type of surfactant system is that which results in the in situ formation of a microemulsion which is immiscible with the oil it is displacing. Such microemulsion systems are very effective in removing residual oil. However, these systems can suffer from a deterioration of the surfactant system as it moves through the formation due to alteration of the cosurfactant concentration.
The surfactant systems employed to produce microemulsion type oil recovery basically contain at least three separate ingredients, brine, a surfactant and a cosurfactant. It is disclosed in Glinsmann, U.S. Pat. No. 4,125,156, issued Nov. 14, 1978, how to systematically optimize a system so as to give a combination of surfactant, cosurfactant and brine which produce low interfacial tension which is associated with good oil recovery.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an improved surfactant flood system;
It is a further object of this invention to recover an extraordinarily high percentage of oil in a post-primary recovery operation; and
It is yet a further object of this invention to minimize the alteration of the cosurfactant concentration as the surfactant system progresses through the oil bearing formation.
In accordance with this invention, a cosurfactant is included in a preflush prior to introduction of a surfactant system.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The surfactant system used in this invention comprises a surfactant, cosurfactant, water and electrolyte. Such a surfactant system is described in detail in Glinsmann, U.S. Pat. No. 4,125,156, issued Nov. 14, 1978, the disclosure of which is incorporated herewith by reference.
Briefly, the applicable surfactants (agents having substantial surface active characteristics) for the surfactant system can include cationic, anionic or nonionic surfactants, and are preferably petroleum sulfonates having an average equivalent weight within the range of 375 to 500, which surfactants are disclosed in more detail in said Glinsmann patent. The surfactant will generally be present in an amount within the range of 0.1 to 10, preferably 1 to 7, more preferably 1.5 to 4.5 weight percent based on the weight of the surfactant system.
Briefly, the electrolyte of the surfactant system is preferably a monovalent metallic salt most preferably sodium chloride, the applicable electrolytes being disclosed in detail in said Glinsmann patent. Generally, the electrolyte is present in the water of said surfactant system in an amount so as to give a brine containing 5,000 to 25,000 parts by weight total dissolved solids per million parts by weight of the surfactant system although this can vary considerably as disclosed in detail in said Glinsmann patent. The concentration of electrolyte in the preflush can be within the same range as in the surfactant system, i.e., 5,000 to 25,000 parts by weight per million parts by weight of the surfactant system in said preflush. The same type of electrolytes described for the surfactant system are also used in the preflush. Generally, the electrolyte of the surfactant system and the preflush will be the same and the electrolyte concentration will be the same.
The cosurfactants (polar solubilizing agents with little or no surface active characteristics) suitable for use in the surfactant system of this invention, and hence in the preflush or in the preflush and subsequent mobility buffer are as disclosed in said Glinsmann patent. By solubilizing agents is meant agents to solubilize oil and water into the microemulsion. Briefly, these can be esters, amines, aldehydes, ketones, phenols, and the like, such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, N,N-diethylamine, isopentylamine, triethylamine, isobutyraldehyde, n-butanal, methyl ethyl ketone, 3-pentanone, p-cresol, and phenol. Unsaturated alcohols can also be used in the instant process. Preferred cosurfactants are alcohols containing 1 to 6 carbon atoms, most preferably containing 3 to 5 carbon atoms. Alcohol cosurfactants which can be used either individually or in various blends in the instant process include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, tert-butyl alcohol, n-pentanol, 2-pentanol, 3-pentanol, isopentanol, n-hexanol, isohexanol, 2-hexanol, 3-hexanol, and the like. Representative alcohol blends which can be used include, e.g., isopropanol/isopentanol, 2-butanol/2-pentanol, isobutanol/n-butanol, n-butanol/2-pentanol, 2-butanol/tert-pentanol, 2-pentanol/isopentanol, and other such blends. Alcohols having a solubility of 0.5 to 20 grams per 100 grams of water at room temperature are particularly suitable.
The following ranges are suitable for the cosurfactant in the various slugs (based on the weight of the slugs):
______________________________________ Broad Preferred Most Range Range Preferred Range______________________________________Surfactant Slug 0.1-10 1-7 1.5-4.5(Wt. % Cosurfactant)Preflush Slug 0.1-10 1-7 1.5-4.5(Wt. % Cosurfactant)Mobility Buffer Slug* 0.1-10 1-7 1.5-4.5(Wt. % Cosurfactant)______________________________________ *If used at all; generally only the preflush will contain the cosurfactant.
EXAMPLE
In order to demonstrate the advantage of practicing the instant inventive process, the following types of core runs were carried out and the results are summarized in Tables I and II.
(a) Control Runs: These runs involved the use of the slug sequence: aqueous saline preflush, alcohol-containing surfactant system and thickened aqueous mobility buffer diluted continuously with brine at constant volume to give an aqueous drive.
(b) Invention Runs: These runs involved the use of the slug sequence: aqueous saline preflush containing alcohol, alcohol-containing surfactant system and thickened aqueous mobility buffer diluted continuously with brine at constant volume to give an aqueous drive.
(c) Invention Runs: These runs involved the same sequence as (b) above except for the addition of alcohol to the thickened aqueous mobility buffer, and the brine used for dilution of the mobility buffer.
TABLE I______________________________________Tertiary Oil Recoveries With Slug Sequences Comprising Decane/TRS 10-410 Surfactant System With Alcohol-Containing PreflushOptionally Followed By Alcohol-Containing Mobility Buffer Run % Tertiary Oil OptimumRun No. Type Cosurfactant Recovery Salinity______________________________________1 Control.sup.a 2-Butanol 73.8 1.702 Invention.sup.b 2-Butanol 84.6 1.703 Invention.sup.c 2-Butanol 90.1 1.704 Control.sup.a 2-Pentanol 74.8 0.585 Invention.sup.b 2-Pentanol 94.8 0.586 Invention.sup.c 2-Pentanol 88.3 0.587 Control.sup.a n-Butanol 88.8 0.868 Invention.sup.c n-Butanol 92.1 0.869 Control.sup.a tert-Pentanol 86.6 1.2510 Invention.sup.c tert-Pentanol 91.0 1.2511 Control.sup.a Isopentanol 72.7* 0.9112 Invention.sup.c Isopentanol 82.1* 0.91______________________________________ *Hexadecane was used in these runs (1.5 percent cosurfactant concentration). .sup.a These runs contained alcohol in the surfactant system slug only. .sup.b These runs contained alcohol in the aqueous preflush and the surfactant system slug. .sup.c These runs contained alcohol in the aqueous preflush, surfactant system slug, mobility buffer slug and mobility buffer dilution brine.
TABLE II______________________________________Tertiary Oil (n-Decane) Recoveries With Slug SequencesComprising Surfactant System With Alcohol-ContainingPreflush Optionally Followed By Alcohol-ContainingMobility Buffer % Opti- Tertiary mumRun Run Oil Sa-No. Type Cosurfactant Surfactant Recovery linity______________________________________13 Control.sup.a Isobutanol TRS 10-395 72.6 1.1014 Invention.sup.b Isobutanol TRS 10-395 97.3 1.1015 Invention.sup.c Isobutanol TRS 10-395 98.3 1.1016 Control.sup.a 2-Pentanol TRS-LB 70.9 0.3317 Invention.sup.b 2-Pentanol TRS-LB 95.7 0.3318 Invention.sup.c 2-Pentanol TRS-LB 90.8 0.33______________________________________ .sup.a These runs contained alcohol in the surfactant system slug only. .sup.b These runs contained alcohol in the aqueous preflush and the surfactant system slug. .sup.c These runs contained alcohol in the aqueous preflush, surfactant system slug, mobility buffer slug and mobility buffer dilution brine.
The above indicated core runs were carried out at the optimum (optimal) salinity which was determined from phase behavior of the several surfactant systems studied. Phase behavior was established by the equilibration of equal volumes (usually 25 milliliters) of oil, e.g., decane or hexadecane and surfactant system. The volumes of the phases were recorded and plotted as a function of salinity to give typical phase volume diagrams such as illustrated in FIG. 9a of FIG. 9 in said Glinsmann patent. In general, phase-volume diagrams are characterized by a three-phase region at intermediate salinities separating two-phase regions at high and low salinities. At low salinities, the system consists of a predominantly oil phase in equilibrium with a water-rich (so-called gamma type) microemulsion phase whereas at high salinities, the system consists of an oil-rich (so-called alpha type) microemulsion in equilibrium with a predominantly water phase. At the intermediate salinities, both oil and aqueous phases exist in equilibrium with a middle microemulsion phase (so-called beta type). Within the three-phase region, there exists a salinity referred to as the optimal salinity at which equal volumes of oil and water are solubilized into the middle microemulsion phase. As is shown by comparing FIG. 9a and FIG. 9b of said FIG. 9 of said Glinsmann patent, the designated optimal salinity corresponds closely to that salinity at which the maximum of the coexisting tensions is minimized. Typically, as a function of salinity, oil recovery is maximized near the optimal salinity (see FIG. 9c of said FIG. 9 of said Glinsmann patent). The microemulsion phase, formed on equilibration of the surfactant system with oil corresponding to that in the reservoir, is immiscible with said oil. In contrast to the behavior shown in FIG. 1 of said Glinsmann patent, some systems will exhibit behavior wherein the middle phase rather than the upper phase will diminish in volume in the beta to alpha transition region. This in general does not interfere with the optimal salinity determination. runs 1, 4, 7, 9, 11 gave lower tertiary oil recoveries than did the respective inventive runs 2, 3; 4, 5; 8, 10, 12. The best tertiary oil recovery of 94.8% (Run 5) involved the use of an alcohol-containing preflush with no alcohol added to the mobility buffer. The runs of Table I involved the use of Witco Chemical Company TRS 10-410 petroleum sulfonate.
Referring to the results in Table II, it can be seen that the control runs 13 and 16 gave lower tertiary oil recoveries than did the respective inventive runs 14;15 and 17;18. The runs of Table II involved the use of Witco Chemical Company TRS 10-395 and TRS-LB petroleum sulfonates. The results in Table II indicate that the presence of the cosurfactant in the preflush is responsible for most of the improvement in oil recovery, the presence of the cosurfactant in the following mobility buffer giving only marginal additional improvement if any at all. It does appear in some instances, to be advantageous to include the cosurfactant in the mobility buffer, preferably however, neither the mobility buffer nor the drive fluid contains a cosurfactant.
The aqueous surfactant systems contained 3 percent active sulfonate (by weight), 3 percent cosurfactant (single component or blend), 0.2 percent sodium tripolyphosphate, 0.1 percent sodium carbonate and varying amounts of sodium chloride for salinity adjustment. Sodium tripolyphosphate and sodium carbonate were used as sacrificial agents to reduce surfactant adsorption in oil displacement tests and their use in these tests is optional. The surfactants used in this work were Witco Chemical Company petroleum sulfonates and possessed the properties shown in Table III.
TABLE III______________________________________Witco Chemical Company Petroleum SulfonatesIngredient (wt. %) TRS 10-395 TRS 10-410 TRS-LB______________________________________Active Sodium Sulfonates 61.7 61.5 62.0 Oil 34.0 34.0 34.0 Water 4.2 4.4 4.0Inorganic Salts 0.1 0.1 NA*Sulfonate AverageEquivalent Weight 407 420 440______________________________________ *NA represents not available.
All cosurfactants and inorganic salts used in this work were reagent grade.
All oil displacement tests were conducted in 3 foot long, 3-inch diameter Berea sandstone cores. The cores were prepared in the following manner: (1) saturated with optimal salinity brine, (2) flooded with the oil of interest to an irreducible brine saturation, and (3) waterflooded with brine to waterflood residual oil saturation. A surfactant flood sequence was then initiated and included: (1) an aqueous saline preflush slug containing 3 weight percent alcohol (inventive runs only) and sacrificial agents; (2) an aqueous surfactant slug comprising petroleum sulfonate and cosurfactant; and (3) thickened water mobility slug optionally containing alcohol. All slugs were prepared in optimal salinity brine. The polymeric viscosifier concentration in the mobility buffer slug (0.5 PV) was graded back logarithmically during the displacement test. Initial polymer concentrations were adjusted to yield a viscosity of 40 cp. Table IV summarizes the details of the surfactant flood sequence.
TABLE IV______________________________________Slug Sequences for Oil Displacement Tests______________________________________Preflush (0.60 PV)0.2% Na.sub.5 P.sub.3 O.sub.100.1% Na.sub.2 CO.sub.3Optimal Salinity brine3.0% CosurfactantSurfactant Slug (0.10 PV)3% Active Petroleum Sulfonate3% Cosurfatant0.2% Na.sub.5 P.sub.3 O.sub.100.1% Na.sub.2 CO.sub.3Optimal Salinity brineMobility Buffer (0.50 PV*)Initial viscosity at 40 centipoise.Prepared in optimal salinity brine optionallycontaining 3% cosurfactant.______________________________________ *A volume of mobility buffer equal to 0.5 PV was diluted continuously wit brine at constant volume; i.e., polymer concentration was graded back logarithmically.
All displacement tests were conducted at 0.6 ft/day (preflush was injected at 3 feet/day). Cores were rotated (0.25 rpm) during surfactantflood tests to minimize gravity segregation effects. All phase, interfacial tension and oil displacement studies were conducted at 86° F. (30° C.).
In each invention run where a cosurfactant was included in the preflush or the preflush and mobility buffer, it was the identical cosurfactant used in the surfactant system which is the preferred situation. However in the practice of this invention, the cosurfactant of the preflush and/or mobility buffer could be different from that of the surfactant system.
In order to improve the economics, a preflush having no cosurfactant can be introduced ahead of the preflush containing the cosurfactant, i.e., the cosurfactant is used only in the later part of the preflush.
Alternatively, although it is less preferred, the preflush containing a cosurfactant as described herein can be used prior to the injection of an immiscible microemulsion formed above ground. That is, an aqueous surfactant-cosurfactant electrolyte system can be equilibrated with oil and the resulting microemulsion separated and injected.
The preflush is generally used in an amount conventional in the art, for instance, 0.1 to 1.5, preferably 0.4 to 0.8 pore volumes.
While this invention has been described in detail for the purpose of illustration, it is not to be construed as limited thereby, but is intended to cover all the changes and modifications within the spirit and scope thereof. | In a post-primary oil recovery process involving the sequential addition of a saline preflush, a surfactant system comprising a surfactant, a cosurfactant and brine, the improvement comprising the addition of cosurfactant to the preflush. If desired, cosurfactant can also be added to a subsequent injected mobility buffer. The resulting system gives extraordinarily high recovery of oil. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates to the use of organo-sulphur compounds in the enhancement of the tarnish resistance of silver alloys, to silver articles of enhanced tarnish resistance that have been surface-treated with the organo-sulphur compounds and to methods of keeping and display of the treated articles. It also relates to a water-based composition that can be used for the treatment of a metal which may be a silver alloy but which may also be another metal requiring surface treatment to impart tarnish resistance e.g. copper, brass or nickel.
BACKGROUND TO THE INVENTION
[0000] Silver Alloys and Their Tarnish-Resistance
[0002] Standard Sterling silver provides manufacturers and silversmiths with a versatile and reliable material but it is inevitable that finished articles will require further cleaning and polishing to temporarily remove undesired tarnish products. It is well-known that with exposure to everyday atmospheric conditions, silver and silver alloys develop a lustre-destroying dark film known as tarnish.
[0003] Since ancient times it has been appreciated that unalloyed ‘fine’ silver is too soft to withstand normal usage, and it has been the practice to add a proportion of a base metal to increase hardness and strength. In the UK, legislation that has existed since the fourteenth century specifies a minimum silver content of articles for sale at 92.5% (the Sterling standard), but does not specify the base metal constituents. Experience convinced early silversmiths that copper was the most suitable of the metals available to them. Modern silver-sheet manufacturers generally adhere to this composition, although sometimes a proportion of copper is replaced by cadmium to attain even greater ductility. Sterling with a 2.5% cadmium content is a standard material for spinning and stamping. Lower grades of silver alloys are common in many parts of Europe for the production of hollow-ware and cutlery. The 800-grade alloys (Ag parts per thousand) are predominantly used in southern and mid-Europe whereas in Scandinavia the 830 standard is predominant.
[0004] In all but the largest manufacturing companies, most of the annealing and soldering required to assemble finished or semi-finished articles is carried out with the flame of an air-gas blowtorch. The oxidising or reducing nature of the flame and the temperature of the articles are controlled only by the skill of the silversmith. Pure silver allows oxygen to pass easily through it, particularly when the silver is heated to above red heat. Silver does not oxidise in air, but the copper in a silver/copper alloy is oxidised to cuprous or cupric oxide. Pickling of the oxidised surface of the article in hot dilute sulphuric acid removes the superficial but not the deeper-seated copper oxide so that the surface consists of fine or unalloyed silver covering a layer of silver/copper oxide mixture. The pure silver is easily permeated during further heating, allowing copper located deeper below the surface to become oxidised. Successive annealing, cold working and pickling produces a surface that exhibits the pure lustre of silver when lightly polished but with heavier polishing reveals dark and disfiguring stains known as ‘firestain’ or ‘fire’. Soldering operations are much more productive of deep firestain because of the higher temperatures involved. When the depth of the firestain exceeds about 0.025 mm (0.010 inches) the alloy is additionally prone to cracking and difficult to solder because an oxide surface is not wetted by solder so that a proper metallurgical bond is not formed.
[0005] Patent GB-B-2255348 (Rateau, Albert and Johns; Metaleurop Recherche) disclosed a novel silver alloy that maintained the properties of hardness and lustre inherent in Ag—Cu alloys while reducing problems resulting from the tendency of the copper content to oxidise. The alloys were ternary Ag—Cu—Ge alloys containing at least 92.5 wt % Ag, 0.5-3 wt % Ge and the balance, apart from impurities, copper. The alloys were stated to be stainless in ambient air during conventional production, transformation and finishing operations, to be easily deformable when cold, to be easily brazed and not to give rise to significant shrinkage on casting. They were also stated to exhibit superior ductility and tensile strength and to be annealable to a required hardness. Germanium was stated to exert a protective function that was responsible for the advantageous combination of properties exhibited by the new alloys, and was in solid solution in both the silver and the copper phases. The microstructure of the alloy was said to be constituted by two phases, a solid solution of germanium and copper in silver surrounded by a filamentous solid solution of germanium and silver and copper. The germanium in the copper-rich phase was said to inhibit surface oxidation of that phase by forming a thin GeO or GeO 2 protective coating which prevented the appearance of firestain during brazing and flame annealing which results from the oxidation of copper at high temperatures. Furthermore the development of tarnish was appreciably delayed by the addition of germanium, the surface turned slightly yellow rather than black and tarnish products were easily removed by ordinary tap water. The alloy was said to be useful inter alia in jewellery. However, the alloy disclosed in the above patent suffers limitations insofar as it can exhibit large grain size, leading to poor deformation properties and formation of large pools from low-melting eutectics resulting in localised surface melting when the alloy is subject to the heat of an air torch.
[0006] Patents U.S. Pat. No. 6,168,071 and EP-B-0729398 (Johns) disclose a silver/germanium alloy which comprised a silver content of at least 77 wt % and a germanium content of between 0.4 and 7%, the remainder principally being copper apart from any impurities, which alloy contains elemental boron as a grain refiner at a concentration of more than 0 ppm and less than 20 ppm. The boron content of the alloy can be achieved by providing the boron in a master copper/boron alloy having 2 wt % elemental boron. It was reported that such low concentrations of boron surprisingly provide excellent grain refining in a silver/germanium alloy, imparting greater strength and ductility to the alloy compared with a silver/germanium alloy without boron. The boron in the alloy. inhibits grain growth even at temperatures used in the jewellery trade for soldering, and samples of the alloy were reported to have resisted pitting even upon heating repeatedly to temperatures where in conventional alloys the copper/germanium eutectic in the alloy would melt. Strong and aesthetically pleasing joints between separate elements of the alloy can be obtained without using a filler material between the free surfaces of the two elements and a butt or lap joint can be formed by a diffusion process or resistance or laser welding techniques. Compared to a weld in Sterling silver, a weld in the above-described alloy has a much smaller average grain size that improved the formability and ductility of the welds, and an 830 alloy has been welded by plasma welding and polished without the need for grinding.
[0007] Ternary and quaternary alloys e.g. Ag—Cu—Ge alloys and Ag—Cu—Zn—Ge alloys include two base metal alloying elements, Cu and Ge, in a noble parent metal, Ag. On exposure to an oxidising atmosphere, two oxidation reactions have to be considered. Firstly, the oxidation of copper to cuprous oxide:
4[Cu] alloy +0 2 ( g )→2Cu 2 0 ( s ) (1)
Secondly, the oxidation of germanium to germanium (di)oxide:
[Ge] alloy +0 2 ( g )→GeO 2 ( s ) (2)
The above equation shows formation of germanium (IV) oxide, GeO 2 , but there may also be formed germanium (II) oxide, GeO or an intermediate material Ge x O y where x is 1 and y is greater than 1 but less than 2. Under standard conditions, i.e. for pure Cu and pure Ge each reacting with pure oxygen gas at 1 atm pressure to form the pure oxide phase, both reactions are feasible, with the chemical driving force for reaction (2) being higher than that of reaction (1) by a factor of 1.65.
[0008] According to WO 02/095082 (Johns) tarnish resistance of ternary alloys of silver, copper and germanium or quaternary alloys of silver, copper, zinc and germanium can be increased by casting a molten mixture to form the alloy and annealing the alloy to reduce its thickness and re-crystallize the grains in the alloy, the annealing being carried out under a selectively oxidizing atmosphere e.g H 2 /H 2 O or CO/CO 2 to promote the formation of GeO 2 while preventing the formation of Cu 2 O.
[0000] Treatment Compositions for Removing or Preventing Silver Tarnish
[0009] Various proposals have been made for cleaning or protecting Sterling silver and other known grades of silver to remove tarnish and/or to inhibit the formation of tarnish.
[0010] U.S. Pat. No. 2,841,501 discloses a silver polish based on an abrasive powder and a C 12 -C 20 n-alkane thiol which is said to be non-toxic, to have a mild odor and to protect silver against tarnishing by forming a monomolecular layer R—S—Ag wherein R represents the alkane chain of the thiol, said layer forming a physical barrier between the silver and reactive ingredients of the atmosphere.
[0011] GB-A-1130540 is concerned with the protection of a finished surface of Sterling or Britannia silver as a step in a production run, and discloses a process that comprises the steps of:
[0012] wetting a clean silver surface of an article with a solution comprising 99 parts by weight of a volatile organic solvent, for example trichloroethylene or 1,1,1-trichloroethane and from 0.1-1.8 parts by weight of an organic solute containing a —SH group and capable of forming a transparent colourless protective layer on the silver surface, for example stearyl and cetyl mercaptan or thioglycollate;
[0013] allowing the solution to react with the surface to form such a layer and allowing the solvent to evaporate; and
[0014] washing the surface with a detergent solution, rinsing the surface with hot water and allowing it to dry. The above process is stated to provide a “long-term finish” intended to last the intended shelf-life until the article reaches the user.
[0015] Halohydrocarbons were said to be the most suitable solvents but their suitability on environmental grounds is now open to question. Ethers were said to be flammable and toxic, and lower alcohols were said to be poor solvents. Water is not mentioned as a solvent. Applicants have seen a report on the Internet from ATOFINA Chemicals Inc that the solubility of mercaptans in water decreases progressively from 23.30 g/litre for methyl mercaptan to 0.00115 g/litre for nonyl mercaptan, and data for for both hexadecyl and octadecyl mercaptan (CAS 2885-00-9) reports them as water-insoluble.
[0016] U.S. Pat. No. 6,183,815 (Enick) also teaches that treatments of the above kind are result in the formation of a self-assembled coating derived from the thiol compounds in which the sulphur atoms are bound onto the metal surface and the alkyl tails are directed away from the metal surface. In the examples of that specification, fluoroalkyl amides e.g. CF 3 (CF 2 ) 5 CONH(CH 2 ) 2 SH in aqueous alcohols e.g. aqueous isopropanol are sprayed onto the surface of silver, after which the surface is rinsed and dried with a soft cloth. The fluoroalkyl amides lack detectable odour and can dissolve in lower alcohols or alcohol/water mixtures, although it is apparent from the description and examples that not all alcoholic solvents produce good films.
[0017] Yousong Kim et al report that the adsorption of thiols onto silver proceeds through an anodic oxidation reaction that produces a shift of the open circuit potential of the substrate metal in the negative direction or if the potential is fixed an anodic current peak:
RSH+ M (0)→RS− M (I)+H + e − ( M ) ( M= Au or Ag), see
http://www.electrochem.org/meetings/past/200/abstracts/symposia/h1/1026.pdf
[0018] Kwan Kim, Adsorption and Reaction of Thiols and Sulfides on Noble Metals, Raman SRS-2000, 14-17 August 2000, Xaimen, Fujian, China, http://pcoss.org/icorsxm/paper/kuankim.pdf, also discloses the formation of self-assembled monolayers and discloses that alkanethiols, dialkyl sulfides and dialkyl disulfides self-assemble on silver surfaces with aliphatic dithiols forming dithoiolates by forming two Ag—S bonds.
[0019] In contrast, the literature on formation of alkylthiols of germanium is relatively sparse. The dissociative adsorption of H 2 S at a Ge 100 surface to yield adsorbed —SH groups and adsorbed hydrides has been reported by Nelen et al., Applied Surface Science, 150, 65-72 (1999), see http://www.chem.missouri.edu/Greenlief/pubs/00005797.pdf, see also a report by Professor Michael Greenlief of the University of Missouri-Columbia http://www.chem.missouri.edu/Greenlief/Research.html that room temperature exposure of H 2 S to Ge(100) results in dissociative adsorption that can be followed easily by ultraviolet photoelectron spectroscopy. The reaction of alkanethiols with Ge to form a high quality monolayer has been reported in the context of semiconductor and nanotechnology by Han et al, J. Am. Chem. Soc., 123, 2422 (2001). In the experiment described, a Ge(111) wafer is sonicated in acetone to dissolve organic contaminants and immersed in concentrated HF to remove residual oxide and produce a hydrogen-terminated surface, after which the wafer is immersed in an alkanethiol solution in isopropanol, sonicated in propanol and dried.
SUMMARY OF THE INVENTION
[0020] Although GB-A-1130540 was alleged to provide a long-term finish, the experience of one of the inventors who is a silversmith is this type of treatment does not fully solve the difficulties created by tarnish in the period between manufacture and supply to the ultimate purchaser or user and suffers from a number of shortcomings. Although a silver product might arrive at the retailer in an untarnished state, it was largely the result of the wrapping applied by the manufacturer, which protected the article from air. Once the wrapping was removed and the article was displayed in a retail environment such as a display case in a hotel where it was subject to ambient air and the heat of artificial lighting, an article of conventional Sterling silver would require re-polishing after one week and after two weeks would normally be so tarnished as to be un-saleable. At an exhibition, the life of an article on display before significant tarnish sets in may be as short as 3-4 days. Re-polishing produces wear and fine handling scratches, so that unless the article can be sold quickly it looses its pristine appearance. The need to polish display silver at frequent intervals adds to the labour cost of a jeweller or other retail establishment, whose management take the view that its staff should be employed to sell products and not to clean stock. Tarnish at point of sale or display is therefore a serious problem that reduces the willingness of those in the distribution chain to stock and display silver products, and which has not yet been adequately solved.
[0021] When the product reaches the ultimate purchaser, it is of course desirable that the task of tarnish removal should be made as infrequent and undemanding as possible.
[0022] Silver alloys according to the teaching of GB-B-2255348 and EP-B-0729398 are now commercially available in Europe and in the USA under the trade mark Argentium, and the word “Argentium” as used herein refers to these alloys. Although they exhibit improved tarnish resistance compared to e.g. Sterling silver, and any tarnish that forms can be removed by simple washing, there is still room for improvement in tarnish resistance. That remains true even when annealing is conducted in a selectively oxidising atmosphere as disclosed in WO 02/095082.
[0023] It has now been found that an alkanethiol, alkyl thioglycollate, dialkyl sulphide or dialkyl disulphide can be used for the surface treatment of an alloy of silver containing an amount of germanium that is effective to reduce firestain and/or tarnishing so as to reduce or further reduce tarnishing of the alloy such that a sample can be subjected to hydrogen sulphide gas above a 20% solution of ammonium polysulphide for at least 30 minutes and typically 45-60 minutes at room temperature while retaining a generally untarnished appearance.
[0024] The invention also therefore relates to the use of an organic compound containing —SH or —S—S— bonds e.g. a C 2 -C 40 (preferably C 12 -C 24 ) alkanethiol, alkyl thioglycollate, dialkyl sulphide or dialkyl disulphide in the preparation of a tarnish inhibitor for an article of a silver/germanium alloy that has a silver content of at least 77 wt % and a germanium content of between 0.1 and 7% so as to reduce tarnishing of said alloy such that a sample can be supported close above a 20% solution of ammonium polysulphide for at least 30 minutes and typically 45-60 minutes while retaining a generally untarnished appearance.
[0025] The invention further provides an alloy of silver, or a shaped article formed of said alloy, containing an amount of germanium that is effective to reduce firestain and/or tarnishing and that has been treated with a C 12 -C 24 alkanethiol, alkyl thioglycollate, dialkyl sulphide or dialkyl disulphide.
[0026] The invention further provides a method for manufacturing a tarnish-resistant silver article, which comprises the steps of:
[0027] forming a shaped article of an alloy of silver containing an amount of germanium that is effective to reduce firestain and/or tarnishing;
[0028] surface treating the article with an alkanethiol, alkyl thioglycollate, dialkyl sulphide or dialkyl disulphide; and
[0029] introducing the article into packaging.
[0030] The above accelerated tarnish test in which the article is subject to hydrogen sulphide gas from the ammonium polysulphide solution above which it is suspended at a height of e.g. 30 mm corresponds to a period of a year or more in a retail environment where an article is on display and exposed to ambient atmosphere and may be subject to elevated temperatures. It is the combination of the protective function of the germanium content of the alloy with the further protection from the organo-sulphur compound that is believed to be responsible for the observed increase in tarnish resistance. The period during which the article retains its untarnished appearance under these severe conditions may be three or more times the corresponding period for an article that has not been treated with an organo-sulphur compound, which is unexpected because the same accelerated tarnish test carried out under the same conditions on a conventional Sterling silver article not containing protective germanium does not reveal a significant increase in untarnished lifetime between its untreated and organo-sulfur treated states. Accelerated tarnishing trials carried out using Argentium and standard Sterling silver samples immersed in solutions of octadecyl mercaptan and hexadecyl mercaptan have shown that the protective thiol is removed from the standard Sterling sample but not from the Argentium silver samples on rubbing with a tissue soaked in a solvent (EnSolv 765, an n-propyl bromide based solvent cleaner discussed below). In accelerated testing the solvent-rubbed regions of standard Sterling silver discolour more rapidly than the un-rubbed regions whereas in Argentium silver no noticeable difference in appearence develops between the rubbed and un-rubbed regions, suggesting that thiol bonding is stronger or more effective.
[0031] Accelerated tarnishing tests with Argentium Sterling using ammonium polysulphide have been reported by the Society of American Silversmiths, see
[0032] http://www.silversmithing.com/1argentium4.htm
[0033] and in a comparative test the Argentium Sterling remained untarnished after one hour whereas conventional Sterling became tarnished after less than 15 minutes. However, in this test 0.5 ml of 20% ammonium polysulfide solution is mixed with 200 ml of distilled water, so that the test is greatly less severe than when samples are exposed to the 20% solution itself. In WO 02/095082, samples were suspended above 20% ammonium polysulphide, but the exposure times were relatively short, and onset of yellowing was reported for Ag—Cu—Ge alloys after 3-5 minutes exposure. Other tests reported in that specification involve placing samples in a desiccator containing flowers of sulphur and calcium nitrate and are less severe than the ammonium polysulphide test.
[0034] As part of their program for developing improved formulations for the treatment agents described above, the applicants have unexpectedly discovered that the treatment agents can be dissolved or dispersed directly in aqueous surfactant without the need for preliminary dissolving of the treatment agent in an organic solvent and subsequent mixing of the resulting solution with aqueous liquid. Embodiments of the above compositions are optically clear and storage-stable at ambient temperatures for a period of weeks or months. The treatment composition may therefore be water-based and comprise an alkanethiol, alkyl thioglycollate, dialkyl sulfide or dialkyl disulfide and a mixture of an anionic surfactant with a neutral or amphoteric surfactant and water.
DETAILED DESCRIPTION OF THE INVENTION
[0000] Silver-Copper-Germanium Alloys
[0035] The alloys that may be treated according to the invention include an alloy of silver containing an amount of germanium that is effective to reduce firestain and/or tarnishing. U.S. Pat. No. 6,406,664 (Diamond) discloses that amounts of germanium as low as 0.1 wt % can be effective provided that substantial amounts of tin are present but although formulation examples are given, no test data for corrosion or firestain is given either for articles made by casting or for articles fabricated from sheet. The inventor considers that 0.5 wt % Ge provides a preferred and more realistic lower limit and that in practice use of less than 1 wt % is undesirable. A two-component copper-free alloy could comprise 99% Ag and 1% Ge, and a tarnish-free casting alloy for jewellery has been reported that comprises 2.5% Pt, 1% Ge, balance Ag and optionally containing Zr, Si or Sn.
[0036] The ternary Ag—Cu—Ge alloys and quaternary Ag—Cu—Zn—Ge alloys that can suitably be treated by the method of the present invention are those having a silver content of at least 30%, preferably at least 60%, more preferably at least 80%, and most preferably at least 92.5%, by weight of the alloy, up to a maximum of no more than 98%, preferably no more than 97%. The germanium content of the Ag—Cu—(Zn)—Ge alloys should be at least 0.1%, preferably at least 0.5%, more preferably at least 1.1%, and most preferably at least 1.5%, by weight of the alloy, up to a maximum of preferably no more than 6.5%, more preferably no more than 4%.
[0037] If desired, the germanium content may be substituted, in part, by one or more elements which have an oxidation potential selected from Al, Ba, Be, Cd, Co, Cr, Er, Ga, In, Mg, Mn, Ni, Pb, Pd, Pt, Si, Sn, Ti, V, Y, Yb and Zr, provided the effect of germanium in terms of providing firestain and tarnish resistance is not unduly adversely affected. The weight ratio of germanium to substitutable elements may range from 100:0 to 60:40, preferably from 100:0 to 80:20. Preferably, the germanium content consist entirely of germanium, i. e. the weight ratio is 100:0.
[0038] The remainder of the ternary Ag—Cu—Ge alloys, apart from impurities and any grain refiner, will be constituted by copper, which should be present in an amount of at least 0.5%, preferably at least 1%, more preferably at least 2%, and most preferably at least 4%, by weight of the alloy. For an ‘800 grade’ ternary alloy, for example, a copper content of 18.5% is suitable. The remainder of the quaternary Ag—Cu—Zn—Ge alloys, apart from impurities and any grain refiner, will be constituted by copper which should be present in an amount of at least 0.5%, preferably at least 1%, more preferably at least 2%, and most preferably at least 4%, by weight of the alloy, and zinc which should be present in a ratio, by weight, to the copper of no more than 1:1. Therefore, zinc is optionally present in the silver-copper alloys in an amount of from 0 to 100% by weight of the copper content. For an ‘800 grade’ quaternary alloy, for example, a copper content of 10.5% and zinc content of 8% is suitable.
[0039] In addition to silver, copper and germanium, and optionally zinc, the alloys preferably contain a grain refiner to inhibit grain growth during processing of the alloy. Suitable grain refiners include boron, iridium, iron and nickel, with boron being particularly preferred. The grain refiner, preferably boron, may be present in the Ag—Cu—(Zn)—Ge alloys in the range from 1 ppm to 100 ppm, preferably from 2 ppm to 50 ppm, more preferably from 4 ppm to 20 ppm, by weight of the alloy.
[0040] In a preferred embodiment, the alloy is a ternary alloy consisting, apart from impurities and any grain refiner, of 80% to 96% silver, 0.1% to 5% germanium and 1% to 19.9% copper, by weight of the alloy. In a more preferred embodiment, the alloy is a ternary alloy consisting, apart from impurities and grain refiner, of 92.5% to 98% silver, 0.3% to 3% germanium and 1% to 7.2% copper, by weight of the alloy, together with 1 ppm to 40 ppm boron as grain refiner. In a further preferred embodiment, the alloy is a ternary alloy consisting, apart from impurities and grain refmer, of 92.5% to 96% silver, 0.5% to 2% germanium, and 1% to 7% copper, by weight of the alloy, together with 1 ppm to 40 ppm boron as grain refiner.
[0000] Protective Agents
[0041] As protective agent there may be used a compound containing a long chain alkyl group and a —SH or —S—S— group, e.g. an alkanethiol, dialkyl sulfide or dialkyl disulfides in which the chain is preferably at least 10 carbon atoms long and may be C 12 -C 24 . The —SH or —S—S— compounds that many be used include straight chain saturated aliphatic compounds containing 16-24 carbon atoms in the chain, for example cetyl mercaptan (hexadecyl mercaptan) and stearyl mercaptan (octadecyl mercaptan) and cetyl and stearyl thioglycollates whose formulae appear below.
[0042] Octadecyl mercaptan is a white to pale yellow waxy solid that is insoluble in water and that melts at 15-16° C. Hexadecyl mercaptan is also a white or pale yellow waxy solid that melts at 30° C.
[0000] Formulations Based on Organic Solvents
[0043] The protective agent may be used in solution in a solvent e.g. a non-polar organic solvent such as an alcohol e.g. methyl or ethyl alcohol, a ketone e.g. acetone or methyl ethyl ketone, an ether e.g. diethyl ether, an ester e.g. n-butyl acetate, a hydrocarbon, a halocarbon e.g. methylene chloride, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene or HCFC 141b. The protective agent may comprise 0.1-1 wt % of the solvent. Solvents based on alkyl or aryl halides may be used e.g. n-propyl bromide which is presently preferred on the ground of the short atmospheric life of that compound, its relatively low toxicity compared to other halocarbons, its favourable chemical and physical properties and its boiling point, specific heat and latent heat of vaporization.
[0044] U.S. Pat. No. 5,616,549 discloses a solvent mixture comprising: 90 percent to about 96.5 percent n-propyl bromide; 0 percent to about 6.5 percent of a mixture of terpenes, the terpene mixture comprising 35 percent to about 50 percent cis-pinane and 35 percent to about 50 percent trans-pinane; and 3.5 percent to about 5 percent of a mixture of low boiling solvents, the low boiling solvent mixture comprising 0.5 percent to 1 percent nitromethane, 0.5 percent to 1 percent 1,2-butylene oxide and 2.5 percent to 3 percent 1,3-dioxolane. The solvent mixture has the following advantages:
[0045] (i) it is properly stabilized against any free acid that might result from oxidation of the mixture in the presence of air, from hydrolysis of the mixture in the presence of water, and from pyrolysis of the mixture under the influence of high temperatures;
[0046] (ii) it is non-flammable and non-corrosive;
[0047] (iii) the various components of the solvent mixture are not regulated by the U.S. Clean Air Act; and
[0048] (iv) none of the various components of the solvent mixture are known cancer causing agents (i.e., the various components are not listed by N.T.I., I.A.R.C. and California Proposition 65, nor are they regulated by OSHA). Moreover, the solvent mixture has a high solvency with a kauri-butanol value above 120 and, more preferably, above 125. In addition, the solvent mixture has an evaporation rate of at least 0.96 where 1,1,1-Trichloroethane=1. Upon evaporation, the solvent mixture leaves a non-volatile residue (NVR) of less than 2.5 mg and, more preferably, no residue. Solvents made in accordance with the above patent are available from Enviro-Tech International, Inc of Melrose Park, Ill., USA under the trade name EnSolv.
[0000] Formulations Based on Organic Solvent and Water
[0049] For many purposes, e.g. light industrial applications, it may be preferred to carry out the anti-tarnish treatment using a predominantly aqueous solvent system. For this purpose, the protective agent may be dissolved in a water-immiscible organic solvent, for example a solvent based on n-propyl bromide, the resulting solution may be mixed with a relatively concentrated water-based soap or detergent composition which acts as a “carrier”, after which water is added to the resulting mixture to provide an aqueous treatment dip or combined degreasing and treatment solution. Thus an aqueous dip has the advantages that a solvent degreasing system is not necessary, the dip is easily made and may be used cold, all areas of immersed articles can come into contact with the stearyl mercaptan or other treatment agent, Argentium Silver only requires 2 minutes-1 hour in the dip, rinsing and drying of articles are made easy as water droplets are repelled from the surface of the polished silver, and the dip can be easily used in a manufacturing environment before articles are sent to retailers.
[0050] Preferred water-based detergents may be based on anionic, alkoxylated non-ionic or water-soluble cationic surface active agents or mixtures of them and preferably have a pH at or close to 7. Anionic surfactants may be based on alkyl sulphates and alkyl benzene sulphonates, whose harshness on prolonged skin exposure may be reduced by the co-presence or use of alkyl ethoxy sulphates (U.S. Pat. No. 3,793,233, Rose et al.; U.S. Pat. No. 4,024,078 Gilbert; U.S. Pat. No. 4,316,824 Pancherni). Other known surfactants e.g. betaines may also be present, see e.g. U.S. Pat. No. 4,555,360 (Bissett). A suitable formulation containing 5-15 wt % non-ionic surfactants and 15-30 wt % anionic surfactants is available commercially in the UK under the trade name Fairy Liquid (Proctor & Gamble).
[0051] An aqueous liquid may also be made by dissolving the treatment agent in a non-organic solvent and adding a relatively concentrated aqueous detergent liquid, for example undiluted Fairy Liquid. This provides a detergent liquid that has a number of advantages: the soapy liquid is easily made, the liquid is easily applied to the Argentium Silver articles with a damp sponge/cotton wool/cloth etc, the liquid and lather enables the stearyl mercaptan or other treatment agent to get into those awkward areas on an article where a cloth may not be able to reach, rinsing and drying of articles are made easy as water droplets are repelled from the surface of the polished silver, the process can be easily used in a manufacturing environment before articles are sent to retailers and can also be easily used in a retail or domestic environment. Furthermore, the hydrophobic properties imparted to silver/silver alloy on treatment with the present thiol-based treatment agents may alleviate or overcome the problems of water-marks or water-staining from rinsing processes in a manufacturing or domestic environment.
[0000] Formulations Based on Aqueous Liquids
[0052] It has surprisingly been found that formulations containing effective amounts of the treatment agents can be made by dissolving them directly in aqueous liquids containing an anionic and a neutral or amphoteric surfactant and free from water-immiscible organic solvents and preferably free from all other solvents. The treatment agents may be dissolved in relatively concentrated surfactant-containing aqueous liquids, which may be used as such or after subsequent dilution with water, see in particular the instructions given in the preceding section.
[0053] The treatment agent may be present in said composition, prior to dilutiuon thereof, in an amount of at least 0.1 wt % and preferably at least 1 wt %, the solids content of the composition being at least 5 wt %, typically 10-40 wt % and possibly 50 wt % or more. The ability of aqueous surfactant liquids to dissolve or disperse such relatively high concentrations of higher alkyl thiols and other treatment agents which are reported to be highly water-insoluble has not been described. The resulting concentrates may be diluted with water to provide an aqueous treatment dip or combined degreasing solution and dip for use as explained above, and it has been found that the treatment agent may remain in solution or suspension following such dilution and may remain effective for the surface treatment of silver-copper or silver-copper-germanium alloys and possibly other metals such as copper, brass and nickel where surface protection films may retard corrosion. Particularly good results from the stability and effectiveness standpoint may be obtained by mixing hexadecyl mercaptan (in the liquid state) straight into a surfactant “carrier” and using the solution as such or on subsequent dilution with water.
[0054] In particular, the present treatment-agents can be successfully dispersed in aqueous liquids containing mixtures of neutral and anionic surfactants with the neutral surfactants providing e.g. about 33 wt % of the total surfactant present. Treatment agents that can be dispersed in such agents include n-hexadecyl thiol and n-octadecyl thiol. They can also be successfully dispersed in aqueous liquids containing mixtures of amphoteric or zwiterionic surfactants and anionic surfactants and such mixtures can provide relatively storage stable optically clear solutions with little or no tendency to re-precipitate the treatment agent. In that case the weight ratio of the amphoteric or zwitterionic surfactant to the anionic surfactant may be from 1:10 to 10:1, typically close to 1:3.
[0055] Amphoteric or zwitterionic surfactants that may be used alone or in admixture with one another and/or with nonionic surfactants and/or with anionic surfactants may be derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic group, straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
[0056] Examples of zwitterionic surfactants that may be employed include betaine surfactants, which are preferred, imidazoline-based surfactants, aminoalkanoate surfactants and iminodialkanoate surfactants. Suitable such surfactants include amidocarboxybetaines, such as cocoamidodimethylcarboxymethylbetaine, laurylamidodimethylcarboxymethyl-betaine, cetylamidodimethylcarboxy-methylbetaine, and cocoamido-bis-(2-hydroxyethyl)carboxymethyl-betaine. Particularly preferred are amidocarboxybetaines betaines of the formula below wherein R represents C 8 -C 18 alkyl e.g. cocamidopropyl betaine. That compound is generally regarded as safe: in an Ames test conducted by BASF it did not prove mutagenic to Salmonella indicator organisms and in a human repeated patch insult test (HRIPT) it did not indicate either contact hypersensitivity or photoallergy (see the MAFO CAB cocamidopropyl amino betaine data sheet published by BASF):
Also useful are sulphobetaine surfactants, e.g amido sulfobetaines such as lauramido-sulfopropylbetaine of formula indicated below,
cocamido-2-hydroxypropylsulfobetaine, cocoamidodimethylsulfopropyl-betaine, stearylamido-dimethylsulfopropylbetaine, and laurylamido-bis-(2-hydroxyethyl)-sulfopropylbetaine. Also useful may be imidazoline-based surfactants including gylcinate and amphoacetate compounds e.g. cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate, and cocoamphoacetate, aminoalkanoate surfactants e.g. n-alkylamino-propionates and n-alkyliminodipropionates such as N-lauryl-β-amino propionic acid and salts thereof, and N-lauryl-β-imino-dipropionic acid and salts thereof.
[0057] Non-ionic surface-active agents that may be used alone or in admixture include compounds produced by the condensation of an alkylene oxide with an organic hydrophobic compound that may be aliphatic or alkyl aromatic. The length of the hydrophilic or polyoxyalkylene moiety that is condensed with any particular hydrophobic compound can be adjusted to yield a water-soluble compound having the desired balance between hydrophilic and hydrophobic moieties. Semi-polar nonionic surface active agents may also be used, including amine oxides, phosphine oxides, and sulfoxides. Suitable classes of compound include:
Polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight or branched chain, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerized propylene, diisobutylene, octene, or nonene. Condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol may either be straight or branched and generally contains from about 8 to about 22 carbon atoms. Condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. Amine oxide surfactants, for example dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis-(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds. Phosphine oxide surfactants, e.g. dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide, bis-(hydroxymethyl)dodecylphosphine oxide, bis-(2-hydroxyethyl)dodecylphosphine oxide, (2-hydroxypropyl)methyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-(2-hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds. Sulfoxide surfactants, for example octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl 2-hydroxyethyl sulfoxide, and dodecylethyl sulfoxide. Ethanolamide-based surfactants e.g. coconut fatty acid monoethanolamide or diethanolamide.
wherein R represents C 10 -C 40 , esp C 12 -C 18 alkyl e.g. oleyl- or coco-. Further surfactants may be based on diethylene triamine (DETA)-based quaternaries, such as diamidoamine ethoxylates and imidazolines, and esterquats. As a class, esterquats can be based on compounds including methyl diethanolamine (MDEA), triethanolamine (TEA), and N,N-dimethyl-3aminopropane-1,2-diol (DMAPD).
[0065] A wide variety of alkyl sulfates may be used as anionic surface-active agents including fatty alcohol sulphates, fatty alcohol ether sulphates, alkyl phenol ether sulphates, alkyl aryl sulphonic acids and salts thereof, cumene, toluene and xylene sulphonates and salts thereof and alkyl sulphosuccinates e.g. sodium or ammonium lauryl sulfate. However, a preferred class of anionic surface active agents is polyol monoalkylether sulfates of the formula RO—(CH 2 CH 2 ) n SO 3 M wherein R represents C 10 -C 18 alkyl, n is 2-6 (preferably about 2-3) and M represents a monovalent cation. Such compounds are sulfonated ethoxylated C 10 -C 18 alkohols which may be derived from coconut oil or tallow or may be synthetic. Sodium laureth sulfate which has been used successfully herein is a sodium lauryl ether sulphate ethoxylated to an average of two moles of ethylene oxide per mole of lauric acid and sulfated, and is of formula CH 3 (CH 2 ) 10 CH 2 (OCH 2 CH 2 ) 2 OSO 3 Na.
[0066] In addition to simple treatment agents, the above compositions may be formulated into metal polishes e.g. for silver or brass. Such products may be formulated as liquid products into which objects such as jewellery or cutlery are to be dipped. After dipping, the objects are usually rinsed under water and dried with a soft cloth. Alternative formulations take the form of creams or paptes which are applied with a soft cloth and then removed.
[0067] For formulation into dipping compositions, the active ingredients are normally an acid having a pKa of not more than 5, e.g. phosphoric, citric, oxalic, or tartaric acid together with thiourea or a derivative thereof e.g. an alkyl derivative such as methyl or ethyl thiourea. For formulation into creams or pastes there may be e.g. about 25 wt % of a mild abrasive such as precipitated chalk, infusorial earth, silica or γ-alumina (e.g. 0.05 μm grade). These ingredients are believed compatible with the surfactants and treatment agents and can be incorporated when convenient by simple mixing.
[0000] Treatment Procedures
[0068] The surface treatment may be carried out after the manufacturing stages for a shaped article made of the alloy have been completed. The article may be of flatware, hollowware or jewellery. Fabrication steps may include spinning, pressing, forging, casting, chasing, hammering from sheet, planishing, joining by soldering brazing or welding, annealing and polishing using buffs/mops and aluminium oxide or rouge.
[0069] An article to be treated may be de-greased by various methods:
Vapour degreasing with or without ultrasonics Aqueous degreasing with or without ultrasonics Organic solvent degreasing with or without ultrasonics (e.g. degreasing with ethanol or acetone prior to thiol treatment which may provide very good accelerated tarnish test results). Simultaneous degreasing and thiol treatment, the thiol being present in an organic or aqueous degreasing medium.
[0074] For example, the article may be degreased ultrasonically in a treatment bath, dipped into a bath containing the treatment agent e.g. 1 wt % stearyl mercaptan in solvent e.g. EnSolv, rinsed in one or more baths of the solvent and allowed to dry by evaporation. Rinsing excess thiol away with the same solvent that is used for thiol treatment is preferred, so that thiols that have not reacted with the metallic surface are removed and are unavailable to react with anything else. The solvent should leave no or substantially no residue, so that subsequent washing with water or aqueous solvents should be unnecessary and the article can be allowed to dry. The article may then be packed for delivery into the distribution chain. This may include wrapping the article in one or more protective sheets, placing it in a presentation box, and wrapping the presentation box in a protective wrapping e.g. of heat-shrunk plastics film. Articles which have been treated with an organic compound containing —SH or —S—S— groups as aforesaid and packaged should not only reach their point of sale in good condition but should if displayed e.g. on a shelf or in a cabinet for an extended period, expected to be at least 6 months and possibly 12 months or more, remain without development of significant tarnish.
[0075] The articles may alternatively simply be polished with a polish containing 1-5wt % of the organo-sulphur compound e.g. stearyl mercaptan together surfactants and a cleaning agent e.g. diatomaceous earth in a solvent. As a further alternative, they may be simply polished with a cloth impregnated with the sogano-sulphur compound e.g. cetyl or stearyl mercaptan e.g by impregnation with a treatment agent in an organic solvent e.g. n-propyl bromide followed by drying. The advantages of a cleaning cloth are that it is easily manufactured, can be easily used in a retail or domestic environment and is good for general upkeep of Argentium Silver (if required).
[0076] The treatment method of the invention would find particular benefit in the tarnish protection of blanks for stamping coins immediately before the stamping operation because it has been found that embodiments of the present films can largely or wholly survive the stamping operation and can provide pritection against tarnishing for the newly minted coins. It will be appreciated that coins in mint condition are packaged for collectors with minimal handling, and that every ocasion of handling e.g. polishing with a soft cloth involves risk of damage to the coin. The risk of such damage is reduced by the present treatment which can impart prolonged tarnish resistance.
[0077] The invention will now be further described, by way of illustration only, with reference to the following examples. Throughout the examples, the term “enhanced tarnish resistance” of samples treated with stearyl mercaptan refers to the comparison with samples of Argentium Silver which have not had any treatment except for polishing and degreasing.
EXAMPLE 1
Solvent Dip Application (Solvent Degreased Samples)
[0078] Solutions were made up containing stearyl mercaptan (0.1, 0.5 and 1.0 gram) in EnSolv 765 (100 ml). Samples of Argentium Sterling which had been polished and ultrasonically degreased in EnSolv 765 for 2 minutes were each immersed in one of the stearyl mercaptan solutions for periods of 2 minutes, 5 minutes and 15 minutes. The samples were then buffed with clean cotton wool.
[0079] In order to evaluate tarnish resistance, the alloy samples were supported on a glass slide in a fume cupboard about 25 mm above the surface of 20% ammonium polysulphide solution so as to be exposed to the hydrogen sulphide that arises from that solution. All of the samples demonstrated good tarnish resistance during a one-hour test, with very slight yellowing after 45 minutes exposure to the hydrogen sulphide. The light film on the samples was easily removed with a cleaning cloth impregnated with stearyl mercaptan.
[0080] By way of comparison, a standard Sterling silver sample started to discolour as soon as it was subjected to the above test and after one hour had formed a heavy black tarnish which could not be removed with a cleaning cloth impregnated with stearyl mercaptan. The results obtained with a second Sterling silver sample that had been wiped with the cleaning cloth were similar and discoloration started as soon as the sample had been placed into the test. An Argentium Sterling alloy produced in accordance with EP-B-0729398 showed onset of tarnishing after 3 minutes. Another sample of the Argentium Sterling alloy that had been annealed in a selectively oxidizing atmosphere as disclosed in WO 02/09502 showed onset of tarnishing after 6 minutes. The markedly increased delay in onset of tarnishing was unexpected in the absence of an increased delay in the case of the standard Sterling Silver article.
EXAMPLE 2
Effect of Post-Treatment Solvent Cleaning
[0081] Example 1 was repeated for the Argentium samples except that instead of buffing with cotton wool after the mercaptan treatment, the samples were ultrasonically degreased in EnSolv 765 for 2 minutes. The samples were then tarnish tested as described in Example 1 and all found to show enhanced tarnish resistance. The ability of the protective effect of the stearyl mercaptan treatment to survive ultrasonic cleaning in EnSolv suggests that the tarnish resistance is being achieved by a surface reaction involving the stearyl mercaptan and possibly the germanium in the Argentium Silver, and not by formation of a grease or oil layer on the surface of the Argentium.
EXAMPLE 3
Aqueous Dip Application (Solvent Degreased Samples)
[0082] An anti-tarnish treatment solution was prepared using the following ingredients:
Stearyl mercaptan 1 g EnSolv 765 5 ml Detergent (Fairy Liquid) 40 ml De-ionised water 100 ml
[0083] The Stearyl Mercaptan was dissolved into the EnSolv 765 after which the resulting solution was mixed with detergent (Fairy Liquid) and diluted with water to provide an aqueous dip. Samples of Argentium silver were polished and ultrasonically degreased in EnSolv 765 for 2 minutes, immersed into the above aqueous dip for 2 minutes at ambient temperatures and then rinsed under running tap water It was noted the water was immediately repelled from the polished surface, which left the samples dry. Samples were tarnish tested as described in Example 1 and all showed enhanced tarnish resistance.
EXAMPLE 4
Aqueous Dip Application 2 (Detergent Degreased Samples)
[0084] Samples of Argentium Sterling were degreased in a 2% aqueous solution of a detergent (Fairy Liquid) and were then immersed in the treatment solution of Example 3. It was noted that the treated samples had become water-repellent as described in Example 3. Samples were tarnish tested as described in Example 1 and all showed enhanced tarnish resistance. The above test was repeated except that the Fairy liquid in the treatment solution was replaced by a liquid hand soap is (40 ml). When exposed to ammonium polysulphide solution, the samples did not show enhanced tarnish resistance. It is possible that this may have been because the hand soap was more dilute.
EXAMPLE 5
Simultaneous Degreasing and Anti-Tarnish Treatment
[0085] The following solutions were prepared:
[0086] 1 gram stearyl mercaptan
[0087] 5 ml EnSolv 765
[0088] 20 ml detergent (Fairy Liquid)
[0089] 100 ml de-ionised water
[0090] 1 gram stearyl mercaptan
[0091] 5 ml EnSolv 765
[0092] 30 ml detergent (Fairy Liquid)
[0093] 100 ml de-ionised water
[0094] 1 gram stearyl mercaptan (Preferred quantities)
[0095] 5 ml EnSolv 765
[0096] 40 ml detergent (Fairy Liquid)
[0097] 100 ml de-ionised water
[0098] 1 gram stearyl mercaptan
[0099] 5 ml EnSolv 765
[0100] 40 ml detergent (Fairy Liquid)
[0101] 500 ml de-ionised water
[0102] 1 gram stearyl mercaptan
[0103] 5 ml EnSolv 765
[0104] 40 ml detergent (Fairy Liquid)
[0105] 1000 ml de-ionised water.
[0106] The solutions were heated to 50° C. in an ultrasonic cleaning tank. Samples of polished Argentium Silver were ultrasonically degreased in the solutions for 2 minutes and were rinsed under running tap water. For the first three of the above treatment solutions, it was observed that water was repelled off of the surface leaving the samples dry. Samples treated with the first three solutions above were tarnish tested as described in Example 1 and all showed enhanced tarnish resistance. However, in the case of the samples treated with the last two solutions, water was not repelled off of the surface during the rinsing stage. When the samples dried they showed streaks on the surface which discoloured during the tarnish test. The sample treated with the 500 ml solution showed less discolouration than the sample treated with the 1000 ml solution. The above experiments show that Argentium silver can be simultaneously degreased and protected against tarnish using a thiol treatment agent applied in an aqueous system, and that the more concentrated the stearyl mercaptan/EnSolv/detergent/Water solution, the better the tarnish resistance produced.
EXAMPLE 6
Direct Application—Neat Detergent Solutions (Solvent Degreased/Aqueous Degreased Samples)
[0107] The following solutions were prepared:
[0108] 1 gram stearyl mercaptan
[0109] 5 ml EnSolv 765
[0110] 40 ml detergent (Fairy Liquid) (Preferred quantities)
[0111] 1 gram stearyl mercaptan
[0112] 5 ml EnSolv 765
[0113] 40 ml soap (liquid hand soap)
[0114] The stearyl mercaptan was initially dissolved into the EnSolv. The detergent was then mixed into the solutions. Samples of Argenium Silver were polished and ultrasonically degreased in EnSolv 765 for 2 minutes. The stearyl mercaptan/EnSolv/detergent solutions were then directly applied to the surface of the Argentium samples using damp cotton wool and massaged into lather. The samples were then rinsed under running tap water. In each case, it was noted that water was repelled off of the polished surface, leaving the samples dry. Samples were tarnish tested as in Example 1 by being exposed to neat ammonium polysulphide solution over a period of 1 hour. They all showed enhanced tarnish resistance. The above direct method for applying the Stearyl Mercaptan was tested on samples degreased in a 2% Fairy Liquid aqueous solution. Enhanced tarnish resistance was again achieved.
EXAMPLE 7
Cloth Application (Solvent Degreased Samples)
[0115] Cloths were prepared by soaking clean cotton cloth in the following solutions:and allowing the cloths to dry
[0116] 0.1 gram Stearyl Mercaptan dissolved in 100 ml EnSolv
[0117] 0.5 gram Stearyl Mercaptan dissolved in 100 ml EnSolv
[0118] 1.0 gram Stearyl Mercaptan dissolved in 100 ml EnSolv (Preferred)
[0119] Samples of Argentium Silver (which had been polished and ultrasonically degreased in EnSolv 765 for 2 minutes) were wiped with the cloths then buffed with clean cotton wool. Samples were tarnish tested as described in Example 1 by being exposed to ammonium polysulphide solution over a period of 1 hour. All of the samples showed enhanced tarnish resistance.
EXAMPLE 8
Hexadecyl and Octadecyl Mercaptan in Fairy Liquid
[0120] Hexadecyl mercaptan (1 g) in the liquid state was mixed with Fairy liquid (surfactant containing anionic and nonionic surface active agents) and with water in the quantities indicated below:
Reference Fairy liquid (ml) Deionised water (ml) 8.1 40 Nil 8.2 100 Nil 8.3 200 Nil 8.4 40 100 8.5 40 200
[0121] The ingredients of solution 8.2 appeared to mix well without needing the hexadecyl mercaptan to be dissolved in an organic solvent beforehand. A sample of Argentium silver was immersed in the resulting solution for 10 minutes and rinsed. The surface of the Argentium sample had become hydrophobic, suggesting the formation of a layer of hexadecyl mercaptan attached to the surface of the Argentium silver. It rinsed well in water without any noticeable deposit being left on the surface after rinsing. A region of the sample was rubbed with cotton wool soaked in EnSolv 765 and then subjected to tarnish testing with neat ammonium polysulphide over a period of 45 minutes. Excellent tarnish resistance was noted, without significant difference between the region that had been treated with EnSolv 765 and the region that had not been so treated. Similar solutions were prepared from octadecyl mercaptan and Fairy liquid. They were transparent at first, but of lesser stability with separation of a surface layer of octadecyl mercaptan after some months.
EXAMPLE 9
Hexadecyl Mercaptan in Simple Shower Gel
[0122] Hexadecyl mercaptan in the liquid state was mixed with Simple shower gel (a clear shower gel from Accentia Health and Beauty Ltd, Birmingham, UK, and believed to contain sodium laureth sulfate and cocamidopropyl betaine as principal surfactants, together with cocamide DEA and incidental ingredients) and with water in the quantities indicated below:
Reference HDM (g) Simple (ml) Deionised water (ml) 9.1 1 100 Nil 9.2 1 100 100 9.3 5 100 100 9.4 1 200 100
[0123] Shortly after mixing, solutions 9.1 and 9.4 were completely transparent viscous gels free from noticeable separation of the hexadecyl mercaptan. Sample 9.2 was also completely transparent but had a water-like consistency and again did not exhibit separation of hexadecyl mercaptan. Sample 9.3 which also had a water-like consistency appeared as a milky emulsion when shaken but exhibited separation of hexadecyl mercaptan at the surface on standing.
[0124] In a preliminary experiment, a sample of Argentium silver was immersed in solution 9.1 for 10 minutes and rinsed. The surface of the Argentium sample had become hydrophobic, suggesting the formation of a layer of hexadecyl mercaptan attached to the surface of the Argentium silver. It rinsed well in water without any noticeable deposit being left on the surface after rinsing. When tested with neat ammonium polysulfide, excellent tarnish resistance was noted.
[0125] Samples of Argentium silver and conventional Sterling silver were prepared as follows. Each sample was polished with Steelbright polish, followed by rouge, and then ultrasonically degreased for two minutes in a 2 wt % Fairy Liquid solution in water at 54° C. It was then further degreased for 5 minutes in ethanol and immersed at ambient temperatures in the test solution. After removal, part of each sample was rubbed with tissue soaked in EnSolv 765 and then subjected to tarnish testing with neat ammonium polysulphide over a period of 45 minutes. Argentium samples showed excellent tarnish resistance and thiol bonding, especially good results being obtained with solutions 9.1 and 9.4 compared to the higher water content solutions 9.2 and 9.3. Solutions 9.1 and 9.4 appeared to provide some tarnish protection for standard Sterling silver also, but the thiol layer could be removed easily as was apparent from the differences between the untreated and the EnSolv 765 treated regions.
EXAMPLE 10
Mixtures of Cocamidopropyl Betaine (CPB) and Sodium Laureth Sulfate (SLS)
[0126] The above materials were supplied as a thick pourable aqueous liquid and as a highly concentrated somewhat gelatinous liquid (70% active) by Surfachem Ltd of Leeds, United Kindgom. Hexadecyl mercaptan (1 ml) in the liquid state was mixed with these materials in the quantities indicated below:
Reference SLS (ml) CPB (ml) Water (ml) 10.1 40 40 100 10.2 40 20 100 10.3 30 10 100 10.4 10 30 50 10.5 30 10 160
[0127] For solution 10.1, hexadecyl mercaptan was added to a thick mixture of sodium laureth sulphate and cocamidopropyl betaine after which water was added and the solution was mixed cold. The resulting mixture initially had a thick foamy-white texture which on settling turned into a transparent gel. Solution 10.2 was somewhat similar. Solution 10.3 was watery and was initially slightly transparent with lots of bubbles on top of the solution., and on settling overnight it became transparent. Solution 10.4 was mixed with gentle heating to about 35° C. Heat appeared to slightly help with the mixing procedure. After a few minutes of mixing the mixture foamed severely. The mixture was allowed to stand overnight and formed a viscous solution. Solution 10.5 was heated to approximately 35° C. whilst mixing. Water was last ingredient to be added. Using heat for mixing proved beneficial. The solution appeared very foamy but this settled over a few hours (within 12 hours) to form a transparent solution slightly thicker than water.
[0128] Argentium silver samples were prepared by polishing in Steelbright and then rouge, ultrasonically degreasing in a 2% aqueous Fairy Liquid solution further degreasing in acetone, immersion in the test solution at ambient temperatures for 10 minutes, and washing under cold running tap water. A lower region of each sample was rubbed with tissue soaked in EnSolv in an attempt to attempt to remove any thiols, after which the sample was left to stand for 45 minutes and were then exposed to a neat ammonium polysuphide accelerated tarnishing test for 45 minnutes.
[0129] All the samples showed extremely good hydrophobic properties during the rinsing process which indicates presence of thiols. Water drops were repelled and there was no need to dry each sample. The samples performed well in the tarnishing test with resistance to tarnishing and little difference between the rubbed and un-rubbed regions. It was concluded that the hexadecyl mecaptan in each sample tested had created a tarnish-protective thiol-bonded layer on the surface of the Argentium silver. | An alkanethiol, alkyl thioglycollate, dialkyl sulfide or dialkyl disulfide may be used to surface treat of an alloy of silver containing an amount of germanium that is effective to reduce firestain and/or tarnishing. The treatment has been found to further reduce tarnishing of the alloy such that a sample can be supported close above a 20% solution of ammonium polysulphide for at least 30 minutes while retaining a generally untarnished appearance. The treatment may be carried out at the end of manufacturing a shaped article to give rise to an article that will preserve its untarnished appearance both during transit to a point of sale but during subsequent display for an extended period. The invention therefore also includes a method for manufacturing a tarnish-resistant silver article, which comprises the steps of forming a shaped article of an alloy of silver containing an amount of germanium that is effective to reduce firestain and/or tarnishing, surface treating the article with an alkanethiol, alkyl thioglycollate, dialkyl sulphide or dialkyl disulphide; and introducing the article into packaging. Also disclosed for use in treating an alloy of silver as aforesaid is a water-based composition comprising a treatment agent selected from an alkanethiol, alkyl thioglycollate, dialkyl sulfide or dialkyl disulfide and a mixture of an anionic surfactant and an amphoteric or nonionic surfactant in a concentration that is effective to solubilise the treatment agent. | 2 |
BACKGROUND
Cabinetry and dressers are often times fitted with latching mechanisms that allow the drawers or doors of the cabinet to maintain a shut position. As the doors or drawers close, a spring loaded latched releases into a catch or cavity and prevents the door or drawer from opening until a handle is released or some other opening mechanism is activated. These may be paddle-type releases, such as those sold by the assignee of the present invention Ryadon Inc. of Foothill Ranch, Calif. These latching mechanisms are well known in the art, and an assortment of these latching mechanisms are shown at http://www.ryadon.com/latches.
One example of a latching mechanism for a cabinet or drawers is a button latch. Button latches typically have cylindrical housings with a spring loaded, beveled latch bolt mounted in the housing for retraction therein. The beveled front edge of the latch bolt is designed to make contact with the surface of the latch and cause the latch bolt to retreat into the housing of the button latch against the biasing of the spring. The latch bolt continues to retreat into the housing as the surface bears against the latch bolt until the latch bolt clears the surface. A cavity sized to receive the latch bolt captures the latch bolt as the spring, no longer compressed by the cabinet surface, releases to secure the drawer or door to the cabinet. The latch bolt may have a tab that projects out of the opposite end of the housing, such that retraction of the tab by a handle or the like withdraws the latch bolt back into the housing. In this event, the door may then again be opened as the interference between the latch bolt and the cabinet is eliminated when the latch bolt is withdrawn.
The foregoing operation and structure is well known in the art. However, because the button latches have substantially cylindrical housings that are inserted into a bore in the cabinet or dresser door/drawer, it is prone to loosening as the drawer/door is repeated opened and closed with the inherent jarring that occurs. As the button latch loosens, it can then become dislodged from the cabinet and there is little that can be done to prevent further detachments. Accordingly, what is needed is a mechanism for preventing a button latch from becoming dislodged once placed in a cabinet, dresser, housing, or the like.
SUMMARY OF THE INVENTION
The present invention is a button-type latch having a housing that retain a spring-loaded latch bolt for releasable deployment in a socket or cavity, and where the latch bolt further includes a release tab that can be coupled to a bar or handle to withdraw the latch bolt and release the button latch. The housing is substantially cylindrical with an annular outer lip at a first end adjacent the projecting portion of the latch bolt, said outer lip adapted to bear against a surface of the door or drawer to provide a stop that limits the further ingress of the button latch into its designated fitting. As is customary, a portion of the cylindrical housing may have a flat portion extending the length of the housing from the lip to the opposite end. The housing of the present invention further comprises a circumferential recess extending around the perimeter, terminating at the respective sides of the flattened portion. The recess further includes first and second channels extending forward from the recess to the lip. The recess holds a leaf spring clip having a circumferential band sized to be retained in the circumferential portion of the recess, and first and second leaf spring extending forward toward the lip of the housing. The leaf springs angle slightly out (in the radial direction) of the forward positioned channels in an undeformed condition, but the leaf springs can be depressed into their respective channels.
In use, the button latch is inserted into a fitted aperture corresponding to the shape of the housing's profile. The button latch will insert into the aperture until the circumferential band of the leaf spring clip, whereupon the leaf springs begin to bear against the sides of the aperture with increasing resistance as the leaf springs are compressed. There is a small gap between the ends of the leaf springs and the inner surface of the housing's lip, that is selected to be slightly larger than the thickness of the panel or door that the button latch is being inserted into. When the button latch is fully inserted into the aperture such that the inner surface of the lip is flush against the outer surface of the door or drawer, the leaf springs clear the edge of the door and separate, trapping the edge of the door between the leaf springs and the lip of the housing. In this manner, the button latch is captured in a reliable manner and cannot easily be dislodged or removed from the aperture.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a cabinet with a handle release and three button latches of an embodiment of the present invention;
FIG. 2 is a perspective, exploded view of the button latch housing and circumferential leaf spring band illustrating the circumferential recess and longitudinal channels;
FIG. 3 is perspective view of the button latch of FIG. 2 showing the leaf springs in their unbiased or undeformed condition; and
FIG. 4 is an enlarged, side view taken along lines 4 - 4 of FIG. 1 showing the button latch captured in the door of the cabinet.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates a cabinet 10 having a pivoting door 12 connected by two hinges 14 that allows the door 12 to open and close inside the opening of the cabinet. The door 12 includes a release handle 16 in the shape of a paddle that can be manually actuated by pulling the handle away from the door. The handle is connected to a series of pull-rods 18 that are used to retract the latch bolts in the button latches. The door's handle can simultaneously retract three different button latches at once using the three pull-rods 18 shown. The cabinet also includes three cavities 20 sized to receive the latch bolts 28 from the button latches 30 in the top surface 22 , the side wall 24 , and the bottom surface 26 .
The button latch 30 is shown in FIGS. 2 and 3 , and includes a hollow, generally cylindrical housing 40 defining a longitudinal axis. The housing is circular in profile except a rectangular face 42 . The aft surface of the housing includes a slot (not shown) that allows a release tab 64 on the latch bolt 50 to extend. At a forward edge of the housing is an annular lip 44 having a cut-out 46 shaped to receive the beveled projecting head 48 of the latch bolt 50 . The annular lip 44 operates to position the button latch 30 in the cabinet 10 as set forth below. The housing 40 further comprises a cylindrical recess 52 spaced from the annular lip 44 in the longitudinal direction, where the cylindrical recess 52 has a depth D. In a preferred embodiment, the cylindrical recess 52 extends around the housing 40 from one edge 56 of the rectangular face 42 to the other edge 58 of the rectangular face 42 . The housing also includes at least two channels 60 that have an approximate depth of D and extends from the circumferential recess 52 to the annular lip 44 . The circumferential recess 52 and channels 60 form a guide for a leaf spring clip 62 that fits over the housing and is seated in the circumferential recess 52 and channels 60 .
The housing holds a latch bolt 50 in the interior that is biased by a spring (not shown) so as to project out of the housing as shown. Connected to the latch bolt 50 is a release tab 64 having a hole 66 for receiving a pin 68 that couples the latch bolt 50 to the associated pull-rod 18 . In operation, when the handle 16 is pulled, it causes the pull-rods 18 to retract. This movement of the pull-rods 18 applies a tension force on the release tab 64 against the force of the biasing spring (not shown) in the housing 40 . The spring collapses, and the latch bolt 50 that is connected to the release tab 64 is withdrawn into the housing, allowing the door to be released from its captured position.
In FIG. 3 , the leaf spring clip 62 is shown on the housing 40 , received in the circumferential recess 52 . The leaf spring clip 62 is formed of a circumferential band 70 and a pair of leaf springs 72 depending from the circumferential band in a longitudinal direction, about one hundred and eighty degrees apart. The leaf springs 72 are not parallel, but open outward slightly as they extend away from the circumferential band 70 in an undeformed condition. The leaf springs 72 should have some resiliency, such that when they are pressed radially inward they flex back out to their undeformed condition when the compressive force is removed. The leaf springs sit in and above the channels 60 , such that the leaf springs 72 can be pressed into the channels 60 during installation of the button latch 30 and not increase the profile of the latch.
FIG. 4 is taken along lines 4 - 4 of FIG. 1 and shows the button latch 30 mounted to the cabinet 10 . The button latch 30 is shown installed in the cabinet 10 at an opening shaped to receive the button latch. The opening is defined by a retaining surface 32 that is formed from a relatively stiff, thin material such as steel or aluminum. The manner in which the button latch 30 is secured to the retaining surface 32 is illustrated in FIG. 4 . As the button latch 30 is inserted into the opening of the cabinet, the release tab 64 passes through the opening first, followed by the back edge 80 of the housing 40 . As the housing continues to pass through the opening, the leaf spring clip 62 is reached. Because the circumferential band 70 sits in the circumferential recess 52 of the housing 40 , there is no discontinuity in the profile of the housing and it continues to pass through the opening. However, further insertion of the button latch causing the retaining surface 32 to bear against the leaf springs 72 , forcing the leaf springs radially inward as the button latch passes through the opening. The leaf springs 72 are compressed into the recesses 60 of the housing 40 as the leaf springs pass through the opening of the cabinet. When the leaf springs 72 clear the opening, which should occur as the annular lip 44 makes contact with the retaining surface 32 , the leaf springs 72 release to their unbiased or undeformed condition slightly splayed outward. As shown in FIG. 4 , the retaining surface 32 is thus captured between the annular lip 44 of the housing 40 and the ends 88 of the leaf springs 72 . The button latch 30 is thus fixed in the cabinet opening, and the clip 62 prevents the button latch from loosening or becoming dislodged. | An improved button-type latch to releasably secure a door, having a spring loaded latch bolt retained within a cylindrical housing. The housing further comprises a pair of leaf springs longitudinally directed toward a front of the button latch, the leaf springs cooperating with a retaining lip on the housing to capture a structure surface to maintain the button latch therein. | 4 |
This is a divisional of application Ser. No. 08/295,125 filed on 8/24/94 now Pat. No. 5,516,558.
The present invention relates to addition curable paper release composition with improved bath life. More particularly, the present invention relates to an inhibitor package that allows for low temperature cure in thermal solventless paper release products while at the same time maintaining reasonable bulk and thin film bath lives.
BACKGROUND OF THE INVENTION
Organosilicon compositions in which a platinum group metal-containing catalyst is inhibited in its cure-promoting activity at room temperature by the presence of a catalyst inhibitor are well known in the organosilicon art. For example, U.S. Pat. No. 4,256,870 issued to Eckberg teaches a method of producing a coating composition that has an improved bath life by mixing in any order a polysiloxane base polymer, a methylhydrogen crosslinking agent, a platinum catalyst, and diallylmaleate is added as an inhibitor to effectively retard the hydrosilation addition cure reaction of the composition at ambient temperature, but which does not retard the cure at elevated temperature.
U.S. Pat. No. 4,476,166 issued to Eckberg teaches a two-part inhibitor system that produces a solventless silicone release coating with improved bath life and cure time by mixing in any order an olefinorganopolysiloxane, an organohydrogenpolysiloxane as a crosslinking agent, a platinum catalyst, and a blend of diallylmaleate and vinyl acetate as an inhibitor.
U.S. Pat. No. 4,587,137 issued to Eckberg provides novel dual cure silicone compositions comprising (a) a polydiorganosiloxane containing silicon-bonded vinyl radicals and silicon-bonded hydrogen atoms, (b) a free radical photoinitiator such as t-butyl peroxybenzoate or mixtures of t-butyl peroxybenzoate and benzophenone, (c) a precious metal or precious metal containing hydrosilation catalyst, (d) optionally a organohydrogen polysiloxane, (e) optionally an olefin containing polyorganosiloxane, and (f) optionally an organic ester of maleic acid as an inhibitor to selectively retard the thermal addition cure reaction. These compositions were cured by exposure to UV light with the option of subsequently applying a thermal post bake after irradiation.
U.S. Pat. No. 4,262,107 issued to Eckberg provides a one-part or two-part inhibitor system which produces a paper release coating composition with an improved bath life and cure time by mixing in any order a silanol polymer, a methylhydrogen crosslinking agent, a rhodium catalyst, and a low molecular weight silanol endstopped diorganopolysiloxane alone or in combination with a diallylmaleate as an inhibitor.
U.S. Pat. No. 4,774,111 issued to Lo discloses a curable organosilicon composition comprising a component having silicon-bonded hydrogen atoms, a component having silicon-bonded olefinic hydrocarbon radicals reactive therewith, a platinum-containing catalyst and an effective amount of a diorgano fumarate cure control, i.e., catalyst inhibitor, component.
U.S. Pat. No. 4,783,552 issued to Lo et al. teaches that organosilicon compositions which cure by way of a metal-catalyzed reaction of silicon-bonded hydroxyl radicals and/or silicon-bonded olefinic hydrocarbon radicals with silicon-bonded hydrogen atoms are stabilized for hours at room temperature by the incorporation of a hydrocarbonoxyalkyl maleate.
U.S. Pat. No. 3,445,420 issued to Kookootsedes et al. provides a mixture of an olefin containing organosilicon polymer, an organosilicon compound containing silicon-bonded hydrogen atoms, a platinum catalyst and an acetylenic compound as inhibitor.
The maleates have been found to be particularly effective for increasing the room temperature bath life, i.e., work time, of solventless coating organosilicon compositions which cure by way of a platinum group metal-catalyzed reaction. However, the heating time and/or temperature needed to cure in these maleate-inhibited systems is sometimes excessive. When one attempts to decrease the cure time and/or temperature of silicone compositions to a commercially desirable interval by using less maleate and/or more catalyst in these inhibitor systems the bath life is frequently decreased to a commercially undesirable interval.
The fumarate inhibitor systems have been found to allow a cure of a solventless coating organosilicon compositions which cure by way of a platinum group metal-catalyzed reaction to take place at a suitable heating time and/or temperature. However, the bath life of such a composition, as measured by gel time at room temperature, is not as long as desired. When one attempts to increase the bath life of these compositions by increasing the amount of fumarate and or decreasing the amount catalyst in the fumarate inhibitor systems the cure and/or temperature increases.
In the coating arts, such as the paper coating art, the coating composition that is used to coat a substrate should not cure to the extent that its viscosity has increased substantially before it has been applied to the substrate; however, it should rapidly cure thereafter, preferably with only a moderate amount of added energy. Typically this means that the coating compositions preferably should not gel for as long as eight hours but should cure rapidly at moderately increased temperature to such an extent that the coated substrate can be further processed, if desired, without damaging the coating. In addition, the cure time of the composition at a given cure temperature desirably should remain substantially constant as the bath ages. Room temperature stability in a thin film is also important in this art, especially in 3-roll differential gravure coating where premature gelation of the material can clog the cells in the gravure roll thereby leading to a drop in silicone coatweight. In other coating methods such as 5-roll coating, insufficient thin film bath life can lead to the formation of residue on the rolls, thus leading to increased downtime for cleaning.
U.S. Pat. No. 5,036,117 issued to Chung et al. discloses that the bulk room temperature bath life of paper release formulations containing these types of inhibitors can be further extended without seriously effecting high temperature cure by adding substantially non-inhibitors such as benzyl alcohol. Chung et al. teaches that the preferred bath life extenders can be any organic or inorganic compound which is free of an inhibiting effect and has a Hansen partial solubility parameter for hydrogen bonding of 8.0, preferably 13-48, and is free of steric hindrance in the polar portion of the molecule (See column 11, lines 65-68 and column 12, lines 1-11).
U.S. Pat. No. 5,125,998 issued to Jones et al. provides a method for improving the bath life and/or cure time of curable compositions. The process comprises first mixing an inhibitor with a catalyst, then adding that mixture to an organosilicon compound, and then adding the resulting mixture to an organohydrogensilicon compound. The process can optionally comprise a bath life extender as taught by Chung et al.
While the art has proposed and provided some solutions for the problem, the quest for the ideal inhibitor package that allows for low temperature cure thermal solventless paper release products while at the same time maintaining reasonable bulk and thin film bath lives continues.
SUMMARY OF INVENTION
The present invention provides a curable organosilicon composition comprising (A) a component having silicon-bonded olefinic hydrocarbon radicals reactive therewith; (B) a component having silicon-bonded hydrogen atoms; (C) a platinum-containing catalyst;, (D) an effective amount of an inhibitor sufficient to retard the reaction at room temperature but insufficient to prevent the reaction at elevated temperature; and (E) an effective amount of a perester.
It has been surprisingly discovered that peresters such as t-butyl peroxybenzoate (hereinafter "TBPB") which have weak inhibitory capability by themselves, have a synergistic effect on the bulk bath life stabilizing potential of a variety of inhibitors, including maleates. This is particularly surprising in that these materials have sterically hindered tertiary alkyl groups in the polar portion of their structure and furthermore are classically thought of not as inhibitor but as catalysts for the thermal crosslinking of polysiloxanes. See W. Knoll, "Chemistry and Technology of Silicones"; 2nd Edition; Academic Press; Orlando, Fla.; 1986; pp.230-231 and 392-395.
Furthermore, it has been found that addition of peresters to typical paper release formulations containing vinyl silicone, platinum catalyst, maleate cure inhibitor and methyl hydrogen functional silicone crosslinker provides enhanced stability at low temperatures.
TBPB is especially effective at improving the bulk bath life stability of inhibitors such as dibutyl maleate (hereinafter "DBM") and bis(2-ethylhexyl)maleate (hereinafter "BEHM"). These inhibitors are effective at providing thin film stability. Therefore, blends of inhibitors such as DBM with TBPB provide a good mixture of bulk and thin film stability.
DETAILED DESCRIPTION OF THE INVENTION
The present invention to a curable composition comprising (A) an organosilicon compound having an average of at from one to three silicon-bonded monovalent radicals per silicon atom selected from the group consisting of hydrocarbon and halohydrocarbon radicals, there being an average of at least two of said monovalent radicals, per molecule of Component (A), selected from the group consisting of olefinic hydrocarbon radicals, the remaining silicon valences thereof being satisfied by divalent radicals free of aliphatic unsaturation selected from the group consisting of oxygen atoms, hydrocarbon radicals, hydrocarbon ether radicals, halohydrocarbon ether radicals and halohydrocarbon radicals, said divalent radicals linking silicon atoms, (B) an organohydrogensilicon compound containing at least two silicon-bonded hydrogen atoms per molecule thereof and an average of from one to two silicon-bonded monovalent radicals free of aliphatic unsaturation, per silicon atom, selected from the group consisting of hydrocarbon and halohydrocarbon radicals, the remaining silicon valences thereof being satisfied by divalent radicals free of aliphatic unsaturation selected from the group consisting of oxygen atoms, hydrocarbon radicals, hydrocarbon ether radicals, halohydrocarbon either radicals and halohydrocarbon radicals, said divalent radicals linking silicon atoms, (C) a platinum group metal-containing catalyst in sufficient amount to accelerate a curing reaction among said silicon-bonded olefinic hydrocarbon radicals with said silicon-bonded hydrogen atoms at room temperature, (D) an inhibitor compound for said platinum-containing catalyst sufficient to retard said reaction at room temperature but insufficient to prevent said reaction at elevated temperature, and (E) a perester in a total amount sufficient to further retard said platinum-containing catalyst at room temperature.
Herein the term "curable" as applied to compositions of this invention, generally denotes a chemical change which leads to a change in the state of the composition from a liquid to a solid.
The curing of the compositions of this invention is accomplished by a reaction between silicon-bonded hydroxy and/or olefinic hydrocarbon radicals in Component (A) and silicon-bonded hydrogen atoms in Component (B). The curing of the composition of this invention is controlled by the platinum group metal-containing catalyst Component (C), the inhibitor Component (D) and the perester. The components are delineated as follows.
Broadly stated, Component (A) of the compositions of this invention can be any organosilicon compound containing two or more silicon atoms linked by divalent radicals and containing an average of from 1 to 3 silicon-bonded monovalent radicals per silicon, with the proviso that the organosilicon compound contains at least two silicon-bonded olefinic hydrocarbon radicals. This component can be a solid or a liquid, free flowing or gum-like.
Examples of said divalent radicals linking silicone atoms in Component (A) include oxygen atoms, which provide siloxane bonds, and aliphatically saturated hydrocarbon, hydrocarbon ether, halohydrocarbon ether and halohydrocarbon radicals which provide silcarbane bonds. The divalent radicals can be the same or different, as desired.
Examples of suitable divalent hydrocarbon radicals include any alkylene radical, such as --CH 2 --, --CH 2 CH 2 --, CH 2 (CH 3 )CH --, --(CH 2 ) 4 --, --CH 2 CH(CH 3 )CH 2 --, --CH 2 ) 6 -- and --(CH 2 ) 18 --; cycloalkylene radical, such as cyclohexylene; arylene radical, such as phenylene and combinations of hydrocarbon radicals, such as benzylene, i.e. --C 6 H 4 CH 2 --.
Examples of suitable divalent halohydrocarbon radicals include any divalent hydrocarbon radical wherein one or more hydrogen atoms have been replaced by halogen, such as fluorine, chlorine or bromine. Preferable divalent halohydrocarbon radicals have the formula --CH 2 CH 2 C n F 2n CH 2 CH 2 -- wherein n has a value of from 1 to 10 such as, for example, --CH 2 CH 2 CF 2 CF 2 CH 2 CH 2 --.
Examples of suitable divalent hydrocarbon ether radicals and halohydrocarbon ether radicals include --CH 2 CH 2 OCH 2 CH 2 --, --CH 2 CH 2 CF 2 OCF 2 CH 2 CH 2 --, --CH 2 CH 2 OCH 2 CH 2 CH 2 -- and --C 6 --H 4 --O--C 6 H 4 --.
Examples of said monovalent radicals in Component (A) include halohydrocarbon radicals free of aliphatic unsaturation and hydrocarbon radicals.
Examples of suitable monovalent hydrocarbon radicals include alkyl radicals, such as CH 3 --, CH 3 CH 2 --, (CH 3 ) 2 CH--, C 8 H 17 --, C 10 H 21 -- and C 2 0H 41 --; cycloaliphatic radicals, such as cyclohexyl; aryl radicals, such as phenyl, tolyl, xylyl, anthracyl and xenyl; aralkyl radicals, such as benzyl and 2-phenylethyl; and olefinic hydrocarbon radicals, such as vinyl, allyl, methallyl, 3-butenyl, 5-hexenyl, 7-octenyl, cyclohexenyl and styryl. Alkenyl radicals are preferable terminally unsaturated. Of the higher alkenyl radicals those selected from the group consisting of 5-hexenyl, 7 octenyl, and 9-decenyl are preferred because of the more ready availability of the alpha, omega-dienes used to prepare the alkenylsiloxanes. Highly preferred monovalent hydrocarbon radical for the silicon-containing components of the compositions of this invention are methyl, phenyl, vinyl and 5-hexenyl. Examples of suitable aliphatically saturated monovalent halohydrocarbon radicals include any monovalent hydrocarbon radical which is free of aliphatic unsaturation and has at least one of its hydrogen atoms replaced with halogen, such as fluorine, chlorine or bromine. Preferable monovalent halohydrocarbon radicals have the formula C n F 2n+1 CH 2 CH 2 -- wherein n has a value of from 1 to 10, such as, for example, CF 3 CH 2 CH 2 -- and C 4 F 9 CH 2 CH 2 --.
Component (A) of the compositions of this invention is typically an organopolysiloxane having the average unit formula R c 2 SiO.sub.(4-c)/2 wherein R2 denotes said monovalent radicals, delineated and limited above, and c has a value of from 1 to 3, such as 1.2, 1.9, 2.0, 2.1, 2.4, and 3.0. Suitable siloxane units in the organopolysiloxanes having the above average unit formula have the formulae R 3 2 SiO 1/2 , R 2 2 SiO 2/2 , R 2 SiO 3/2 and SiO 4/2 . Said siloxane units can be combined in any molecular arrangement such as linear, branched, cyclic and combinations thereof, to provide organopolysiloxanes that are useful as Component (A).
A preferred organopolysiloxane Component (A) for the composition of this invention is a substantially linear organopolysiloxane having the formula XR 2 SiO(XRSiO) x SiR 2 X. By substantially linear it is meant that the component contains no more than trace amounts of silicon atoms bearing 3 or 4 siloxane linkages. It is to be understood that the term substantially linear encompasses organopolysiloxanes which can contain up to about 15 percent by weight cyclopolysiloxanes which are frequently co-produced with the linear organopolysiloxanes.
In the formula shown immediately above each R denotes a monovalent hydrocarbon or halohydrocarbon radical free of aliphatic unsaturation and having from 1-20 carbon atoms, as exemplified above. The several R radicals can be identical or different, as desired. Additionally, each X denotes an R radical or an olefinic hydrocarbon radical having from 2-12 carbon atoms, as exemplified above. Of course, at least two X radicals are olefinic hydrocarbon radicals.
The value of the subscript x in the above formula is such that the linear organopolysiloxane (A) has a viscosity at 25° C. of at least 25 millipascal-seconds (25 centipoise). The exact value of x that is needed to provide a viscosity value falling within said limit depends upon the identity of the X and R radicals; however, for hydrocarbyl-terminated polydimethylsiloxane x will have a value of at least about 25.
In terms of preferred monovalent hydrocarbon radicals, noted above, examples of preferred linear organopolysiloxanes of the above formula which are suitable as Component (A) for the composition of this invention include
PhMeViSiO(Me 2 SiO) 100 SiPhMeVi,
HexMe 2 SiO(Me 2 SiO) 150 SiMe 2 Hex,
ViMe 2 SiO(Me 2 SiO) 100 (HexMeSiO) 2 SiMe 2 Vi,
ViMe 2 SiO(Me 2 SiO) 0 .95x (MeViSiO) 0 .5x SiMe 2 Vi,
HexMe 2 SiO(Me 2 SiO) 150 (HexMeSiO) 4 SiMe 2 Hex,
Me 3 SiO(Me 2 SiO) 0 .9x (MeViSiO) 0 .1x SiMe 3 ,
Me 3 SiO(Me 2 SiO) 100 (MeHexSiO) 8 SiMe 3 ,
PhMeViSiO(Me 2 SiO) 0 .93x (MePhSiO) 0 .07x SiPhMeVi and
ViMe 2 SiO(Me 2 SiO) x SiMe 2 Vi
wherein Me, Vi, Hex and Ph denote methyl, vinyl, 5-hexenyl and phenyl, respectively.
For Coating composition of this invention it is highly preferred that the linear organopolysiloxane (A) have the formula XMe 2 SiO(Me 2 SiO) b (MeXSiO) d SiMe 2 X wherein X is noted above and the sum of b plus d is equal to x, also noted above. The values of the subscripts b and d can each be zero or greater; however, the value of d is typically less than 0.1b such as zero, 0.02b or 0.08b. Examples of highly preferred linear organopolysiloxanes (A) for adhesive-release coating compositions of this invention include
Me 3 SiO(Me 2 SiO) b (MeHexSiO) d SiMe 3 ,
Me 3 SiO(Me 2 SiO) b (MeViSiO) d SiMe 3 ,
HexMe 2 SiO(Me 2 SiO) b (MeHexSiO) d SiMe 2 Hex and
ViMe 2 SiO(Me 2 SiO) b (MeViSiO) d SiMe 2 Vi
In a preferred embodiment of the present invention, wherein the curable composition, preferably solventless, is used to coat a solid substrate, such as paper, with an adhesive-releasing coating, the value of b plus d in the highly preferred organopolysiloxane (A) is sufficient to provide a viscosity at 25° C., for the Component (A) of at least 100 mPa.s, such as from about 100 mPa.s to about 100 Pa.s, preferable from about 100 mPa.s to 10 Pa.s and, most preferably, from 100 mPa.s to 5 Pa.s; said 25 viscosity's corresponding approximately to values of b+d of at least 60, such as from 60 to 1000, preferably to 520 and, most preferably, to 420.
Broadly stated, Component (B) of the compositions of this invention can be any organohydrogensilicon compound which is free of aliphatic unsaturation and contains two or more silicon atoms linked by divalent radicals, an average of from one to two silicone-bonded monovalent radicals per silicon atom and an average of at least two, and preferably three or more, silicon bonded hydrogen atoms per molecule thereof.
Examples of said divalent radicals linking silicon atoms in Component (B) are as delineated above for Component (A), including preferred examples. As with Component (A), the divalent radicals within Component (B) can be identical or different, as desired. Furthermore, the divalent radicals that are present in Component (B) can, but need not, be the same as the divalent radicals that are present in Component (A).
Examples of said monovalent radicals in Component (B) include hydrocarbon and halohydrocarbon radicals, as delineated above for Component (A)including preferred examples, which are free of aliphatic unsaturation. The monovalent radicals that are present in Component (B) can, but need not, be the same as the monovalent radicals that are present in Component (A).
Component (B) must contain an average of at least two silicon-bonded hydrogen atoms per molecule thereof. Preferably Component (B) contains an average of three or more silicon-bonded hydrogen atoms such as, for example, 5, 10, 20, 40 and more.
Component (B) typically has a 100 percent siloxane structure, i.e., and organohydrogenpolysiloxane structure having the average unit formula R e 3 H.sub.ƒ SiO.sub.(4-c-ƒ)/2 wherein R3 denotes said monovalent radical free of aliphatic unsaturation, f has a value of from greater that 0 to 1, such as 0.001, 0.01, 0.1 and 1.0 and the sum of e plus f has a value of from 1-2, such as 1.2, 1.9, and 2.0.
Suitable siloxane units in the organohydrogenpolysiloxane having the average unit formula immediately above have the formulae R 3 3 SiO 1/2 , R 2 3 HSiO 1/2 , R 2 3 SiO 2/2 , R 3 HSiO 2/2 , R 2 SiO 3/2 , HSiO 3/2 , HSiO 3/2 and SiO 4/2 . Said siloxane units can be combined in any molecular arrangement such as linear, branched, cyclic and combinations thereof, to provide organohydrogenpolysiloxane that are useful as Component (B).
A preferred organohydrogenpolysiloxane Component (B) for the compositions of this invention is a substantially linear organohydrogenpolysiloxane having the formula YR 2 SiO(YRSiO) y SiR 2 Y wherein each R denotes a monovalent hydrocarbon or halohydrocarbon radical free of aliphatic unsaturation and having from 1-20 carbon atoms, as exemplified above. The several R radicals can be identical or different, as desired. Additionally, each Y denotes a hydrogen atom or an R radical. Of course, at least two Y radicals must be hydrogen atoms.
The value of the subscript y is not critical: however it is preferably such that the organohydrogenpolysiloxane Component (B) has a viscosity at 25° C., up to 100 millipascal-seconds. The exact value of y needed to provide a viscosity value falling within said limits depends upon the number and identity of the R radicals; however, for organohydrogenpolysiloxanes containing only methyl radicals as R radicals y will have a value of from about 0 to about 100.
In terms of preferred monovalent hydrocarbon radicals, noted above, examples of linear organohydrogenpolysiloxanes of the above formula which are suitable as Component (B) for the Compositions of this invention include
HMe 2 SiO(Me 2 SiO)ySiMe 2 H,
Me 3 SiO(MeHSiO) y SiMe 3 , HMe 2 SiO(Me 2 SiO) 0 .5y (MeHSiO) 0 .5y SiMe 2 H,
HMe 2 SiO(Me 2 SiO) 0 .5y (MePhSiO) 0 .1y (MeHSiO) 0 .4y SiMe 2 H,
Me 3 SiO(Me 2 SiO) 0 .4y (MeHSiO) 0 .6y SiMe 3 , (MeHSiO)y,
(HMe 2 SiO) 4 Si and MeSi(OSiMe 2 H) 3 .
Highly preferred linear organohydrogenpolysiloxane (B) for the coating compositions of this invention have the formula YMe 2 SiO(Me 2 SiO) p (MeYSiO) q SiMe 2 Y wherein Y denotes a hydrogen atom or an R radical, free of aliphatic unsaturation. Again, an average of at least two Y radicals per molecule of Component (B) must be hydrogen atoms. The subscripts p and q can have average values of zero or more and the sum of p plus q has a value equal to y, noted above. For the adhesive-releasing coating compositions of this invention Y should be H or methyl.
The amounts of Components (A) and (B) that are used in the compositions of this invention are not narrowly limited. Said amounts, expressed in terms of the ratio of the number of silicon-bonded hydrogen atoms of Component (B) to the number of silicon-bonded olefinic hydrocarbon radicals of Component (A), as is typically done, are sufficient to provide a value for said ratio of from 1/100 to 100/1, usually from 1/20 to 20/1, and preferably from 1/2 to 20/1.
For the liquid coating compositions of this invention which are to be used in the coating method of this invention, hereinbelow delineated, the value of said ratio should have a value of from 1/2 to 3/1, and preferably about 1.2/1-2.5/1.
Organosilicon polymer are, of course, well known in the organosilicon art. Organopolysiloxanes are clearly the most significant and most widely used form of organosilicon polymers in the art, and in this invention; many are commercially prepared. The preparation of the organosilicone components that are used in the compositions of this invention is well documented and needs no intensive delineation herein.
Broadly stated, Component (C) of the composition of this invention is a catalyst component which facilitates the reaction of the silicon-bonded hydrogen atoms of Component (B) with the silicon-bonded olefinic hydrocarbon radicals of Component (A) and can be any platinum-containing catalyst component. For example, Component (C) can be platinum metal; a carrier such as silica gel or powdered charcoal, bearing platinum metal; or a compound or complex of a platinum metal.
A typical platinum-containing catalyst component in the organopolysiloxane compositions of this invention is any form of chloroplatinic acid, such as, for example, the readily available hexahydrate form or the anhydrous form, because of its easy dispersibility in organosiloxane systems. A particularly useful form of chloroplatinic acid is that composition obtained when it is reacted with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, as disclosed by U.S. Pat. No. 3,419,593 incorporated herein by reference.
The amount of platinum-containing catalyst component that is used in the compositions of this invention is not narrowly limited as long as there is a sufficient amount to accelerate a room temperature reaction between the silicon-bonded hydrogen atoms of Component (B) with the silicon-bonded olefinic hydrocarbon radicals of Component (A). The exact necessary amount of said catalyst component will depend upon the particular catalyst and is not easily predictable. However, for chloroplatinic acid said amount can be as low as one part by weight of platinum for every one million parts by weight of organosilicon Components (A) plus (B). Preferably said amount is at least 10 parts by weight, on the same basis.
For compositions of this invention which are to be used in the coating method of this invention the amount of platinum-containing catalyst component to be used is preferably sufficient to provide from 10 to 500 parts by weight platinum per one million parts by weight of organopolysiloxane Components (A) plus (B).
Component (D) of the compositions of this invention is any material that is known to be, or can be, used as an inhibitor for the catalytic activity of platinum group metal-containing catalysts. By the term "inhibitor" it is meant herein a material that retards the room temperature curing of a curable mixture of Components (A), (B), and (C), when incorporated therein in small amounts, such as less than 10 percent by weight of the composition, without preventing the elevated temperature curing of the mixture. Of course, it is known that materials, such as hydrocarbons, which are not inhibitors when used in solvent amounts, have an inhibiting effect when used in solvent amounts, such as from 35 to 95% by weight. These materials are not considered inhibitors for the purposes of this invention.
Inhibitors for the platinum group metal catalysts are well known in the organosilicon art. Examples of various classes of such metal catalyst inhibitors include unsaturated organic compounds such as ethylenically or aromatically unsaturated amides, U.S. Pat. No.4,337,332; acetylenic compounds, U.S. Pat. No. 3,445,420 and 4,347,346; ethylenically unsaturated isocyanates, U.S. Pat. No. 3,882,083; olefinic siloxanes, U.S. Pat. No. 3,989,667; unsaturated hydrocarbon diesters, U.S. Pat. No. 4,256,870; 4,476,166 and 4,562,096, and conjugated ene-ynes. U.S. Pat. No. 4,465,818 and 4,472,563; other organic compounds such as hydroperoxides, U.S. Pat. Nos. 4,061,609; ketones, 3,418,731; sulfoxides, amines, phosphines, phosphites, nitriles, U.S. Pat. No. 3,344,111; diaziridines, U.S. Pat. No. 4,043,977; and various salts, such as U.S. Pat. No. 3,461,185. It is believed that the compositions of this invention can comprise an inhibitor from any of these classes of inhibitors.
Organic inhibitor compounds which bear aliphatic unsaturation and one or more polar groups, such as carbonyl or alcohol groups, display useful bath life extension benefits when combined with Component (E) of the present invention. Examples thereof include the acetylenic alcohols of Kookootsedes and Plueddemann, U.S. Pat. No. 3,445,420, such as ethynylcyclohexanol and methylbutynol; the unsaturated carboxylic esters of Eckberg, U.S. Pat. No. 4,256,870, such as diallyl maleate and dimethyl maleate; and the maleates and fumatates of Lo, U.S. Pat. No. 4,562,096 and 4,774,111, such as diethyl fumarate, diallyl fumarate and bis-(methoxyisopropyl)maleate. The half esters and amides of Melanchon, U.S. Pat. No. 4,533,575; and the inhibitor mixtures of Eckberg, U.S. Pat. No. 4,476,166 would also be expected to behave similarly. The above-mentioned patents relating to inhibitors for platinum group metal-containing catalysts are incorporated herein by reference to teach how to prepare compounds which are suitable for use as Component (D) in our compositions.
Preferred inhibitors for the compositions of this invention are the maleates and fumarates. The maleates and fumarates have the formula R 1 (OD) h O 2 CCH═CHCO 2 (DO) h R 1 wherein R 1 denotes an hydrocarbon radical having from 1 to 10 carbon atoms and each D denotes, independently, an alkylene radical having from 2 to 4 carbon atoms. R 1 can be, for example, an alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl, pentyl or hexyl; an aryl radical such as phenyl or benzyl; an alkenyl radical such as vinyl or allyl; alkynyl radicals; or a cyclohydrocarbon radical such as cyclohexyl. D can be, for example, --CH 2 CH 2 --, --CH 2 (CH 3 )CH--, --CH 2 CH 2 CH 2 --, --CH 2 CH 2 CH 2 CH 2 --, --CH 2 (CH 3 CH 2 )CH-- and --CH 2 CH 2 (CH 3 )CH--. The individual R 1 radicals and D radicals of the maleates and fumarates can be identical or different, as desired. The value of subscript h in the formula immediately above can have a value equal to zero or 1. The individual values of h can be identical or different, as desired.
The amount of Component (D) to be used in the compositions of this invention is not critical and can be any amount that will retard the above-described platinum-catalyzed hydrosilylation reaction at room temperature while not preventing said reaction at moderately elevated temperature. No specific amount of inhibitor can be suggested to obtain a specified bath life at room temperature since the desired amount of any particular inhibitor to be used will depend upon the concentration and type of the platinum group metal-containing catalyst, the nature and amounts of Components (A) and (B). The range of Component (D) can be 0.1-10% by weight, preferably 0.15-2% by weight, and most preferably 0.2-1% by weight.
Broadly stated, Component (E) of the compositions of this invention is a perester having the formula
R.sub.1 CO.sub.3-- R.sub.2
wherein R 1 is hydrocarbon or halohydrocarbon radical or O--R 3 , R 3 is a monovalent hydrocarbon radical, R 2 is a tertiary alkyl radical. Some of the peresters which can be used are for example ##STR1##
The amount of peresters to be used in the compositions of this invention is not critical and can be any amount that the combination the peresters and the inhibitors will retard the above-described platinum-catalyzed hydrosilylation reaction at room temperature while not preventing said reaction at moderately elevated temperature. For example, the range for component (E) can be 0.1-10%, with 0.1-2% being preferred, and 0.3-1% being most preferred.
The following examples are disclosed to further teach, but not limit, the invention which is properly delineated by the appended claims. All amounts (parts and percentages) are by weight unless otherwise indicated. Viscosities were measured with a rotating spindle viscometer.
EXAMPLE 1
t-Butyl Peroxybenzoate as an Inhibitor
Composition 1 was prepared by combining 10 parts of a 200 cps vinyl dimethyl silyl stopped polydimethyl siloxane polymer containing 25 ppm Pt as a Pt-divinyltetramethyl disiloxane complex with 0.4 parts t-butyl peroxybenzoate, and 0.30 parts of a methyl hydrogen dimethyl polysiloxane crosslinker. The resulting mixture gelled in about 60 mins.
Composition 2 was the same as Composition 1, except no t-butyl peroxybenzoate was added to the system. The resulting mixture gelled in less than three minutes.
Composition 3 was the same as Composition 1, except the mixture was allowed to stand at room temperature overnight before addition of the 0.30 parts of the methyl hydrogen dimethyl polysiloxane crosslinker. The resulting mixture was a free flowing liquid for 5 hours.
The results clearly indicate that t-butyl-peroxybenzoate has a small amount of inhibitive capacity.
EXAMPLE 2
t-Butyl Peroxybenzoate/Maleate Mixed Inhibitor Systems
The following inhibitors were mixed with 100.0 g portions of a blend of a 200 cps vinyl dimethyl silyl stopped polydimethyl siloxane polymer and 150 ppm Pt as a Pt-divinyltetramethyl disiloxane complex:
______________________________________Comp. No Inhibitor (wt in grams) t-ButylPeroxybenzoate (g)______________________________________4 DBM (0.50) --5 DBM (O.50) 1.06 BEHM (0.80) --7 BEHM (0.80) 1.08 DAM (0.25) --9 DAM (0.25) 1.0______________________________________ DBM = Dibutyl Maleate BEHM = Bis (2ethylhexyl) Maleate DAM = Diallyl Maleate
Examples 4,6 & 8 correspond to prior art examples whereas examples 5, 7, and 9 correspond to examples of the current invention. To all of these formulations were added 5.0 g of a methyl hydrogen dimethyl polysiloxane crosslinker. After the bubbles dissipated (ca 15 mins) initial viscosities were measured and the viscosities were than monitored over time at room temperature. The results are summarized below:
______________________________________ 1 HrComp. Initial Visc 2 Hr Visc 17 Hr Visc 24 Hr ViscNo. Visc(cps) (cps) (cps) (cps) (cps)______________________________________4 320 560 710 Gel --5 235 255 265 334 3756 520 Gel -- -- --7 265 290 304 498 6358 230 265 272 332 3659 215 230 234 262 280______________________________________
These results clearly indicate that the t-butyl peroxybenzoate and maleate mixed inhibitor system has a synergistic effect on enhancing the bulk bath life of these compositions.
EXAMPLE 3
Composition 10 was prepared by combining 10.0 g of the 200 cps vinyl dimethyl silyl stopped polydimethyl siloxane polymer containing 150 ppm Pt as a Pt-divinyltetramethyl disiloxane complex with 0.025 g DAM, and then 0.50 g of the methyl hydrogen dimethyl polysiloxane crosslinker. Composition 11 was prepared in the same way as Composition 10, except 0,050 g DBM and 0.10 g t-butylperoxybenzoate were substituted for the DAM.
A sample of each formulation was coated in a 1 mil film on a plastic substrate and the tack free time as determined at room temperature. In addition, samples of each were drawn down on 42# super calendered kraft (SCK) paper and the minimum curetime at 200° F. was determined by noting at what cure time was required to attain a cured film that did not migrate to Scotch 610 tape. The following results were obtained:
______________________________________ Min. Curetime at 200° F. Tack Free TimeComp. No. (sec) (hrs)______________________________________10 14 511 13 >8 but <17______________________________________
This clearly shows that with the same bulk bath life and minimum curetime at 200° F., the DBM/TBPB combination gave better thin film stability than DAM.
EXAMPLE 4
Composition 12 was prepared by combining 2500 g of the 200 cps vinyl dimethyl silyl stopped polydimethyl siloxane polymer containing 150 ppm Pt as a Pt-divinyltetramethyl disiloxane complex with 6.25 g DAM and 125 g of the methyl hydrogen dimethyl polysiloxane crosslinker. Composition 13 was prepared in the same way as Composition 12 except that 12.5 g DBM+25 g TBPB was added as inhibitor.
These formulations were coated via 3-roll differential offset gravure at coatweights of 0.9-1 lb/ream. The coated paper samples were cured by passing the web through a 10 foot oven at 300° F. with oven residence times of both 3 and 6 secs. The resulting release liners were then laminated with Flexcryl 1625 emulsion acrylic adhesive and a 50# smudge proof facestock. The release force (in g/2in) required to separate the constructions at 0.17 m/s (400 in/min) delamination speed and 180° was then monitored over time at room temperature. The following results were obtained:
______________________________________ Residence Initial 1-Day 8-Day 14-DayBath Time (sec) Release Release Release Release______________________________________10 3 52 56 61 6412 6 38 42 51 51.511 3 30 33 37 4113 6 31 34 38 39.5______________________________________
As can be seen, lower more stable release was exhibited by Composition 13.
EXAMPLE 5
The following inhibitors were mixed with 100.0 g portions of a blend of a 275 cps vinyl dimethyl silyl stopped dimethyl methylvinyl polysiloxane polymer and 100 ppm Pt as a Pt-divinyltetramethyl disiloxane complexs:
______________________________________Comp No. Inhibitor (wt in grams) t-ButylPeroxybenzoate (g)______________________________________14 DAF (0.60) --15 DAF (0.60) 0.816 BMMEM (0.80) --17 BMMEM (0.80) 0.8______________________________________ DAF = Diallyl Fumarate BMMEM = Bis(Methoxymethyl) Ethyl Maleate
To these formulations were added 5.0 g portions of a trimethylsilyl stopped methyl hydrogen polysiloxane crosslinker. The viscosities were then monitored over time at room temperature as shown below:
______________________________________ 24 HrComp Initial 8 Hr Visc Visc 48 Hr Visc 72 Hr ViscNo. Visc(cps) (cps) (cps) (cps) (cps)______________________________________14 257 339 407 546 87115 247 316 368 475 66116 260 309 364 549 202517 249 295 346 474 891______________________________________
In addition, minimum curetimes were measured at 250° F. on SCK (time to no smear and no migration to Scotch 610 tape). Compositions 14 and 15 gave minimum curetimes of 15 secs while Compositions 16 and 17 were 13 secs. Therefore, it can be seen that the t-butyl peroxybenzoate aided room temperature stability but did not impair cure at high temperatures.
EXAMPLE 6
Composition 18 was prepared by combining 100.0 g portions of a blend of a 275 cps vinyl dimethyl silyl stopped dimethyl methylvinyl polysiloxane polymer and 100 ppm Pt as a Pt-divinyltetramethyl disiloxane complex with 0.40 g DAF and 7.5 g of a methyl hydrogen dimethyl polysiloxane crosslinker. Composition 19 was prepared in the same way as Composition 18, except 1.5 g t-Amyl Peroxybenzoate (TAPB) was added in the system. The minimum curetimes of these compositions at 225 ° F. were both found to be 14 sec. In addition, the following viscosity measurements were made over time:
______________________________________ 2 HrComp Initial Visc 4 Hr Visc 8 Hr Visc 24 Hr ViscNo. Visc(cps) (cps) (cps) (cps) (cps)______________________________________18 275 332 356 394 54219 255 290 305 330 419______________________________________
Again, essentially the same cure performance was obtained on paper at 225° F., whereas addition of the TAPB gave better bath life under ambient conditions.
EXAMPLE 7
Composition 20 was prepared by combining 100.0 g portions of a blend of a 225 cps vinyl dimethyl silyl stopped dimethylpolysiloxane polymer and 150 ppm Pt as a Pt-divinyltetramethyl disiloxane complex with 0.15 g Mono(2-Ethylhexyl) Maleate (MEHM). Composition 21 was prepared in the same way as Composition 20, except that 0.15 g MEHM+1.1 g TAPB was added in the system. 5.0 g portions of methyl hydrogen dimethyl polysiloxane crosslinker were added in Compositions 20 and 21. The minimum curetimes at 225° F. were 7 secs for each formulation. In addition, the following viscosities were measured:
______________________________________Comp No. Initial Visc(cps) 2 Hr Visc(cps) 4 Hr Visc(cps)______________________________________20 239 366 74121 225 320 590______________________________________
The results indicate that TAPB aided room temperature stability but did not impair cure at high temperature.
EXAMPLE 8
Two 50.0 g portions of a 225 cps vinyl dimethyl silyl stopped dimethylpolysiloxane polymer were mixed with 0.15 g Di(3-Butynyl) Maleate (DBTYNM). Composition 22 was prepared by adding 5.0 g of methyl hydrogen dimethyl polysiloxane crosslinker followed by 50.0 g of a blend of a 225 cps vinyl dimethyl silyl stopped dimethylpolysiloxane polymer and 300 ppm Pt as a Pt-divinyltetramethyl disiloxane complex. Composition 23 was prepared in the same way as Composition 22, except that 1.0 g of TBPB was added after the DBTYNM and before the crosslinker. Both Compositions 22 and 23 exhibited minimum curetimes of 10 sec at 225° F. In addition, the following viscosity data was obtained:
______________________________________Comp No. Initial Visc(cps) 2 Hr Visc(cps) 4 Hr Visc(cps)______________________________________22 228 765 Soft Gel23 211 299 450______________________________________
EXAMPLE 9
A masterbath was prepared by combining 600 g of a blend of a 225 cps vinyl dimethyl silyl stopped dimethylpolysiloxane polymer and 150 ppm Pt as a Pt-divinyltetramethyl disiloxane complex and 3.0 g dibutyl maleate (DBM). To 100.0 g portions of this masterbath was then added the following peresters:
______________________________________Example No. Perester (Amnt in Grams)______________________________________24 None25 TBPB (1.0)26 TAPB (1.07)27 TBEC (1.27)28 TAEC (1.34)______________________________________ TBPB = tButyl Peroxybenzoate TAPB = tAmyl Peroxbenzoate TBEC = OOt-Butyl 1(2-Ethylhexyl) Monoperoxy Carbonate TAEC = OOt-Amyl 1(2-Ethylhexyl) Monoperoxy Carbonate
At this point 5.0 g portions of methyl hydrogen dimethyl polysiloxane crosslinker were added and the viscosities of the resulting formulations were monitored over time at room temperature.
______________________________________Example No. Initial Visc(cps) 6 Hr Visc(cps) 22 Hr Visc(cps)______________________________________24 309 1350 Gel25 230 310 47526 223 318 50027 222 334 62328 221 324 572______________________________________
Once again the change in viscosity was much lower in the presence of the peresters.
EXAMPLE 10
100.0 g portions of a blend of a 265 cps 5-hexenyl dimethylsilyl stopped dimethylpolysiloxane polymer and 150 ppm Pt as a Pt-divinyltetramethyl disiloxane complex were mixed with 0.40 g Dibutyl Maleate (DBM) and 4.0 g of a methyl hydrogen dimethyl polysiloxane crosslinker in the case of Composition 30 and 0.40 g DBM, 1.0 g t-Butyl Peroxybenzoate (TBPB), & 4.0 g crosslinker in Composition 31. The minimum curetimes of these formulations at 200° F. were 14 sec for Composition 30 and 16 sec for Composition 31. In addition, the following viscosity measurements were made over time:
______________________________________ Initial 1 Hr 2 Hr 4 HrComp Visc Visc Visc Visc 8 Hr Visc 24 Hr ViscNo. (cps) (cps) (cps) (cps) (cps) (cps)______________________________________30 265 425 492 575 783 Gel31 250 325 344 367 405 660______________________________________
These comparative examples again show that an improvement in bulk bath life can be achieved without a substantial decrease in curespeed via the addition of a perester.
EXAMPLE 11
50.0 g portions of a 225 cps vinyl dimethyl silyl stopped dimethylpolysiloxane polymer were mixed with 0.15 g 1-ethynyl cyclohexanol (ECH). Then to Composition 32 was added 5.0 g of methyl hydrogen dimethyl polysiloxane crosslinker followed by 50.0 g of a blend of a 225 cps vinyl dimethyl silyl stopped dimethylpolysiloxane polymer and 300 ppm Pt as a Pt-divinyltetramethyl disiloxane complex. Composition 33 was prepared similarly except that 2.0 g of t-Amyl Peroxybenzoate (TAPB) was added after the ECH and before the crosslinker. Composition 32 exhibited a minimum curetime of 9 sec at 200° F. whereas Composition 33 was 10 sec. In addition, the following viscosity data was obtained:
______________________________________ Initial 1 HrComp Visc Visc 2 Hr Visc 4 Hr Visc 8 Hr ViscNo. (cps) (cps) (cps) (cps) (cps)______________________________________32 202 217 223 240 27533 194 202 207 217 246______________________________________
EXAMPLE 12
The Use of a Maleate/Perbenzoate Blend to Inhibit a Different Platinum Catalyst
100.0 g portions of a blend of a 225 cps vinyl dimethylsilyl stopped dimethylpolysiloxane polymer and about 75 ppm Pt as a Pt-octanol complex were mixed with 0.30 g Dibutyl Maleate (DBM) and 3.0 g of a methyl hydrogen polysiloxane crosslinker in the case of Composition 34 and 0.30 g DBM, 1.1 g t-Amyl Peroxybenzoate (TAPB), & 3.0 g crosslinker in Composition 35. The minimum curetimes of these formulations at 250° F. were 67 sec for Composition 34 and 54 sec for Composition 35. In addition, the following viscosity measurements were made over time:
______________________________________ InitialExample Visc 2 Hr Visc 6 Hr Visc 22 Hr ViscNo. (cps) (cps) (cps) (cps)______________________________________34 186 212 287 Hard Gel35 176 206 251 810______________________________________
These comparative examples again show that an improvement in bulk bath life can be achieved via the addition of a perester.
Although specific examples of the invention have been described herein, it is not intended to limit the invention solely thereto but to include all variations and modifications falling within the spirit and scope of the appended claims. | The present invention relates to an inhibitor package that allows for low temperature cure in thermal solventless paper release products while at the same time maintaining reasonable bulk and thin film bath lives. | 3 |
FIELD OF THE INVENTION
[0001] The present invention relates to an apparatus that aids in the transportation of objects having at least one side with a smooth, flat surface. The vacuum lifter is autoclavable and washable by disinfectants routinely used in the pharmaceutical and food industries.
BACKGROUND OF THE INVENTION
[0002] Currently, commercially available suction (vacuum) lifters typically are constructed of a rubber suction cup affixed to an aluminum handle. The rubber suction-cup is placed on the smooth, flat, non-porous surface of the object to be transferred. Air is evacuated out of the suction cup and the edge of the vacuum cup forms a seal with the surface of the object. The ensuing vacuum grips the surface of the object and holds it, thus allowing the object to be lifted and transferred to a desired location. The vacuum is broken to release the suction lifter from the object. There are many models of suction lifters commercially available such as those offered by Allstates Rubber & Tool, Inc. (Tinly Park, Ill.) and All-Vac Industries, Inc. (Skokie, Ill.).
[0003] In industries with very high hygienic demands, such as the food, biotech, semiconductor, aerospace, and pharmaceutical industries, it is desirable to minimize contamination of products, product packaging or manufacturing equipment with bacteria and foreign particulates. One way to minimize surface contamination is to physically avoid touching the product or product containers during routine transfer operations. This reduces the chance that bacteria, oils, skin, hair and other contaminants will contact the surface. Use of suction lifters would aid in this endeavor because a vacuum lifter could be employed without physically touching the surface of the object to be transferred.
[0004] Additionally, because of the stringent hygiene standards required industries such as the pharmaceutical and food industries, it is highly desirable to ensure that any vacuum lifter relied upon can be treated to maintain aseptic compliance. Typically, this means that the vacuum lifter selected must be able to withstand standard disinfection protocols (cleaning with a series of highly caustic and acidic washes) as well as high temperature exposures found in the sterilization process using an autoclave.
[0005] The currently available vacuum lifters found in the market today, do not hold up well to the standard disinfection/autoclave protocols previously mention. Particularly, vacuum lifters having aluminum parts have the disadvantage that the aluminum oxidizes readily and generates a black surface that flakes off after a few weeks of use when exposed to the standard aseptic compliance protocols. The foreign particulates that flake off may contribute to the contamination of the final product. To address this problem, the vacuum lifter of the present invention is manufactured from Federal Drug Agency (FDA) approved materials that can withstand the harsh disinfection procedures required. The vacuum lifter of the present invention has also been designed to make the autoclave process easy.
SUMMARY OF THE INVENTION
[0006] The present invention relates to an apparatus that aids in the transportation of objects having at least one side with a smooth, flat surface. The vacuum lifter is autoclavable and washable by disinfectants routinely used in the pharmaceutical and food industries. The vacuum lifter of the present invention is manufactured from Federal Drug Agency (FDA) approved materials that can withstand the harsh disinfection procedures required. In addition the vacuum lifter of the present invention includes a check valve assembly that can be optionally maintained in the open position during the autoclave or disinfection operation.
[0007] The vacuum lifter of the present invention comprises
a) a suction cup having a hub and an axial bleed hole in the hub, b) a center-piece sleeve member molded in the hub and having threaded extensions above the and forming a continuation of the axial bleed hole, c) a handle over the cup and above the center-piece sleeve member, d) a lock-nut, threaded on the center-piece sleeve member and securing the handle to the cup and forming a chamber between the lock-nut and the sleeve member, e) a means to establish communication between the chamber and the atmosphere, d) a check valve assembly in the chamber between the bleed hole and the means, wherein the check valve assembly is operatively connected to the means and the check valve assembly normally closing the bleed hole and wherein the means is optionally capable of maintaining the check valve assembly and the bleed hole open.
[0014] The suction cup end of the vacuum lifter of the present invention is placed on a smooth, flat, non-porous surface. Pressure is applied to the handle of the vacuum lifter to compress the suction cup downward toward the surface thus evacuating the air from the cup and forming a vacuum seal with the surface. When the check valve assembly is in normal operating position, the check valve stops the back flow of air into the cup and helps to maintain the vacuum. Consequently, since the vacuum is sustained, the hold or “grip” on the object is maintained. As a consequence, the lifting power of the vacuum lifter is maintained.
[0015] The materials of construction chosen for the vacuum lifter of the present invention are required to withstand stringent disinfection conditions required for aseptic sterilization. Typical disinfection protocols require use of highly caustic solutions such as CIP200, pH 2, and highly acidic solutions such as CIP100, pH 14. In order to minimize microorganism growth, the vacuum lifter must be able to withstand autoclave steam pressures of typically of from about 15-20 psig of steam (approx. 125-130° C.).
[0016] During the autoclave procedure, it is desirable to have the check valve assembly open to the atmosphere to allow steam to penetrate the interior portions of the vacuum lifter. As such, the vacuum lifter of the present invention is equipped with a mechanism that locks the check valve assembly in the open position.
BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWINGS
[0017] The above and other objects, features, advantages and technical significance of the present invention will be better understood by reading the following detailed description of preferred embodiments of the invention, when considered in connection with the accompanying drawings, in which:
[0018] FIG. 1 is an oblique view of the vacuum lifter.
[0019] FIG. 2 shows the top and side view of the silicon cup.
[0020] FIG. 3 shows the placement of the threaded center piece in the silicon cup.
[0021] FIG. 4 depicts the assembly of the various elements of the vacuum lifter.
[0022] FIG. 5 depicts a vertical sectional view of the lock nut.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The present invention is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. As used in the specification and in the claims, “a”, “an,” and “the” can mean one or more, depending upon the context in which it is used. The preferred embodiment is described with reference to the figures, in which like numbers indicate like parts throughout the figures.
[0024] The various elements of the vacuum lifter of the present invention are depicted in FIGS. 1 through 5 . A resilient suction cup ( 101 ), which is made from materials, such as for example, silicon, which can withstand high temperatures and be strong enough to support the objects to be transported can be employed. The suction cup has a bleed hole ( 404 ) in the hub ( 405 ). A threaded center piece ( 301 ) is tightly fitted inside the bleed hole ( 404 ) of the hub ( 405 ). The threaded center piece ( 301 ) is equipped with a bottom opening ( 302 ) which opens to the interior of the suction cup. A threaded portion of the threaded center piece ( 406 ) projects above the top of the hub. The threads are located on the outside upper section of the center piece ( 301 ). The threaded center piece ( 301 ) may be constructed of any material that can withstand the pH and temperature requirements previously mention. Suitable materials include, for example, 304 , and 316 stainless steel.
[0025] The handle ( 102 ) comprises substantially u-shaped arms that are permanently affixed to a sleeve. The sleeve is of such dimension that it can readily and securely slip over the threaded portion of the threaded center piece ( 406 ). A lock nut ( 103 ) is applied to the threaded portion ( 406 ) and, when fully employed, the lock nut ( 103 ) rests flush with the contacting upper part of the sleeve that is part of the handle ( 102 ), thereby firmly securing the handle ( 102 ) to the hub ( 405 ). When engaged, the lock nut ( 103 ) and the threaded center piece ( 406 ) form a housing for the check valve assembly. Suitable materials of construction for the handle ( 102 ) and lock nut ( 103 ) include, for example, 304 , and 316 stainless steel.
[0026] The lock nut ( 103 ) is roughly cylindrical in shape. At one end of the lock nut ( 103 ) a channel is carved out of the center of a cylinder, down the vertical axis leaving two wings ( 502 ) on the outer edges. The opposite end of the lock nut is machined to receive the threaded section of the center piece ( 301 ). See FIG. 5 for a cross sectional view of the lock nut ( 103 ). Additionally, the lock nut ( 103 ) has a hole ( 502 ) through which a stem ( 407 ) can be extended. On one end of the stem ( 407 ), a pull ring ( 104 ) is attached. The other end of stem is threaded.
[0027] Inside the housing formed by the lock nut ( 103 ) and the threaded center piece ( 301 ), the check valve assembly is found. The check valve assembly comprises a spring ( 401 ), a plunger ( 402 ), and an O-ring ( 403 ). The spring ( 401 ) is coiled about the stem ( 407 ) and sits between the lock nut ( 103 ) and the threaded end of the stem ( 407 ). The plunger ( 402 ) is fashioned in a way that it receives the threaded portion of the stem ( 407 ). Additionally, the plunger ( 402 ) is machined to mimic the contour of the interior of the bottom of the threaded center piece ( 301 ) where the bleed hole ( 302 ) is located. An O-ring ( 403 ) is placed between the plunger ( 402 ) and the bottom of the threaded center piece ( 406 ). The O-ring acts as a seal for the check valve assembly. The O-ring ( 403 ) is made from resilient material that can withstand the high temperature and chemical resistancy required. Examples of suitable O-ring materials include, but are not limited to, silicon, and KALREZ®, a perfluoroelastomer. Examples of suitable materials of construction for the plunger and spring include 304 and 316 stainless steel. These materials are FDA approved for the food and pharmaceutical industries.
[0028] When the vacuum lifter is ready for use, the pull ring ( 104 ) is positioned in channel between the wings ( 501 ) of the lock nut ( 103 ). This position, allows for the proper seating of the plunger ( 402 ) against the bleed hole ( 302 ) at the bottom of the threaded center piece ( 301 ) thus sealing the bleed hole ( 302 ). The vacuum lifter is then positioned, suction cup ( 101 ) side down, onto an object having at least one smooth, flat, non-porous surface. The suction cup ( 101 ) is then evacuated by applying downward pressure on the handle ( 102 ) thus depressing the resilient suction cup ( 101 ) and expelling air to produce a vacuum. The object can then be lifted and transported to the desired location. To release the vacuum lifter from the object, the pull ring ( 104 ) is lifted. To prepare the vacuum lifter for the autoclave and other disinfection protocols, the pull ring ( 104 ) is lifted from the channel of the lock nut ( 103 ), rotated 90° and allowed to rest on top of the wings ( 501 ) of the lock nut ( 103 ). In this manner, the bleed hole ( 302 ) at the bottom of the threaded center piece ( 301 ) remains open to the atmosphere. This allows steam to penetrate through the interior of the threaded center piece ( 301 ) during high temperature disinfection of the unit. In this manner, the interior parts of the vacuum lifter can be sterilized without totally disassembling the vacuum lifter.
[0029] Additionally, the vacuum lifter of the present invention is designed in such a manner as to make maintenance simple. The metal parts of the vacuum lifter are constructed from non-rusting material which can withstand harsh environments including high temperatures, and acidic and basic conditions. Replacement of the check valve assembly O-ring is accomplished by simply unscrewing the lock nut ( 103 ) from the threaded center piece ( 301 ) and removing and replacing the warn O-ring. | The present invention relates to an apparatus that aids in the transportation of objects having at least one side with a smooth, flat surface. The vacuum lifter is autoclavable and washable by disinfectants routinely used to maintain aseptic compliance in industries such as the pharmaceutical and food industries. In addition the vacuum lifter of the present invention includes a check valve assembly that can be optionally maintained in the open position during the autoclave or disinfection operation. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of the filing date of United States Provisional Patent Application No. 60/830,301 filed Jul. 11, 2006 and United States Provisional Patent Application No. 60/851,706 filed on Oct. 13, 2006, the disclosures of which are hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Pyruvic acid (C 3 H 4 O 3 ) has the chemical name 2-oxopropanoic acid, and has a molecular mass of 88.06 grams per mol.
[0003] Pyruvic acid is a colorless organic liquid formed as an intermediate in carbohydrate metabolism and as an end product in glycolysis. Pyruvic acid has a melting point ranging from about 11° C. to about 12° C. and is soluble in water.
[0004] In the laboratory, pyruvic acid may be prepared by heating a mixture of tartaric acid and potassium hydrogen sulfate, or by the hydrolysis of acetyl cyanide, formed by a reaction of acetyl chloride with potassium cyanide. Production under these conditions, however, leaves undesirable impurities, which can be toxic or harmful if not removed in entirety.
[0005] Pyruvic acid also occurs naturally as an intermediate product in carbohydrate and protein metabolism in the human body. Pyruvic acid is important in metabolism as it can be converted to carbohydrates via gluconeogenesis, to fatty acids or energy through acetyl-CoA (which is the main input for a series of reactions known as the Krebs cycle), to the amino acid alanine, and to ethanol.
[0006] In industry, pyruvic acid is used to produce its salts and esters (pyruvates) for the use as dietary supplements and as an effective means of weight loss. Pyruvic acid is also used for the synthesis of amino acids and used for biomedical research. Its derivatives are used in making food additives and flavoring agents.
[0007] Unfortunately, due to the highly reactive nature of pyruvic acid, storage of the molecule over extended periods of time is very difficult and undesirable.
[0008] U.S. Pat. No. 6,753,446 describes diethyl oxalate analogs useful for asymmetric labeling of synthetic compounds. The compounds have the general structure RO-C(O)C(O)—X
[0009] United States Patent Publication No. 2007/0106085 describes intermediates useful in the preparation of [ 13 C 1-5 ]metacrylic acid.
[0010] United States Patent Publication No. 2006/0178534 describes labeled compounds useful for the preparation of labeled compounds, including pyruvic acid.
SUMMARY OF THE INVENTION
[0011] In accordance with one embodiment of the present invention there is provided a process for preparing an isotopically labeled compound of Formula (IIIa)
[0000]
[0000] comprising reacting a compound having Formula (IIIa′)
[0000]
[0000] with a base and R 2 X,
wherein X is F, Cl, Br or I; and
R 2 is a C 1 -C 36 substituted or unsubstituted, saturated, or unsaturated, linear, branched, cyclic, aromatic, or substituted aromatic group, wherein R 2 may include a heteroatom including O, N, S, Si, and P wherein any of the carbon atoms or heteroatoms may be isotopically labeled.
[0012] In accordance with another embodiment of this invetion, the base is selected from the group consisting of K 2 CO 3 , NaHCO 3 , Li 2 CO 3 , Cs 2 CO 3 , t-ButOK, t-ButOLi, hydroxides, alkyl salts, lithium salts, metal hydrides, and heteroatom bases.
[0013] In accordance with another embodiment of this invention, R 2 is —CH 2 —R 4 , and R 4 is selected from the group consisting of phenyl, napthyl, benzofuran, isobenzofuran, indole, benzothiophenee, benzimidazole, indazole, benzoxazole, benzisoxazole, benzothiazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, pyridazine, cinnoline and the substituted variants thereof.
[0014] In accordance with another embodiment of the present invention there is provided a process of forming an isotopically labeled compound of Formula (V)
[0000]
[0000] comprising hydrogenating a compound of Formula (IIIb)
[0000]
[0015] In accordance with another embodiment of this invention, R 2 is —CH 2 —R 4 , and R 4 is selected from the group consisting of phenyl, napthyl, benzofuran, isobenzofuran, indole, benzothiophenee, benzimidazole, indazole, benzoxazole, benzisoxazole, benzothiazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, pyridazine, cinnoline and the substituted variants thereof.
[0016] In accordance with another embodiment of the present invention there is provided a process for the preparation of an isotopically labeled compound of Formula (IIIa′)
[0000]
[0000] comprising reacting a compound of Formula (IIb)
[0000]
[0000] with carbon dioxide in a solvent.
[0017] In accordance with another embodiment of this invention, each R and each R 1 is hydrogen.
[0018] In accordance with another embodiment of the present invention there is provided a process for the preparation of an isotopically labeled compound of Formula (IIb)
[0000]
[0000] comprising reacting a compound of Formula (IIa)
[0000]
[0000] with magnesium in a solvent.
[0019] In accordance with another embodiment of this invention, each R and each R 1 is hydrogen.
[0020] In accordance with another embodiment of the present invention there is provided a process for the preparation of an isotopically labeled pyruvic acid analog having Formula (V)
[0000]
[0000] comprising the steps of:
a) reacting a compound of Formula (IIa)
[0000]
[0000] with magnesium in a solvent to yield the Grignard having Formula (IIb)
[0000]
[0000] b) reacting said compound of Formula (IIb) with carbon dioxide in a solvent to yield a compound of Formula (IIIa′)
[0000]
[0000] c) reacting said compound of Formula (IIIa′)) with a weak base and R 2 X to yield a compound of Formula (IIIa), wherein X is F, Cl, Br or I; and
R 2 is a C 1 -C 36 substituted or unsubstituted, saturated, or unsaturated, linear, branched, cyclic, aromatic, or substituted aromatic group, wherein R 2 may include a heteroatom including O, N, S, Si, and P wherein any of the carbon atoms or heteroatoms may be isotopically labeled;
[0000]
[0000] d) reacting said compound of Formula (IIIa) with ozone in a solvent to yield the compound of Formula (IIIb);
[0000]
[0000] e) hydrogenating said compound of Formula (IIIb) to form said isotopically labeled pryuvic acid analog.
[0021] In accordance with another embodiment of this invention, R 2 is —CH 2 —R 4 , and R 4 is selected from the group consisting of phenyl, napthyl, benzofuran, isobenzofuran, indole, benzothiophenee, benzimidazole, indazole, benzoxazole, benzisoxazole, benzothiazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, pyridazine, cinnoline and the substituted variants thereof.
[0022] Recently, isotopically enriched pyruvic acid was studied for its use in a variety of medical diagnostic applications. The use of pyruvic acid that is isotopically enriched with at least one carbon 13 isotope allows for its use in medical diagnostics. Due to the highly reactive nature of pyruvic acid, storage of the molecule over extended periods of time is difficult and undesirable. Fortunately, storage of pyruvic acid is possible by forming shelf stable precursors of pyruvic acid, and then converting the precursor to pyruvic acid prior to its use, for example, as a medical diagnostic agent.
[0023] Disclosed are two synthetic pathways for the synthesis of precursors of pyruvic acid. The synthesis described herein provides pyruvic acid precursors of the present invention and derivatives in high yield which are shelf stable and which are of a high purity. Moreover, the pyruvic acid precursors allow conversion to pyruvic acid in one step. Finally, the synthetic methodologies of the present invention avoid the use of dangerous reagents, such as potassium cyanide.
DETAILED DESCRIPTION
[0024] The present invention provides compounds having Formula (I)
[0000]
[0000] wherein:
G represents a halogen or a Grignard-halogen complex such as MgF, MgBr, MgCl, and MgI;
[0000]
[0025] wherein + A represents a positively charged counterion;
[0026] Q represents C or O, each of which may be isotopically labeled;
[0027] Q′ represents O or N, each of which may be isotopically labeled;
[0028] each R, each R 1 , and each R 2 may be the same or different and independently may represent hydrogen, deuterium, tritium or a C 1 -C 36 substituted or unsubstituted, saturated, or unsaturated, linear, branched, cyclic, aromatic, or substituted aromatic group, wherein R or R 1 may include a heteroatom including O, N, S, Si, and P wherein any of the carbon atoms or heteroatoms may be isotopically labeled;
[0029] m is 1 if Q′ is O or 2 if Q′ is N;
[0030] n is 0 if Q is O or 2 if Q is C; and
[0031] y is independently 12, 13, or 14;
[0032] wherein the compound is not unlabeled pyruvic acid, the salts of pyruvic acid, unlabeled benzyl pyruvate, unlabeled benzyl methacrolate, propanoic-3- 13 C acid-2-oxo-phenylmethyl ester; or 2-propenoic acid-2-(methyl- 13 C-d3)-phenylmethl ester.
[0033] As used herein, the terms “isotope”, “isotopic” or “isotopically labeled” refer to an atom having the same number of protons but a different number of neutrons as compared with the most abundant form of the element. Accordingly, carbon may be isotopically labeled as 13 C, nitrogen may be isotopically labeled as 15 N, sulfur may be isotopically labeled as 32 S and oxygen may be isotopically labeled as 16 O, 17 O or 18 O. These terms as used herein also refer to radio-labeled elements. Further, these terms as used herein also refer to molecules which contain isotopic atoms.
[0034] The terms “aromatic” or “cyclic group” as used herein, encompasses not only the group but also the substitutions in one or more positions. Substitutions may include, and without limitation, halogens, hydroxyl, nitro, amino, substituted amino having the formula —N(R 3 ) (R 3 ), (wherein R 3 is a C 1 -C 6 linear, branched, or cyclic alkyl group), C 1 -C 5 alkoxy, or C 1 -C 5 alkyl groups. Thus, for example, a reference to a benzyl group can include, for example, meta-chloro benzene, 3,4,5 tri-bromo benzene, p,m,o-methyl, p,m,o-methoxy, and trifluoromethyl.
[0035] Hydrogen atoms, which by convention are not shown, may be deuterium or tritium.
[0036] In a preferred embodiment, at least one atom in Formula (I) is isotopic. More preferably, at least one carbon or y C is C 13 or C 14 .
[0037] The present invention also provides compounds of Formula (II)
[0000]
[0000] wherein:
[0038] X represents F, Cl, Br, I, MgF, MgCl, MgBr and MgI;
[0039] Q represents C which may be isotopically labeled;
[0040] each R, each R 1 , and each R 2 may be the same or different and independently may represent hydrogen, deuterium, tritium or a C 1 -C 36 substituted or unsubstituted, saturated, or unsaturated, linear, branched, cyclic, aromatic, or substituted aromatic group, wherein R or R 1 may include a heteroatom including O, N, S, Si, and P wherein any of the carbon atoms or heteroatoms may be isotopically labeled;
[0041] n is 2; and
[0042] y is independently 12, 13, or 14.
[0043] In some embodiments, each R and each R 1 each may be the same or different and independently may be selected from hydrogen, deuterium, tritium or a C 1 -C 24 substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic, aromatic or substituted aromatic moiety optionally containing one or more heteroatoms including O, N, S, P, and Si, any of which may be isotopically labeled.
[0044] In other embodiments, each R and each R 1 may be the same or different and independently may be selected from hydrogen, deuterium, tritium or a C 1 -C 16 substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic, aromatic or substituted aromatic moiety optionally containing one or more heteroatoms including O, N, S, P, and Si, any of which may be isotopically labeled.
[0045] In yet other embodiments, each R and each R 1 may be the same or different and independently may be selected from hydrogen, deuterium, tritium or a C 1 to C 6 linear or branched, substituted or unsubstituted, cyclic, or aromatic moiety, optionally containing one or more heteroatoms including O, N, S, P, and Si, any of which may be isotopically labeled.
[0046] In preferred embodiments of the compositions of Formula (II), each R, each R 1 , and each R 2 may be the same or different and independently may be selected from hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, butyl, secbutyl, tertbuytl, allyl, 2-butenyl, 3-butenyl, phenyl, benzyl, napthyl, cyclopropyl, cyclopentyl, and cyclohexyl, thienyl, furyl, pyridyl, imidazoylyl, benzimidazoyl, or benzothiazolyl.
[0047] In a preferred embodiment, at least one atom in Formula (II) is isotopic. More preferably, at least one carbon is 13 C or 14 C. Most preferably, at least one y C is 13 C or 14 C.
[0048] In some embodiments, the compounds of Formula (II) have the structure of Formula (IIa):
[0000]
[0000] wherein R and R 1 are as defined previously.
[0049] In other embodiments, the compounds of Formula (II) have the structure of Formula (IIb):
[0000]
[0000] wherein R and R 1 are as defined previously.
[0050] Non-limiting examples of compounds falling within the scope of the compounds of Formula (II) include:
[0000]
[0051] The present invention also provides compounds of Formula (III)
[0000]
[0000] wherein:
[0052] Q represents C or O, each of which may be isotopically labeled;
[0053] Q′ represents O, or N, each of which may be isotopically labeled;
[0054] each R, each R 1 , and each R 2 may be the same or different and independently may represent hydrogen, deuterium, tritium or a C 1 -C 36 substituted or unsubstituted, saturated, or unsaturated, linear, branched, cyclic, aromatic, or substituted aromatic group, wherein R or R 1 may include a heteroatom including O, N, and S, wherein any of the carbon atoms or heteroatoms may be isotopically labeled;
[0055] m is 1 or 2;
[0056] n is 0 or 2; and
[0057] y is independently 12, 13, or 14;
[0058] wherein the compound is not unlabeled pyruvic acid, the salts of pyruvic acid, unlabeled benzyl pyruvate, unlabeled benzyl methacrolate, propanoic-3- 13 C acid-2-oxo-phenylmethyl ester; or 2-propenoic acid-2-(methyl- 13 C-d3)-phenylmethl ester.
[0059] In a preferred embodiment, at least one atom in Formula (III) is isotopic. More preferably, at least one carbon or y C is C 13 or C 14
[0060] In some embodiments, each R, each R 1 , and each R 2 may be the same or different and independently may be selected from hydrogen, deuterium, tritium or a C 1 -C 24 substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic, aromatic or substituted aromatic moiety optionally containing one or more heteroatoms including O, N. S, Si, and P any of which may be isotopically labeled.
[0061] In other embodiments, each R, each R 1 , and each R 2 may be the same or different and independently may be selected from hydrogen, deuterium, tritium or a C 1 -C 16 substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic, aromatic or substituted aromatic moiety optionally containing one or more heteroatoms including O, N, and S, any of which may be isotopically labeled.
[0062] In yet other embodiments, each R, each R 1 , and each R 2 may be the same or different and independently may be selected from hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, butyl, secbutyl, tertbuytl, allyl, 2-butenyl, 3-butenyl, phenyl, benzyl, napthyl, cyclopropyl, cyclopentyl, cyclohexyl, thienyl, furyl, pyridyl, imidazoylyl, benzimidazoyl, or benzothiazolyl.
[0063] In yet further embodiments, R 2 is selected from a protecting group including but not limited to methoxymethyl ether, tetrahydropyranyl ether, t-Butyl ether, allyl ether, benzyl ether, trimethylsilyl ethers, triethylsilyl ethers, t-butyldimethylsilyl ether, t-butyldiphenylsilyl ether, acetic acid ester, benzoic acid ester, methylthiomethyl ethers, benzyloxymethyl ethers, 2-napthylmethyl ethers, p-methoxybenzyl ethers, trityl ethers, and methoxytrityl ethers.
[0064] In some embodiments, Q is C; Q′ is O; and R 2 is H, and at least one y C group is 13 C or 14 C.
[0065] In other embodiments, Q is C; Q′ is O; and R 2 is benzyl, and at least one y C group is 13 C or 14 C.
[0066] In further embodiments, Q is O; Q′ is O; and R 2 is benzyl, and at least one y C group is 13 C or 14 C.
[0067] In yet other embodiments, the compounds of Formula (III) have the structure of Formula (IIIa):
[0000]
[0000] wherein y C, R, R 1 , and R 2 are as defined previously.
[0068] In yet further embodiments, the compounds of Formula (III) have the structure of Formula (IIIb):
[0000]
[0000] wherein y C, R, R 1 , and R 2 are as defined previously.
[0069] In preferred embodiments, the compounds of Formula (III) have the structure of Formula (IIIc)
[0000]
[0000] wherein:
Q, y C, R, and R 1 are as defined previously; and
R 4 represents a C 1 -C 10 aromatic ring optionally substituted with one or more nitro, amino, substituted amino having the formula —N(R 3 ) (R 3 ), halogen, deuterium, tritium, C 1 -C 4 alkoxy, or C 1 -C 4 alkyl groups, wherein the aromatic ring optionally includes a heteroatom selected from the group consisting of O, N, and S.
[0070] Examples of aromatic rings representative of R 4 include, but are not limited to, phenyl, napthyl, benzofuran, isobenzofuran, indole, benzothiophenee, benzimidazole, indazole, benzoxazole, benzisoxazole, benzothiazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, pyridazine, cinnoline and the substituted variants thereof.
[0071] It has been found that the inclusion of a single carbon spacer adjacent to R 4 , as in Formula (IIIc) and the Formulas which follow, allows for cleavage of the R 2 group (Formula (III)) by means of hydrogenation rather than acid hydrolysis. As discussed herein, hydrogenation provides an efficient means by which the compounds of Formula (IIIc) can eventually be converted to pyruvic acid or its derivatives thereof. Moreover, hydrogenation allows for the production of pyruvic acid under neutral conditions and where the only byproduct is toluene. Other methods, including acid hydrolysis, leave inorganic or organic acids as impurities.
[0072] In more preferred embodiments, the compounds of Formula (III) have the structure of Formula (IIId):
[0000]
[0000] wherein Q, y C, R, and R 1 each are as defined previously; and R 5 represents at most 5 substitutions on the aromatic ring, wherein R 5 independently represents nitro, amino, substituted amino having the formula —N(R 3 ) (R 3 ), halogen, deuterium, tritium, C 1 -C 4 alkoxy, or C 1 -C 4 alkyl group.
[0073] In one particularly preferred embodiment, the compounds of Formula (IIId) have the structure of Formula (IIIe):
[0000]
[0000] wherein y C, R, R 1 , and R 5 are as defined previously.
[0074] In another particularly preferred embodiment, the compounds of Formula (IIId) have the structure of Formula (IIIf):
[0000]
[0000] wherein y C, R 1 , and R 5 are as defined previously.
[0075] In another particularly preferred embodiment, the compounds of Formula (IIIe) have the structure of Formula (IIIg):
[0000]
[0000] wherein y C, R, and R 5 are as defined previously.
[0076] In another particularly preferred embodiment, the compounds of Formula (IIIe) have the structure of Formula (IIIh):
[0000]
[0000] wherein y C and R 5 are as defined previously.
[0077] In yet another particularly preferred embodiment, the compounds of Formula (IIIf) have the structure of Formula (IIIi):
[0000]
[0000] wherein y C and R 5 are as defined previously.
[0078] In a most preferred embodiment of Formula (IIIi), each R 5 is hydrogen.
[0079] In yet another particularly preferred embodiment, the compounds of Formula (IIId) have the structure of Formula (IIIj):
[0000]
[0000] wherein y C, Q, n, R, R 1 , and R 5 are as defined previously.
[0080] As illustrated below in Formula (IIIj), in a preferred embodiment in accordance with the present invention and particularly for those isotopically labeled compounds discussed herein having the structures generally shown in Formulas IIIa through IIIi, as well as Formula V, it is preferred that the double bond oxygen on the ester forming carbonyl, the carbon of the ester forming carbonyl and/or the carbon of the methacrylate or ketone group be isotopically labeled. In a particularly preferred embodiment in accordance with the present invention, the isotopic labeling of the compounds described above would occur at some atom other than the carbon bound to the various R 1 groups. Isotopically labeling may occur at a plurality of other groups as well.
[0081] Non-limiting examples of the compounds of Formulas (IIIe) and Formula (IIIf) include:
[0000]
[0082] In other embodiments, the compounds of Formula (I) have the structure of Formula (IV):
[0000]
[0000] wherein y C, Q, R, and R 1 are as defined previously.
[0083] Non-limiting examples of the compounds of Formulas (IV) include:
[0000]
[0000] wherein R represents R 2 of Formula (IV).
[0084] In the propamides of Formula (IV) above, R is preferably a C 1 -C 4 alkyl, more preferably methyl or ethyl.
[0085] The present invention also provides a method of synthesizing isotopically labeled compounds including analogs of pyruvic acid.
[0086] One synthetic method, according to the following scheme, comprises reacting a compound of Formula (IIa) with magnesium turnings in a solvent to yield a compound having Formula (IIb):
[0000]
[0087] Preferably, the solvent is an aprotic solvent. More preferably, the solvent is an ether or toluene.
[0088] Preferably, the reaction is run at room temperature, more preferably the reaction is initially run at room temperature with a subsequent increase in temperature to drive the reaction to completion. As used herein, “room temperature” means a temperature ranging from about 22° C. to about 26° C.
[0089] In a preferred embodiment, each R and each R 1 may be the same or different and independently may be selected from hydrogen or C 1 -C 4 alkyl, more preferably each R and each R 1 are hydrogen.
[0090] Another synthetic method, according to the following scheme, comprises reacting a compound of Formula (IIb)) with labeled or unlabeled carbon dioxide in a solvent to yield a compound having Formula (IIIa′):
[0000]
[0091] Preferably, the solvent is selected from ether, tetrahydrofuran, dioxane, and glymes.
[0092] Preferably, the reaction is run with cooling, more preferably at a temperature of about 0° C. or below, most preferably at about −50° C. or below.
[0093] In a preferred embodiment, each R and each R 1 may be the same or different and independently may be selected from hydrogen and C 1 -C 4 alkyl, more preferably each R and each R 1 are hydrogen.
[0094] Another synthetic method, according to the following scheme, comprises reacting a compound of Formula (IIIa′) with a weak base in the presence of a reagent having a halogenated leaving group to yield a compound having Formula (IIIb):
[0000]
[0095] Preferably, bases include K 2 CO 3 , NaHCO 3 , Li 2 CO 3 , Cs 2 CO 3 , t-ButOK, t-ButOLi, hydroxides, alkyl salts, lithium salts, metal hydrides, and heteroatom bases. More preferably the base is K 2 CO 3 .
[0096] In a preferred embodiment, R 2 X is benzyl chloride or benzyl bromide.
[0097] In a preferred embodiment, the reaction is run at room temperature or below. One skilled in the art would recognize that the reaction may be run at temperatures lower than room temperature (between room temperature and −78° C.) to accommodate certain bases.
[0098] In a preferred embodiment, each R and each R 1 may be the same or different and independently may be selected from hydrogen and C 1 -C 4 alkyl, more preferably each R and each R 1 are hydrogen.
[0099] In a preferred embodiment R 2 is —CH 2 —R 4 , wherein R 4 includes, but is not limited, to phenyl, napthyl, benzofuran, isobenzofuran, indole, benzothiophenee, benzimidazole, indazole, benzoxazole, benzisoxazole, benzothiazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, pyridazine, cinnoline and the substituted variants thereof.
[0100] Yet another synthetic method, according to the following scheme, comprises reacting a compound for Formula (IIIa) with ozone in a solvent to yield a compound having Formula (IIIb):
[0000]
[0101] Preferably, this reaction is run in a C 1 -C 6 alcohol (straight chain or branched), methylene chloride, chloroform and the like.
[0102] Preferably, the reaction is run at a reduced temperature, more preferably at about 0° C. or below. As used herein, the term “reduced temperature” refers to a temperature below room temperature.
[0103] In a preferred embodiment, each R and each R 1 may be the same or different and independently may be selected from hydrogen and C 1 -C 4 alkyl, more preferably each R and each R 1 are hydrogen.
[0104] In a preferred embodiment R 2 is —CH 2 —R 4 ,wherein R 4 includes but is not limited to, phenyl, napthyl, benzofuran, isobenzofuran, indole, benzothiophenee, benzimidazole, indazole, benzoxazole, benzisoxazole, benzothiazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, pyridazine, cinnoline and the substituted variants thereof. In a more preferred embodiment, R 2 is benzyl.
[0105] Yet a further synthetic method, according to the following scheme, comprises converting a compound having Formula (IIIb) to isotopically labeled pyruvic acid or an analog thereof by means of hydrogenation, preferably in a solvent selected from a C 1 -C 6 alcohol (straight chain or branched), a ketone, water, an ether, or mixtures thereof.
[0000]
[0106] The reaction is preferably run under a pressure of about 4 to about 12 psig, more preferably the reaction is run using a palladium catalyst, even more preferably the palladium catalyst is on charcoal.
[0107] The reaction is preferably run at room temperature.
[0108] In a preferred embodiment, each R 1 is independently selected from hydrogen or C 1 -C 4 alkyl, more preferably each R 1 is hydrogen.
[0109] The above conversion can also be carried out via acid hydrolysis using techniques known to those of skill in the art. United States Patent Publication No. 2006/0178534, incorporated herein by reference, describes a method of performing acid hydrolysis. For example, acid hydrolysis may be accomplished by treating a compound with 1M HCl and then extracting the final product with an organic solvent, preferably ethyl acetate.
[0110] Yet a further synthetic method, according to the following scheme, comprises converting a compound having Formula (IIIf) to isotopically labeled pyruvic acid or an analog thereof by means of hydrogenation, preferably in a solvent selected from a C 1 -C 6 alcohol (straight chain or branched), a ketone, water, an ether, or mixtures thereof.
[0000]
[0111] The reaction is preferably run under a pressure of about 4 to about 12 psig, more preferably run using a palladium catalyst, even more preferably the palladium is on charcoal.
[0112] In a preferred embodiment, each R 1 is independently selected from hydrogen or C 1 -C 4 alkyl, more preferably each R 1 is hydrogen.
[0113] Yet a further synthetic method, according to the following scheme, comprises converting a pyruvate salt or an analog thereof to the respective pyruvate analog of Formula (IIIb) as follows:
[0000]
[0114] Preferably, the solvent is a polar aprotic solvent. More preferably, the solvent is dimethylformamide.
[0115] In a preferred embodiment, each R 1 is independently selected from hydrogen or C 1 -C 4 alkyl, more preferably each R 1 is hydrogen.
[0116] Preferably R 2 X is R 2 Br. More preferably, R 2 X is benzyl bromide.
[0117] This method of converting an isotopically labeled pyruvate salt to the respective pyruvate analog is particularly useful in isolating or purifying pyruvate salts from materials which contain dimerized pyruvic acid.
[0118] The compounds of Formula (IIIb), formed occurring to the reaction, are separated by techniques known in the art, preferably by distillation or chromatography.
[0119] The compounds of Formula (IIIa) synthesized by this process can then be converted to the respective isotopically labeled pyruvic acid analogs as described previously or even converted to the same pyruvate salt (but having a higher purity than the original pyruvate salt).
[0120] Accordingly, one synthetic route to pyruvic acid or the intermediates of pyruvic acid using the compounds generally described in Formulas (I), (II), and (III) is as follows:
[0000]
[0121] In general, magnesium turnings are combined with Formula IIa to yield the Gringard reagent Formula IIb. Formula IIb is then reacted in the presence of isotopically labeled carbon dioxide (wherein the oxygen atoms may optionally be isotopically labeled) to yield the intermediate of Formula IIIa′. This reaction can be run in an organic solvent selected from ether and related solvents including tetrahydrofuran, dioxane, glymes and the like.
[0122] The reaction is preferably run with cooling and more preferably at a temperature of about 0° C. or below, more preferably about −50° C. or below. The reaction is also preferably run in an inert atmosphere.
[0123] Intermediate Formula IIIa′ is then reacted with a weak base in a solvent including methylene chloride, THF, or acetone at room temperature or above and with a reagent having a halogenated leaving group to arrive at the compound of Formula IIIa. One of ordinary skill in the art would be able to determine the necessary reagent having a halogenated leaving to arrive at the desired pyruvate derivative. For example, the reagent having a halogenated leaving group may be selected from benzyl chloride. Bases useful in the processes of the present invention include K 2 CO 3 , NaHCO 3 , Li 2 CO 3 , Cs 2 CO 3 , t-ButOK, t-ButOLi, hydroxides, metal hydrides, and alkyl salts.
[0124] Ozonolysis is then carried out in the presence of Formula IIIIa to yield the compound of Formula IIIb. Preferably, this reaction can be run in a C 1 -C 6 alcohol (straight chain or branched), methylene chloride, chloroform and the like at a reduced temperature, more preferably at about 0° C. or below.
[0125] Finally, the compound of Formula IIIb is hydrogenated to yield the isotopically labeled pyruvic acid of Formula V. This can be run in a C 1 -C 6 alcohol (straight chain or branched), a ketone, water, an ether, or mixtures thereof. The reaction is preferably run under a pressure of about 4 to about 12 psig, more preferably run using a palladium catalyst, even more preferably on charcoal. The hydrogenation could also be run in acetone.
[0126] This step could also be undertaken using by means of acid hydrolysis under conditions known to those of skill in the art.
[0127] Although the scheme shown above is one method of producing pyruvic acid, one of skill in the art would understand that any of the intermediates described above can be synthesized, isolated, and recovered independently of one another. The intermediates may be used to produce pyruvic acid intermediates or other compounds not disclosed herein.
[0128] Isotopically labeled pyruvic acid analogs can also be prepared by hydrolyzing compounds having Formula (IV) under acidic conditions. By means of example, the production of [1- 13 C]pyruvic acid by means of acid hydrolysis is illustrated below.
[0000]
[0129] Compounds having Formula (IV) can be produced from isotopically labeled N,N-dialkyl-2-oxo-oxamates by Grignard addition, as follows:
[0130] Synthesis of [1- 13 C] Propanamide, N,N-dialkyl-2-Oxo
[0000]
[0000] wherein R is as defined as R 2 in Formula (IV).
[0131] Synthesis of [2- 13 C] Propanamide, N,N-dialkyl-2-Oxo
[0000]
[0000] wherein R is as defined as R 2 in Formula (IV).
[0132] Synthesis of [1,2- 13 C 2 ] Propanamide, N,N-dialkyl-2-Oxo
[0000]
[0000] wherein R is as defined as R 2 in Formula (IV).
[0133] Starting materials for the above conversion to compounds having Formula (IV) may be produced in accordance with U.S. Pat. No. 6,753,446, incorporated herein by reference. For example, an oxamide may be prepared according to the following: [ 13 C]Methyl phenyl sulfide was reacted with sec-butyl lithium followed by [ 13 C]carbon dioxide to form intermediate (I). This intermediate (I) was then reacted with oxalyl chloride followed by dimethyl amine to form intermediate (II). This intermediate (II) was then reacted with sulfuryl chloride followed by 10 percent water in ethanol to form [1- 13 C]acetic acid, (dimethylamino)oxo-, ethyl ester.
[0134] Compounds of Formula (IV) can also be prepared by reacting compounds having Formula (IIIa′) with oxalyl chloride to form an acid halide intermediate, followed by reaction with an amine to form the di-substituted amide having Formula (IV). For example, the reaction with oxalyl chloride, and amine, proceeds as follows:
[0000]
[0135] Preferably, the reaction with oxalyl chloride is run in a non-polar aprotic solvent, more preferably dichloromethane. Preferably, the reaction with the amine is run in a non-polar solvent, more preferably THF.
[0136] Synthetic examples of the production of isotopically labeled benzyl pyruvate and isotopically labeled pyruvic acid are as follows:
[0137] Step 1: Synthesis of [1- 13 C]methacrylic acid.
[0000]
[0138] An oven dried 2L 3-neck round bottom flask equipped with a 300 mm Allihn reflux condenser with gas adapter, heating mantle, 125 mL addition funnel with septa, and mechanical stirrer was placed under vacuum and back filled with Argon. Isopropenyl magnesium bromide (0.6 moles) was then added to the round-bottom flask, and cooled and maintained at—keep with 78 C with a dry ice/acetone bath. The 13 CO 2 was bubbled into the Grignard via a needle and measured with a flow meter set at about 200 mL per minute, 27 g, 0.6 moles. The addition took about 55 minutes. After addition, the reaction was stirred for fifteen minutes. Meanwhile, 100 mL of concentrated 12M HCl, 1.2 moles, was diluted with 100 mL of water and transferred to the addition funnel in portions and added as a steady stream to the Grignard over about ten minutes. After addition, the cold bath was removed and replaced with water, to warm the reaction to room temperature. The resulting mostly colorless biphasic mixture was transferred to a 2 L separatory funnel. The lower aqueous phase was made acidic by addition of 0.6 moles of HCl. The aqueous was extracted with dichloromethane (3×200 mL)and was separated. The organic layers were combined and washed with 0.7 moles of NaOH. The aqueous layer was separated and evaporated to dryness. The [1- 13 C]sodium methacylate was used in the subsequent reaction without purification.
[0139] Step 2: Synthesis of Benzyl [1- 13 C]methacrolate.
[0000]
[0140] The [1- 13 C]sodium methacylate was added to dimethyl formamide (DMF) (250 mL) in a 2 L round bottom flask at room temperature. This mixture was allowed to stir for about five minutes and then benzyl chloride (77.195 g, 0.6098 mol, 70.18 mL) was added at a quick drip rate over a twelve minute period. The reaction proceeded for six hours. Dichloromethane (750 mL) was added to the mixture and this mixture was filtered through a frit funnel. It was then transferred to a separatory funnel and was washed with DI water (3×150 mL). The last wash (4th) was done using sodium thiosulfate (15 g in 150 mL) to remove iodine from the solution. The organic extract was dried over sodium sulfate and evaporated in vacuo to a slightly yellow oil containing the desired product with some DMF. The DMF was removed under vacuum by heating the flask to 40oC until about all of the DMF solvent was removed.
[0141] Step 3: Synthesis of Benzyl [1-13 C]pyruvate
[0000]
[0142] A stirred solution of 25 mL (147.5 mmole) of benzyl methacrylate in 500 mL of dichloromethane and 125 mL of methanol was cooled to −78° C. and ozonized until the solution was pale blue, indicating excess ozone. The solution was purged with nitrogen until the blue color of ozone had dissipated, and then 14.1 mL (192 mmole, 1.3 equivalents) of dimethyl sulfide was added rapidly dropwise under nitrogen. After stirring for one hour more at −78° C. the solution was removed from the cold bath and allowed to stir at room temperature for 3 hours. The solution may be stored overnight in the freezer at this point. Volatiles were removed on the rotary evaporator at 40° C. and the residue was taken up in 100 mL of dichloromethane and washed with 100 mL of water to remove dimethyl sulfoxide. The water layer was back extracted with a small volume of dichloromethane. The combined organics were washed with water in this fashion twice more. The final organic layer was filtered through cotton, concentrated on the rotary evaporator, and high-vacuum dried leaving an essentially quantitative yield of benzyl pyruvate as a colorless liquid. A small amount of formaldehyde methyl hemiacetal and/or the methyl hemiacetal of benzyl pyruvate may be present but do not interfere in the next step.
[0143] Step 4: Synthesis of [1-13 C]Pyruvic Acid
[0000]
[0144] 5 g (28 mmole) of the above benzyl pyruvate was dissolved in 100 mL of absolute ethanol in a heavy-walled bottle and blanketed with nitrogen. 0.5 g of 5% palladium on charcoal catalyst was added and the mixture was in a Parr shaker hydrogenation apparatus. The mixture was deaerated three times by evacuation followed by refilling with hydrogen. Hydrogenation was then commenced at 8 psi for one hour. Hydrogen was then removed by evacuation followed by refilling with nitrogen. Catalyst was removed by vacuum filtration through a bed of Celite. The filter cake was washed with ethanol and the colorless to pale yellow filtrate was concentrated on the rotary evaporator at room temperature. Excessive vacuum or higher temperature must be avoided to prevent loss of product. The product obtained still contained a little ethanol and showed pyruvic acid, varying amounts of its ethyl hemiacetal, and a very small amount of ethyl pyruvate by NMR. Water may be added and distilled off at a bath temperature of less than 50° C. under high vacuum with liquid nitrogen cooling of the receiver. After most of the water was removed, additional water was added to the pot and the process repeated. What remained was a concentrated solution of pyruvic acid and its hydrate possibly contaminated by a little formaldehyde hydrate and ethyl pyruvate. Titration with 1N aqueous sodium hydroxide to an endpoint of pH 5.8 and removal of water and other volatiles yielded solid sodium pyruvate.
[0145] The reaction above could also be run in other solvents for example the reaction was run using acetone and at the end of the process [1-13 C]Pyruvic acid was isolated as a mixture of 2 parts pyruvic acid to 1 of acetone. For example, the Hydrogenation of benzyl [1- 13 C]pyruvate using acetone is accomplished as follows: Benzyl [1- 13 C]pyruvate (5.1 g, 0.0285 moles) was dissolved in acetone (51 mL) and placed in a hydrogenation vessel which had 10% Pd/carbon (0.28 g). The reaction was purged with argon and then the reaction was evacuated under vacuum. The reaction vessel was filled with hydrogen to 10 psi and then shaken for 24 hours. The reaction was filtered to remove the catalyst and then concentrated. This mixture, which now contained toluene and [1- 13 C]pyruvic acid, was treated with hexane. The layers were then separated and the hexane layer which contained the [1-13C]pyruvic acid was evaporated to give a quantitative yield of the desired product as a mixture of acetone to [1- 13 C]pyruvic acid (1:2).
Shelf Stability of Isotopically Labeled Pyruvic Acid:
[0146] Samples of isotopically labeled [1- 13 C] pyruvic acid, having Formula VI and synthesized as discussed immediately below, were subjected to various conditions as depicted in Table 1, in order to establish the compound's shelf storage stability.
[0000]
[0147] The [1- 13 C] pyruvate of Formula VI was synthesized as follows:
[0148] Benzyl [1- 13 C] pyruvate, Formula VIA, was synthesized according to the methods discussed previously. The benzyl [1- 13 C] pyruvate was hydrogenated and the hydrogenation mixture was diluted with water and then extracted with dichloromethane. The organic phase contained toluene and some methanol while the aqueous phase contained the [1- 13 C] pyruvic acid and methanol. The aqueous phase was then distilled until all of the methanol was removed, thereby leaving [1- 13 C] pyruvic acid (purity: 98+/−2%, by NMR).
[0000]
[0149] The resulting [1- 13 C] pyruvic acid was tested as follows in Table 1:
[0000]
TABLE 1
Samples of isotopically labeled pyruvic acid were subjected to
various storage conditions.
Condition
Duration
Sample
Temperature
Storage
12 weeks
17 weeks
1
−10° C.
Dark
Stable
Stable
2
4° C.
Dark
Stable
Stable
3
Room
Dark
Stable
Stable
temperature*
4
Room
Light
Stable
Stable
temperature*
*Room temperature denotes a temperature ranging from about 22° C. to about 26° C.
[0150] 1 H and 13 C NMR spectra of the distilled [1- 13 C] pyruvic acid in water (0.025M) were acquired at the onset of the study and prior to exposing the samples to the various conditions specified in Table 1. 1 H and 13 C NMR spectra were again acquired for each of the samples after being exposed to the aforementioned conditions on a weekly basis for 12-weeks. The spectra acquired after exposure were compared visually and appeared to remain unchanged as compared with the spectra acquired prior to exposure, i.e. the spectra were as expected for [1- 13 C] pyruvic acid in water. As such, it was concluded that each of the samples were shelf stable. Similarly, 1 H and 13 C NMR spectra acquired after 17-weeks of exposure remained unchanged as compared with the spectra acquired prior to exposure. Once again, it was concluded that each of the samples were shelf stable under the conditions provided in Table 1.
[0151] Concentration studies were also performed to show that [1- 13 C] pyruvic acid solutions would also be expected to be stable at higher concentrations. To demonstrate such stability, the [1- 13 C] pyruvic acid solutions were compared to commercial samples of pyruvic acid (Formula VIB) obtained from Sigma-Aldrich Co. in water at higher concentrations. Commercial pyruvic acid was dissolved in water to arrive at the various concentrations listed in Table 2 below. Each of these commercial solutions were subjected to light for 6-weeks at temperatures ranging from about 22° C. to about 26° C. At each of the concentrations listed below, it was discovered that the pyruvic acid solutions were stable. As the purity of the commercial pyruvic acid samples were comparable to the purity of the materials produced in accordance with the present invention, and as the commercial materials were stable in water for at least 6 weeks at relatively high concentrations, it is believed that [1- 13 C] pyruvic acid solutions having at least those concentrations in water would also be stable.
[0000]
TABLE 2
Pyruvic acid, of varying concentrations, was found to be stable
after 6-weeks.
(Formula VIB)
Concentration
After 6-weeks
11.3
Stable
5.7
Stable
3.8
Stable
2.8
Stable
2.3
Stable
[0152] The molarity of sample 4 was confirmed to be 0.025M by titrating the aqueous sample with sodium hydroxide. The titration with the sodium hydroxide also revealed that in acidic conditions, such as at pHs ranging from about 5.8 to about 1, pyruvic acid may be present either as the acid or as sodium [1- 13 C] pyruvate, depending on the sodium hydroxide concentration. It was also discovered that at pHs greater than 5.8, such as at a pH of about 6.2, some of the pyruvic acid was present in the form of a dimerized sodium salt. For example, at a pH of about 6.2, the pH attained in titrating the solution of sample 4, HPLC revealed that sample 4 consisted of 89% sodium [1- 13 C] pyruvate and about 2-4% dimerized [1- 13 C] pyruvate salt (accounting for about 4-6% of the pyruvic acid). As such, it was discovered that to minimize dimmer formation, it may be necessary to control the pH of [1- 13 C] pyruvate solutions, and in particular, any aqueous solution should be maintained at a pH of about 6.5 or less, more preferably 6.0 or less, and even more preferably 5.8 or less.
[0153] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | Isotopically labeled alpha-keto acids and esters are disclosed herein. Also disclosed are methods of synthesizing isotopically labeled alpha-keto acids and esters. | 2 |
This is a divisional of application Ser. No. 364,474, filed Mar. 31, 1982.
BACKGROUND OF THE INVENTION
The present invention relates generally to a system for protecting threads. More particularly, the invention relates to a system for protecting machine threads as well as methods for producing and attaching such protective devices to machine threads.
Threads are found, for exmple, on machine parts and pipes. Threads typically represent delicate areas that must be protected against harmful mechanical and chemical effects during their transportation and storage.
Consequently, it often becomes necessary to protect machine parts and pipes from damage by using protective caps and the like. When pipes are transported, for example, they are often subjected to very rough treatment. If pipes are to be used in a drilling operation, they are often first pulled up a drilling tower and, as a result, suffer damage. The actual threads, as well as the sealing flanges on the ends of the threads, are often damaged. Even a slightly damaged thread can render an expensive pipe unusable.
In addition to mechanical damage to pipes, the effect of the environment also can render pipes unusable. Salt water, sand, dust, as well as snow, rain, and wind have adverse effects on pipes. Corroded or rusted threads and sealing flanges render pipes unusable; repair of such chemically damaged pipes is expensive. Thus, it is imperative that threads and sealing flanges remain in good condition if the threads are to maintain good connections.
In conventional practice, threads have been protected by screwing protective caps onto them. Such caps may be either open sleeves or closed plugs. Protective caps may be screwed onto the pipes having threads on their outer surface (pivots). Similarly, protective caps may be used which have threads on their exterior surface which are screwed onto the inside threads (bushings) of a pipe.
Protection against chemical influences may be achieved by coating the threads with grease. In addition, there are now protective caps made of synthetic material; such caps often provide sufficient protection for threads.
There are many cases, however, where very high demands are made on the mechanical strength of a protective cap. For example, it is common to pull pipes, which are to be used in an oil drilling operation, into a drilling tower. During such an operation, the lower end of the pipe experiences considerable mechanical stress as a result of the fact that the end of the pipe is dragged on the ground.
Oil drilling operations require that once the pipe is moved into position, the device for protecting the threads must be removed in a very short time. For the steel protective caps now often used, removal is performed by unscrewing the cap. However, this process is time consuming.
In order to reduce the time that is necessary to remove such a steel protective cap, it is frequently loosened before the pipe is pulled onto the drilling tower. Such loosening, however, often causes the protective cap to become cross-threaded such that the thread is damaged by further forced loosening.
Other types of caps are available which are used especially for transporting a pipe onto a drilling tower. Such caps, however, have the disadvantage that they do not sufficiently protect the threads from dirt. Also, such caps often wear out quickly. Moreover, the installation of such a special cap requires time and consequently increases the labor costs of the drilling operation.
Use of steel caps is often undesirable, since they do not protect threads against stronger impacts. Rather, such impacts destroy both the cap and pipe. Furthermore, steel caps often become cross-threaded, and turning the cap then leads to the destruction of the thread. Moreover, steel caps cannot protect threads against the effects of water, moisture, sand, and dust. When pipes are stored for extended periods in the open, the threads thus are exposed to corrosion.
To avoid these disadvantages, pipe users occassionally use protective caps made of metal which are lined with an elastomeric material. The elastomeric material thus provides a better seal between the steel cap and the thread, as well as providing a cushion between the cap and the thread. This helps to protect against the effects of moisture as well as mechanical impact.
It is clear, however, that manufacturing protective caps with an inside lining of elastomeric material requires increased technical expertise as well as added expense. Moreover, such lined caps are ineffective to fully protect threads against moisture, water, and dust.
A type of protective cap currently available is made of synthetic material. Such synthetic caps may be produced with threads; after such caps have been placed on the threads of pipes, they may only be removed by the time-consuming process of unscrewing them. Some synthetic caps do not have threads; this type of construction is also undesirable, since such caps do not fit tightly on the pipes. Thus, the caps are subject to being pulled off inadvertently and do not provide good protection against the penetration of water and dirt.
In order to protect the outer and inner threads of pipes, protective caps, consisting of steel, plastic, or a combination of the materials, are often used. Even if such protective caps are screwed onto the threads and do provide some protection for the threads against damage, such devices provide no protection for the inside of a pipe. As a result, foreign substances, such as water, dirt, ice, and sand, become lodged in the interior of the pipe.
Pipes are often inserted into wells having depths as great as several thousand meters. Thus, a large number of pipes must be screwed together. The threads of the upper pipes must absorb the weight of the entire pipe line. Moreover, the screw connections between the pipes must often be gas-tight. Therefore, complicated thread designs are frequently used. It is clear that such threads must remain intact after their manufacture.
Pipes are also often connected by welding them together. The ends of such pipes are often provided with precise welding chamfers which, like the pipe threads, must be protected.
Pipes used in drilling operations frequently are transported or stored for extended periods. During such times, the pipes are exposed to weather and dirt. If left without protection, the pipe ends are in contact with foreign substances and often corrode, causing a lessening of the integrity of the pipe ends. When such pipes are then to be used, it is a time consuming and expensive task to sort out which pipes are usable.
SUMMARY OF THE INVENTION
In a principal aspect, the present invention is a method for protecting machine or pipe threads. The thread is first cleaned and then coated with a separating agent that will prevent the thread from adhering to a protective material. Next, a mold is loosely mounted around the thread. The mold and thread bear a spaced relationship to each other and thus provide an interspace between them. Finally, the interspace is filled with a protective material such as an elastomer.
In another primary aspect of the invention, a tear-open element is arranged in the interspace before it is filled with the protective material. Thus, after the mold is removed, the protective material may be quickly removed by pulling on the tear-open element.
In yet another primary aspect of the invention, a device for protecting threads is provided which includes a cap of molded, protective material. The cap also includes a tear-open element for easily removing the cap from the thread.
Thus, the present invention helps solve the problem of protecting devices which are to be connected with each other. The invention also protects the insides of such parts, such as pipe interiors. Such protection is most useful immediately after such devices have been manufactured. However, the method may be used independently of the manufacturing process. In addition, once the devices are to be used, the protective devices can be removed with little effort and in an extremely short time. The invention hermetically seals the devices against such elements as weather, dust, sand, and salt water.
A protective material may be in the mold as it is placed around the threads or it may be injected into the interspace after the mold has already been attached to the pipe. The protective material may have elastomeric properties. Polyurethane is particularly useful with the present invention.
By using a casted cap, the threads and sealing flanges are properly sealed; rain water, snow, ice, dust, and particularly salt water and humid air cannot penetrate the cap and cause corrosion. Thus, the time consuming task of cleaning and greasing the pipe ends so that they may be connected is eliminated. Moreover, the physical strength of the cap, particularly if the mold is left on with the casted protective material, provides protection against damage from impact.
The protective device can be made simply. Moreover, it may be quickly detached from the protected objects. This feature is particularly advantageous if it is undesirable to spend time unscrewing a protective cap in the conventional manner.
For instance, the protective caps used on pipes in earth drilling projects must be removed very fast. Labor costs in such projects are high and the unscrewing of conventional protective caps for a large number of pipes causes considerable expense. In order to avoid these disadvantages, the present invention allows quick separation of the protective cap from the pipe.
The protective device also may include a tearing lug, a tearing thread, or, generally, a predetermined breaking line so that the cap may be readily removed. The method has the additional advantage that it may be used everywhere; it is not limited to use at the factory that manufactures the pipe.
The protective cap includes weak spots, cutting surfaces, or other means which make it possible to remove the protective cap by tearing it. The protective cap may be made in a separate mold or be put onto the threads directly by extruding.
It is thus the object of the present invention to produce a covering that may be removed with little effort and within a very short time. In yet another primary aspect of the present invention, a stopper is made of elastic material and can be pressed into the pipe. The outside of the stopper bears against the inside surface of the pipe, hermetically sealing it.
For the protection of outside threads, the stopper can be made in the form of a cylinder with a closure on one end. The outer jacket of the cylinder has flexible sealing lips surrounding its periphery.
A stopper can also be made by pressing it directly into the pipe end. In one form of the present invention which protects inside threads, the stopper is disk-shaped and includes a production which surrounds the periphery of the stopper. The stopper is preferably somewhat conical in shape, pointing inward toward the rest of the pipe. In addition, a wide end of the stopper pointing out of the pipe can be provided with a conical projection which surrounds the entire periphery of the pipe.
It is an object of the present invention to provide a hermetical sealing against the interiors of pipes and of other cylindrical housings. The sealing lips on the preferred form of the closing stopper are usable with pipes having different inside diameters. Thus, the production of such stoppers may be limited to a few sizes, each size having the ability to protect many different size diameter pipes. The outer edge of the stopper provides sufficient sealing for the front side of the pipe.
The disk-like stopper, which protects the insides of pipes and other such devices, has a shoulder which extends beyond the end of a protector sleeve made of steel. The conical narrowing of this shoulder facilitates the mounting of the stopper inside the pipe. The conical widening provided on the disk-shaped stopper assures that the stopper will properly seal the inside of the pipe.
The stoppers can be mounted easily because they can be pushed in by hand into the end of a pipe or into the sleeve of a protective device. As a result, the stoppers are protected against displacement. Unlike conventional protectors, this keeps the present stoppers from being lost while the pipes are being transported over great distances. Yet another object of the present invention is to provide a simple, yet highly reliable, system for sealing the interiors of cylindrical pipes or housings.
BRIEF DESCRIPTION OF THE DRAWING
A preferred embodiment of the present invention is described herein with reference to the drawing wherein:
FIG. 1 is a side view of a preferred embodiment of the present invention showing a pipe end with threads in a casting mold;
FIG. 2 is a side view of the preferred embodiment of FIG. 1 showing the casting mold in use and the interspace filled;
FIG. 3 is a side view of a variation of the preferred form of the present invention shown in FIG. 1 showing a shaft with an inside thread and a mold core;
FIG. 4 is a side view of the shaft shown in FIG. 3 with the interspace filled;
FIG. 4a is a side view of a variation of the preferred form of the invention shown in FIG. 1 with a mold core and a pipe end with inside threads;
FIG. 5 is a cross-sectional view of the protective cap shown in FIG. 1 with different types of weakened areas shown;
FIG. 6 is a graphical illustration of the protective cap shown in FIG. 5 with an inserted tearing line;
FIG. 7 is a graphical illustration of a narrow cross-sectional area that may be used with the protective cap shown in FIG. 1;
FIG. 8 is a graphical illustration of the protective cap shown in FIG. 1 with markings showing the course of a tearing line;
FIG. 9 is a perspective view of a variation of the preferred form of the embodiment of FIG. 1 with a common type of thread covering for a sleeve;
FIG. 10 is a perspective view of the thread covering shown in FIG. 9 with four weak spots arranged on its periphery;
FIG. 11 is a perspective view of a preferred form of the present invention showing a covering for the threads in a closed type of protective cap;
FIG. 12 is a cross-sectional view of a weak spot shown in FIG. 10;
FIG. 13 is a cross-sectional view of a variation of a weak spot shown in FIG. 12;
FIG. 14 is a cross-sectional view of a variation of a weak spot shown in FIG. 12;
FIG. 15 is a cross-sectional view of a variation of the preferred form of the present invention shown in FIG. 1 with the protective device having an inserted wire;
FIG. 16 is cross-sectional view of a sleeve showing a preferred form of the present invention;
FIG. 17 is a side view of a pipe end having a protective cap screwed on;
FIG. 18 is a side view of a closing stopper;
FIG. 19 is a cross-sectional view of a pipe end with a protective cap screwed on and a closing stopper inserted;
FIG. 20 is a cross-sectional view of a pipe end showing a closing stopper inserted and wherein the outer end of the stopper surrounds the collar-like pipe ends and welding chamfer;
FIG. 21 is a cross-sectional view of a pipe end having an outer thread which is protected by a closing stopper with a collar-like formation at its outer end;
FIG. 22 is a cross-sectional view of a pipe end having an inside thread, a device for protecting threads screwed on, and a closing stopper inserted; and
FIG. 23 is a side view of an individual stopper.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in FIG. 1, a pipe 1 has an end thread 2 which is to be protected against corrosion and mechanical damage. A mold 3, which can be slid over the thread 2, provides the protection. In the upper zone, the mold 3 is equipped with a filling projection 4; this filling projection allows material to be inserted and form the protective device.
FIG. 2 shows the use of the mold 3. The material is applied in the direction of the arrow 6 into the space formed between the thread and the inside surface of the mold 3. After a short hardening time, the resulting device 5 hermetically seals the thread 2 and protects it from mechanical damage. As illustrated in FIGS. 1 and 2, the connecting end piece of the thread of pipe 1 serves, as a practical matter, as the mold core during the formation of the protective device.
According to FIG. 3, an end piece 8 rests on a shaft 7. The shaft 7, which can be replaced by pipe, includes a hollow space 9 and an inside thread 10. The mold 11, which acts as a core in this example, slides into the hollow space 9. Thus, as shown in FIG. 4, the interspace between the mold 11 and the shaft 7 can be filled through the filling opening 11a with the material forming the protective device 12.
According to another example of the preferred embodiment shown in FIG. 4a, the end of the pipe 1 has an inner thread 21 provided with a protective covering 24. The mold 22 is made with a ring-shaped thickening 23 that seals against the pipe 1. The material inserted through the openings 22a thus cannot pass beyond thickening 23 and into the interior of the pipe.
FIG. 5 shows a sleevelike protective device 5 with several different, weakened cross-sectional areas. According to one aspect of the preferred embodiment, a simple weakened cross-sectional area 13 exists on the protective device 5. Because of its slight thickness, the protective device can be opened with a simple, common cutting tool. As shown in FIG. 5, for example, the weak portion of the elastomeric material defines at least one imaginary plane that intersects the pipe.
The insertion of a tearing wire 14 allows the protective device 5 to be opened without any other tools. According to FIG. 6, the end of the wire 14 is equipped with a ring 15 for a better grip. A double-side weakening 16 can also be provided in the protective device 5 if a corresponding core is put in.
FIG. 7 shows another aspect of the preferred embodiment that uses a tearing lug 17. By pulling the tearing lug 17, the protective device can also be opened without the help of outside tools.
The example according to FIG. 8 shows the straight course of the tear-off line 18 and inserted tearing wire 14'. Another possibility for enabling the protective device to be quickly torn open is shown by a spiral arrangement of a tearing line within a weakening of the cross-sectional area 13.
From the illustration according to FIG. 8, it can be seen clearly that when making the protective device by casting it, thread turns are formed on the protective device. Such thread turns are a mirror image, or negative, of the turns actually found on the pipe.
By means of the example shown, it can be recognized easily that, if sufficient time for the unscrewing of the connecting device is not available, it is possible to remove the protective device by a tearing element along a defined line. Thus, considerable expense may be saved.
For the production of the protective device, the hollow, or outer, end of the parts to be protected (thread turns and seals) are cleaned and coated with a separating agent. The mold may consist of two parts which are connected to each other by a hinge. Alternatively, the mold may be made of one part which can be put around the end to be protected or be slid into the hollow space to be protected.
The mold can also be provided with a separating agent in order to ease the removal of the mold after it has been filled with the elastomeric material. The material forming the device, such as, for example, elastomeric material, is subsequently put into the interspace between the mold and the part to be protected. The filling can effectively take place without applying pressure to the material.
After a period of about five minutes, the material will have hardened sufficiently, and the mold can be pulled off and used again on the next part to be protected. The mold can also be left on the part to be protected for increased protection. In such a case, where the mold acts shell on the object to be protected, the use of a separating medium on the mold can be omitted.
The broken lines shown in FIG. 9 indicate two possible weak spots 30 provided on the periphery. These weak spots 30 divide the sleeve 32 into halves 34, 36.
By the arrangement according to FIG. 10, it is possible to separate the two center strips 38. This facilitates the removal of the remaining halves 40, 42 or of an enclosed protective device.
The broken lines in FIG. 11 signify two continuous weak spots.
FIG. 12 shows a weak spot which is formed by strips of material 44, 46. The cross-sectional area over the strip (arrow) may be severed, for example, by cutting it with a knife from the outside or by pulling a wire inserted between the strips. The halves 34, 36 can then be removed. The illustration of FIG. 12 also shows a groove 48.
FIG. 13 shows a weak spot which is formed by the strip 50. Because of its profile, the strip 50 has a dovetailed shape. This area of separation guarantees that even after the destruction of the cross-sectional area above the strip, the halves 34, 36 remain next to the threads until they can be pulled off.
FIG. 14 shows a weak spot that is formed by the strips 52, 54. The strips 52, 54 also have a "dovetail profile" and the same purpose as explained in the description pertaining to FIG. 13.
FIG. 15 shows a longitudinal, cross-sectional view of a sleeve. A wire 56 is inserted in the protective device. One end of the wire 56 includes an indicator, variously referred to as a "lug" or an "ear" 58, and the other end includes an anchor 60. The anchor 60 is embedded away from the cutting surface into one of the halves 34, 36. In addition, a recess 62 is shown over the ear 58. Thus, the recess 66 visually indicates, or marks, the location of the lug or ear 58. The recess 66 may thus be referred to as marking means.
FIG. 16, like FIG. 15, shows a longitudinal cross-sectional view of a sleeve. However, a wire 56' is bent into loops.
Reference is made now to FIGS. 17-23. A protective device 73 for threads consists of a steel sleeve 74 with a lining 75 of elastomeric material. The protective device 73 is screwed onto the end of a pipe 71 having an outer thread 72. On the front side of the steel sleeve there are pivots 76. A tool can attach onto the pivots in order to transfer torque to the sleeve and screw it onto the pipe. A cylindrical closing stopper 77 has an inner end with a bottom 78. The closing stopper slides into the pipe 71.
The outer periphery of the closing stopper 77 is provided with sealing lips 79. When pressing the closing stopper into the pipe 71, the sealing lips are bent over to the extent required by the diameter of the pipe. Thus, different sizes of pipe diameters may be blocked with the same closing stopper. Simultaneously, the frictional force to be overcome during the pressing in of the stopper is kept low. Hermetic sealing against the penetration of such elements as moisture, aggressive gases, and dust can be achieved by the arrangement of several lips as shown in FIGS. 17 to 19.
According to other aspects of the present invention shown in FIGS. 20 and 21, the closing stopper has a collar 85 or a collar 86. These collars surround the pipe ends and thereby protect the outside threads or welding chamfers 87.
In order to protect the inside threads on pipe ends, one may alternatively use a steel sleeve 80. The steel sleeve 80 presses an elastomeric material 81 into the individual thread turns (FIG. 22).
The inner, open end of the steel sleeve 80 is closed by a disk-shaped stopper 82 (FIGS. 22 and 23). The end of the stopper that would normally point inward toward the pipe includes a projection 83 that narrows conically in the direction of the pipe. The end of the closing stopper that points outward, away from the pipe, is also made with a conical projection 84 that is capable of yielding when the closing stopper is pressed into the sleeve 80. Thus, the entire inside cross-sectional area of the sleeve is sealed.
The projection 83 points inward and attaches onto the end of the sleeve 80, behind the innermost edge. Thus, it keeps the closing stopper from being pulled out.
In the lower half of FIG. 22, the sleeve 80 is shown with a collar 85 that reaches radially inward into the interspace between the projections 83, 84. Thus, the sealing effect is enhanced. The conical slanting of the projections facilitates pressing the stopper into the steel sleeve of the protective device. By means of these simple embodiments, the pipes can be exposed to weather for a long period without the danger of a corrosion of either the threads or interiors of the pipes. | System for protecting machine parts, such as threads, from physical and chemical damage. The parts to be protected are cleaned, coated with a separating agent, and a mold is placed around them. A protective material is inserted in the interspace between the mold and pipe end. The protective material forms a tough, protective jacket. If desired, the mold can later be removed by means of a tear-open element or integrated weak spots. For the protection of pipe interiors, plastic material can be pressed into the end of the pipe such that it seals against the inside lining of the pipe. | 1 |
Reference is made to U.S. patent applications Ser. No. 374,897 which was filed on June 30, 1989, and Ser. No. 395,234 which was filed on Aug. 17, 1989. This and the referenced applications are copending and assigned to a common assignee.
TECHNICAL FIELD
The present invention relates generally to butterfly valves. More specifically, the invention relates to butterfly valves which incorporate novel means for moving or retaining the position of a butterfly plate subjected to aerodynamic or hydrodynamic forces which tend to resist such movement or retention.
BACKGROUND OF THE INVENTION
FIG. 7 of the accompanying drawings schematically illustrates a conventional butterfly valve structure 10 in which a butterfly plate 12 positioned in a duct 14 is rotated about an axis 16 defined by a spindle or shaft 18 in order to vary the rate at which fluid flows through the duct. Typically, the plate 12 is rotated via torque applied by an external actuator 20 through the shaft 18.
A series of arrows 22 generally illustrates the static pressure profile resulting from the hydrodynamic forces acting on the butterfly plate 12. The overall effect of the static pressure may be represented by a center of pressure (indicated by the dashed arrow 24) which tends to force the plate 12 to the closed position. This force must be countered or overcome by energy supplied to the actuator 20 in order to retain the position of the plate 12 or further open the valve 10.
As a general matter, in order to lower the externally-supplied energy required to match or exceed the hydrodynamic forces acting on the plate 12, the center of pressure 24 should be favorably altered in relation to the axis of rotation 16. That is, either the center of pressure 24 should be aligned with or moved closer to the shaft 18, or the shaft should be aligned with or moved closer to the center of pressure. Given a particular rotational position of the plate 12 within the duct 14, the center of pressure 24 can be moved in the manner disclosed in U.S. Pat. No. 3,971,414 Illing, for example, by angling a portion of the plate 12 to partially compensate for excessive hydrodynamic forces otherwise acting on the plate at that position. However, this partial compensation is achieved at the expense of splitting the plate 12. This creates problems in applications which demand sealing engagement of the plate 12 with the duct 14 when the valve 10 is closed, and still requires the use of an external actuator 20 to torque the shaft 18.
Butterfly valve structures 10 are in some environments subjected to considerable vibration which can adversely effect both performance and longevity. Vibrational effects are aggravated to the degree that the center of mass of the structure 10 is distanced from the center of the duct 14. Such distancing is the typical state of affairs when a single external actuator 20 is used to torque the shaft 18.
If a butterfly valve structure 10 were designed such that the plate 12 could be translated (rather than simply rotated) relative to the shaft 18, then it would be possible to align or more closely align the center of pressure 24 with the axis 16, thus eliminating or minimizing the externally-supplied energy required to maintain a given flow rate. Furthermore, if the center of mass of the actuator 20 more closely coincided with the center of the duct 14, then the forementioned vibrational effects would be minimized. Accordingly, the present invention is directed to the objective of providing a butterfly valve that is more energy-efficient than conventional butterfly valves. An additional objective of the invention is to provide a structurally stable butterfly valve that is less sensitive to vibration than conventional butterfly valves.
SUMMARY OF THE INVENTION
This invention achieves the forementioned objectives by providing a butterfly valve that comprises a hollow shaft, a plate-like valve member in facing relationship with the shaft, and actuator means, at least partially disposed within the shaft and mechanically coupled to the valve member through the shaft, for effecting revolutionary and translational movement of the valve member relative to the longitudinal axis of the shaft in response to externally-supplied energy.
Preferably, the actuator means comprises two spaced-apart pistons slidably disposed in the hollow shaft, and a cam arrangement is employed to convert linear movement of the pistons to revolutionary and/or translational movement of the valve member relative to the longitudinal axis of the shaft.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a generally cross-sectional view illustrating the preferred embodiment of the invention.
FIG. 2 is a generally elevational, partially cross-sectional view taken along line 2--2 of FIG. 1.
FIG. 3 is a partially elevational, partially cross-sectional, and slightly schematic view taken along line 3--3 of FIG. 1.
FIG. 4 is a generally cross-sectional and slightly schematic view taken along line 4--4 of FIG. 1.
FIG. 5 is a schematic drawing generally illustrating control of movement for the pistons illustrated in FIG. 4.
FIG. 6 corresponds in kind to FIG. 1 and is included to aid description.
FIG. 7 is a generally schematic drawing of a conventional butterfly valve structure.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1-4 illustrate a butterfly valve 30 in accordance with the preferred embodiment of the invention. In FIG. 1, a plate-like valve member 32 (hereinafter "plate") having a suitable rim seal (not shown) abuts the exterior surface of a hollow shaft 34. The abutment location 36 defines a pivot axis for the plate 32. As is further developed hereinafter, the abutment location 36 varies with the angle of rotation (indicated generally in FIG. 6 by the arrow 38) of the plate 32.
Viewing FIG. 2, two slots 40, 42 are formed through the plate 32. Each slot 40, 42 has a portion (as at 44) that is substantially parallel to the shaft 34 but continuous with the remainder of the slot. The remainder of the slot 40 is angled relative to the shaft. The slots 40, 42 converge toward a centerline (not shown) that bisects the plate 32 and is perpendicular to the shaft 34, and are symmetric with respect to the centerline.
Viewing FIG. 3, two arcuate slots 46, 48 are formed through the shaft 34 between its exterior and interior surfaces. The slots 46, 48 have substantially the same overall length as the slots 40, 42 (FIG. 2) formed in the plate 32 but are angularly convergent along their entire lengths. That is, portions of the slots 46, 48 that correspond to the parallel portions 44 (FIG. 2) are not parallel to the shaft 34. The general, positional relationship of the slots 46, 48 formed in the shaft 34 to the slots 40, 42 formed in the plate 32 can be understood by imagining the plate 32 as a piece of paper having the slots 40, 42 formed therein, wherein the parallel portions 44 are colinear with the remainder rather than parallel to the shaft 34. If the imaginary paper plate is then folded around the shaft 34, the slots 40, 42 will nominally locate the positions of the slots 46, 48 to be formed in the shaft 34.
Although not illustrated in the accompanying drawings, it may also be desirable to provide the shaft 34 with a centrally-disposed annular boss extending circumferentially around the shaft and engaging a third slot or recess formed in the plate 32. The third slot would extend linearly along the forementioned centerline. The purpose of the annular boss/third slot combination would be to minimize or eliminate binding as the cam followers 58, 60 ride along the non-parallel portions of the slots 40, 42 formed in the plate 32.
Viewing FIG. 4, two pistons 50, 52 are coaxial with the shaft and slidably disposed therein. The pistons 50, 52 are separated by a variable-length center chamber 54 in which a spring 56 is disposed. Two cam followers 58, 60 extend through the slots 46, 48, 40, 42 and are rigidly secured to the pistons 50, 52 by any suitable means. Annular flanges (as at 62 in FIG. 3) on the cam followers 58, 60 mechanically couple the plate 32 to the pistons 50, 52. The cam followers 58, 60 may be of any conventional construction suitable for the use described herein, and should employ bearings to eliminate friction otherwise encountered in moving along the slots 46, 48, 40, 42. An exemplary method of construction would be to provide a central cylindrical post, to provide a bearing surrounding all but an axially-extending end portion of the post, and to provide a generally cylindrical sleeve surrounding the bearing. The axially-extending end portion of the post would be press-fitted into a hole drilled in the piston, and the annular flange would be a larger-diameter integral portion of the post at the opposite end of the latter. A plate-like cover 64, suitably adapted to form a cavity 66 that accommodates movement of the cam followers 58, 60, is rigidly secured to the plate 32 in order to prevent flow through the slots 40, 42.
Referring to FIGS. 1, 2 and 4, the shaft 34 is supported across a duct 68 which defines a flow path 70, the direction of flow being indicated by the arrow 72. The shaft 34 is rotatable via bearings 74 positioned in duct bosses 76, 78. Typically, the shaft 34 is supported by a duct-member mounting body 80 to which upstream and downstream duct members 81, 83 are secured by suitable means to form the duct 68.
Referring now to FIG. 5, the outward ends 82, 84 of the pistons 50, 52 are in fluid communication with a conventional pressure regulator 86 via separate conduits 88, 90 and separate pressure chambers 92, 94, the pressure chambers being formed in part by the shaft 34. The pressure regulator 86 is in fluid communication with a source 96 of pressurized air via a conduit 98, and in electrical communication with an electronic control system 100 via wires 102. In operation, the control system 100 receives electronic sensor data (indicated by arrow 104) from a remote sensor (not shown) positioned downstream from the plate 32, the sensor data being indicative of the flow rate in the duct 68. The control system 100 also receives electronic demand data (indicated by arrow 106) from a remote control device (not shown), the demand data being indicative of the required flow rate in the duct 68. In response to the sensor and demand data 104, 106, the control system 100 communicates control signals to the pressure regulator 86, which in response thereto equally regulates air pressure in the chambers 92, 94.
Referring now to FIGS. 1-6, annular stops 108, 110 (FIG. 5) rigidly secured to the ends of the shaft 34 define null positions for the pistons 50, 52. The null position is the position at which, for a given design, the angle of rotation 38 is at its minimum. This defines a reference position of the plate 32 relative to the shaft 34. If in a given design it is necessary to fully close the valve 30, then the minimum angle of rotation is zero, as exemplified by the preferred embodiment illustrated herein. When the valve 30 is in the closed position illustrated in FIGS. 1 and 2, the pistons 50, 52 are in their null positions and the air pressure in the chambers 92, 94 is insufficient to overcome the opposing force exerted on the pistons by the spring 56. At the same time, the shaft 34 is centered in relation to the plate 32 as indicated in FIGS. 1 and 2, and the cam followers 58, 60 occupy their outermost positions in the slots 40, 42, 46, 48 as indicated in FIGS. 2 and 3. By now it will be recognized that the slots 40, 42, 46, 48 define cams along which the followers 58, 60 ride during actuation of the valve 30.
When it is desired to open the valve 30, the pressure in the chambers 92, 94 is increased to overcome the force exerted by the spring 56, and the pistons 50, 52, carrying the cam followers 58, 60, begin moving toward each other. As the cam followers 58, 60 ride along the parallel portions 44 of the slots 40, 42, they ride along associated convergent portions of the slots 46, 48 and thereby exert force on the wall 116 (FIG. 3) of the shaft 34. This causes the shaft 34 to rotate in a clockwise direction as determined by reference to FIG. 1 and, since rotation of the shaft transfers force to the walls 118 (FIG. 3) of the plate 32, causes the plate to rotate with the shaft to an open position, thereby effecting revolutionary movement of the plate relative to the longitudinal axis of the shaft. Once the plate 32 is in an open position, further pressurization of the chambers 92, 94 causes the cam followers 58, 60 to ride along the convergent, non-parallel portions of the slots 40, 42. The consequent force transferred to the walls 118 of the plate 32 results in translational movement of the plate relative to the longitudinal axis of the shaft 34. Thus, whereas the areas (indicated in a single dimension by arrows 112, 114) of the plate 32 on each side of the abutment location 36 are the same in FIG. 1, the one area 114 is greater than the other area 112 in FIG. 6. The possible range of translational movement associated with a given angle of rotation 38 is of course limited by the duct 68. However, the energy required to maintain a given angle of rotation 38 can be minimized by translating the plate 32 relative to the shaft 34 so that the center of pressure 24 (FIG. 7) acting on the former is as closely aligned with the abutment location 36 as possible, given the constraints imposed by the duct 68. Moreover, the limitations on translational movement imposed by the duct 68 can be minimized or eliminated by appropriately shaping the inside surfaces of the downstream duct member 83 and the mounting body 80.
In the illustrated embodiment parallel portions 44 of the slots 40, 42 are provided to enable initial opening of the valve 30. It will be recognized that in applications which demand a closing function, other arrangements for effecting initial opening are possible. For example, the valve 30 could be modified to provide a pilot valve or a displaceable shaft as disclosed in the above-referenced '897 application. However, it should also be recognized that the parallel portions 44, in cooperation with the cam followers 58, 60 and arcuate slots 46, 48, provide a means for rotating the combination of the shaft 34 and plate 32 in response to movement of the pistons 50, 52. Thus, if translational movement of the plate 32 relative to the shaft 34 is undesired in a particular application, the more conventional motion of simple rotation (differing from convention, however, in that the plate 32 undergoes revolutionary movement relative to the longitudinal axis of the shaft 34) can be provided by forming a single slot in the plate 32. The single slot would be parallel to the shaft 34 and sufficiently long to function as two separate cams for the followers 58, 60. Under that arrangement, although the advantages associated with translational movement are sacrificed, those associated with the positioning of actuators in the shaft are retained.
The reader should understand that the foregoing text and accompanying drawings are not intended to restrict the scope of the invention to specific details which are ancillary to the teaching contained herein. The invention should be construed as broadly as is consistent with the following claims and their equivalents. | A butterfly valve (30) is described in which the plate member (32) is in facing relationship with a hollow shaft (34) and is moved by pistons (50, 52) disposed in the shaft. The pistons (50, 52) are mechanically coupled to the plate member (32) by cam followers (58, 60) which ride along cams (40, 42, 46, 48) formed in the shaft (34) and plate member. The plate member (32) is capable of both revolutionary and translation movement relative to the longitudinal axis of the shaft (34) toward the end of minimizing the externally supplied energy required to operate the valve (30). The pistons (50, 52) collectively have a center of mass that coincides with the center of the duct (68) toward the end of minimizing vibrational effects. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the general art of static molds, and to the particular field of molding processes using static molds.
2. Discussion of the Related Art
Many people enjoy displaying theme-related items. These items can be related to a holiday, such as Christmas, or a party theme. The items range from statues to candles and food items.
Ice sculptures are popular forms of this type of display item. Ice sculptures are often displayed at parties to enhance the theme of the party. Ice sculptures can be expensive to form and thus there are only limited variations of ice sculptures available. Birds and the like are common examples of ice sculptures that are available. However, these sculptures may not be relevant to certain themes. In some instances, a theme may be dictated or influenced by the ice sculptures that are available to the planners. In other instances, the ice sculpture is so generic that it adds little or nothing to the overall theme. Holiday themes are particularly susceptible to this drawback.
Therefore, there is a need for a method of forming sculptures, such as ice sculptures, which is easy and inexpensive.
PRINCIPAL OBJECTS OF THE INVENTION
It is a main object of the present invention to provide a method of forming sculptures which is easy and inexpensive.
It is another object of the present invention to provide a method of forming sculptures, such as ice sculptures, which is easy and inexpensive.
SUMMARY OF THE INVENTION
These, and other, objects are achieved by a method that includes providing a re-usable metal form and forming temporary plastic or rubber like molds in the metal mold. Freezable liquid, such as water, is placed in the temporary mold and then frozen. Once the liquid is frozen, the temporary mold is broken away from the frozen liquid and is discarded. An electric light can be placed in the form defined when the liquid freezes for display purposes.
The temporary molds are easy to use and are inexpensive. Thus numerous different molds can be supplied whereby various themes can be supported.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
FIG. 1 is a perspective view of an ice sculpture formed in accordance with the method embodying the present invention.
FIG. 2 is a perspective view of an insert that is used to house a light in the ice sculpture shown in FIG. 1 .
FIG. 3 is a perspective view of a light that can be used in conjunction with the ice sculpture shown in FIG. 1 .
FIG. 4 is a flow chart showing the method steps embodying the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Other objects, features and advantages of the invention will become apparent from a consideration of the following detailed description and the accompanying drawings.
Referring to FIGS. 1, 2 and 3 , it can be understood that a FIG. 10, such as a Santa Claus figure, formed according to the method of the present invention, includes a base 12 having a top surface 14 , a bottom surface 16 and a side wall 18 . A concave indentation 20 is defined in bottom surface 16 for a purpose that will be understood from the following disclosure. The remainder of the bottom 16 of the base 12 is planar so the base 12 can rest on a supporting surface. A desired FIG. 22 is supported on the top surface 14 of the base 12 and extends upwardly therefrom. The desired FIG. 14 includes detailed features, such as a beard 24 , shoes 26 , or the like.
Desired FIG. 10 is formed of ice, and thus water is poured into a mold to make desired FIG. 10. A funnel 30 is indicated in FIG. 1 to show how the liquid is poured into a mold. Funnel 30 is located in a temporary mold formed according to the teaching of the present invention. The funnel 30 provides a volume into which water can move during a freezing process. Other freezable fluids, such as gels, can be used without departing from the scope of the present invention.
An insert 40 is shown in FIG. 2 . Insert 40 includes a dome-shaped cover 42 and an annular base 44 having a top surface 46 and a bottom surface 48 . The dome shaped cover 42 is accommodated in concave indentation 20 with top surface 46 of the base abutting the bottom surface 16 of the base 12 . An annular cutout can surround indentation 20 so base 44 will be received in the base 12 and bottom surface 48 will be planar with bottom surface 16 of the base 12 . This will add stability to the overall desired figure.
An electric light unit 50 is shown in FIG. 3 and includes a light bulb 52 that is secured to a base 54 with a dome-shaped cover 56 there over. Base 54 includes circuitry to electrically connect bulb 52 to a suitable power source via cable 58 . Dome 56 is sized and shaped to be snugly accommodated in dome-shaped cover 42 of insert 40 whereby the electric light bulb 52 will direct light upwardly into the desired figure. The circuitry in base 54 can include timers, and the like as well as circuitry that permits the light to flash on and off. Such circuitry is known to those skilled in the art and thus will not be discussed.
The figure for display is formed according to the following method. The method of the present invention comprises providing a metal mold having an interior surface having a desired shape in step 200 . The metal mold will have an interior surface that is shaped to correspond to the desired outer surface of the figure, such as a negative of the outer surface shown in FIG. 1. A funnel shape is defined in the metal mold in step. 202 ; a base portion corresponding to base 12 is defined in the metal mold in step 204 . A concave area corresponding to concave indentation 20 is defined in the base portion of the metal mold in step 206 . A solid resin is melted into a viscous liquid in step 208 and the viscous liquid is poured into the metal mold in step 210 . The viscous liquid is pressurized in the metal mold in step 212 , and is heated in the metal mold in step 214 . Once the liquid is at the desired consistency, the heated and pressurized viscous liquid in the metal mold is allowed to cool and harden into a solid form having a funnel therein and having an appearance corresponding to the interior surface of the metal mold in step 216 . The solid form is a plastic or rubberlike mold and has an interior surface that is a negative of the outer surface shown in FIG. 1 . The metal mold can be re-used whereas the plastic or rubberlike mold is a temporary mold. The temporary mold is sold to a customer while a manufacturer retains the metal mold.
The solid form is removed from the metal mold in step 218 . When a figure is desired, the solid form is filled with freezable liquid via the funnel in step 220 . The freezable liquid in the solid form is then frozen and forms into a desired product having an outer appearance corresponding to the appearance of the solid form in step 222 . The freezable liquid is, allowed to expand into the funnel during the freezing step in step 224 . The solid form is then broken in step 226 and the desired product is removed from the broken form in step 228 . The broken form is discarded in step 230 .
An electric light is placed in the desired product in step 232 and the desired product is displayed in step 234 . The electric light in the desired product is illuminated in step 236 .
The desired product can be the Santa Claus figure shown in FIG. 1, and the base portion of the mold will define the base shown for the figure. The concave area defined in the base portion will accommodate the insert shown in FIG. 2 and the electric light shown in FIG. 3 will be accommodated in the insert in the base of the figure. This will allow light to shine up through the figure thereby enhancing the display. Various colors of light can be used to further enhance the display as well as flashing lights. The freezable liquid used is generally water, but other gels can be used without departing from the scope of the present disclosure.
It is also noted that the exact details of the metal mold and the exact details of the temporary mold are not provided because those skilled in the molding art will understand what type of mold is required and its details based on the teaching of the present disclosure.
It is 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 arrangements of parts described and shown. | An ice sculpture is formed using a temporary mold that has been formed of plastic or rubber like material. Liquid, such as water, is poured into the temporary mold and the liquid-containing temporary mold is then frozen to form the desired shape. The temporary mold is then broken away from the desired shape and is discarded. An area which accommodates an electric light can be included in the desired shape. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 12/500,658 filed Jul. 10, 2009 and now issued as U.S. Pat. No. ______, which is a continuation of U.S. application Ser. No. 11/458,285 filed Jul. 18, 2006 and now issued as U.S. Pat. No. 7,575,163, with both applications incorporated herein by reference in their entireties.
TECHNICAL FIELD
[0002] The present disclosure is generally related to electronic communications and, more particularly, is related to interactive media.
BACKGROUND
[0003] Almost every home has a television today. With the advent of cable and satellite programming, a wide variety of channels are available on today's television sets. Further, today's technology allows media network operators to offer such services as home shopping, games, and movies on demand.
[0004] Generally, the downstream bandwidth from a content provider to a customer in television communications is large while upstream bandwidth is significantly less. Newer technologies and innovations have allowed the upstream bandwidth to become wider, thereby allowing for increased interactivity between the customer and a service provider.
[0005] In spite of the new advances, a television, like other appliances and media tools, has still remained more of a static-type of appliance that displays information, rather than a dynamic and interactive household tool that facilitates integral tasks within a household.
[0006] Thus, a heretofore unaddressed need exists in the industry to address the aforementioned deficiencies and inadequacies.
SUMMARY
[0007] Embodiments of the present disclosure provide systems and methods for interactive management of storefront purchases. Briefly described, one embodiment of the system, among others, includes a media server configured to transfer storefront interface data to a client device, where the storefront interface data enables a graphical storefront interface to be displayed on the client device. The graphical storefront interface enables a first user to communicate with the media server for the purpose of browsing graphical descriptions of items that are offered for sale. The graphical storefront interface further enables the first user to make purchases of offered items. The system further includes a profile database maintaining profile records of users of the graphical storefront interface. At least one profile record comprises a profile for an administrator of an interactive management service, where the administrator authorizes other users to participate in the service including the first user. Further, the administrator sets parameters maintained in the profile database that limit which items are displayed to the first user and offered for sale by the media server to the first user. Also, payment for items purchased by the first user are charged to the administrator.
[0008] Embodiments of the present disclosure can also be viewed as providing methods for interactive management of storefront purchases. In this regard, one embodiment of such a method, among others, can be broadly summarized by the following steps: comprising the steps of: displaying a virtual storefront guide, the virtual storefront guide enabling a first user to browse graphical descriptions of items that are offered for sale, the virtual storefront guide further enabled to allow the first user to make purchases of offered items; limiting which items are displayed to the first user and offered for sale on the virtual storefront guide in accordance with parameters defined by an administrator, the administrator authorizing the first user to participate in activities of the virtual storefront guide; and charging payment of purchases made by the first user to the administrator.
[0009] Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description and be within the scope of the present disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
[0011] FIG. 1 is a block diagram of one embodiment of an interactive management system in accordance with the present disclosure.
[0012] FIG. 2 is a diagram of an embodiment of a virtual storefront guide being displayed on a television set, such as that shown in FIG. 1 .
[0013] FIGS. 3-19 are diagrams of embodiments of interfaces to a virtual storefront guide, such as that shown in FIG. 2 .
[0014] FIG. 20 is a flow chart describing one embodiment of a method for interactive purchasing within a system, such as that shown in FIG. 1 .
[0015] FIG. 21 is a block diagram illustrating components of one embodiment of a set-top client device, such as that shown in FIG. 1 .
[0016] FIGS. 22-23 are flowchart diagrams describing embodiments of methods for interactive management of storefront purchases.
DETAILED DESCRIPTION
[0017] One embodiment of an interactive management system is shown in FIG. 1 .
[0018] The interactive management system 100 includes a media server 110 . The media server 110 is connected to a client device 160 of a user via a communications network 120 . The media server 110 is network equipment that provides the storage for media program material (e.g., video, web pages, etc.), which can be requested by a user. In a cable communications environment, the media server 110 may comprises a video server that performs many functions, such as admission control, request handling, data retrieval, guaranteed stream transmission, stream encryption, and support of functions such as pause, rewind, and fast forward. In a web environment, the media server may comprise a web server that provides Internet content.
[0019] A communication network 120 connects the media server 110 and the equipment at a customer's premise (e.g., set-top device, personal computer, etc.). In some embodiments, the interactive management system 100 involves the transfer of large volumes of data at very high speed. Also, in some embodiments, a user may utilize more than one communication network 120 to access the media server 110 . For example, a user could connect with the media server 110 utilizing the Internet to register for an interactive management service and establish profiles of authorized users that are maintained in database 115 . Then, an authorized user could access available services of the interactive management service over a cable television network.
[0020] An Asymmetric Digital Subscriber Line (ADSL) system 130 is an asymmetrical bi-directional transmission system used as the local subscriber loop between the local telephone switch and the subscriber's home, thus allowing the economical transmission of broadband services without signal regenerators. In combination with the telephone signals, which may be analogue or digital (ISDN), control (e.g., 16 and 24 kbit/s) and video (e.g., 2 to 6 Mbit/s) information channel may be transmitted downstream towards the user. In the upstream direction there are at least telephone and control channels. In some embodiments, the communication network 120 may utilize an ADSL system 130 to provide Internet-based services to a customer's premises.
[0021] A cable TV (CATV) distribution system 140 is based on a tree-and-branch topology in some embodiments and on a star topology in some others. The audio and video signals are transmitted via coaxial cables in the subscriber line area. The trunk lines are usually made by fiber. Due to the high bandwidth, it has many channels available, which are multiplexed onto the cable using Frequency Division Multiplexing (FDM). Channel transmission on the cable is primarily unidirectional. Signals are inserted on the downstream channels by a head-end.
[0022] Signals from customer sites are allowed on upstream channels and they are transmitted towards the head-end. Also, there is provision for upstream message transmission. In some embodiments, the communication network 120 may utilize a CATV distribution system 140 to provide Internet-based services to a customer's premises.
[0023] A cable head-end is the facility at a cable TV center that originates and communicates cable TV services and cable modem services to subscribers. In distributing cable television services, the head-end includes a satellite dish antenna for receiving incoming programming. When a cable company provides Internet access to subscribers, the head-end includes the computer system and databases needed to provide Internet access.
[0024] A switching office 150 includes both the telephone company's central office and the cable company's head-end. It is the place where services are fed and distributed to individual subscribers. It contains the head-end, switches, and media servers 110 . In the head-end equipment, the video streams are formatted and organized for transmission in the communication network. If ADSL 130 is used, the switching office 150 switches the video streams onto the subscriber loops with telephone calls.
[0025] A user interacts with the services by a client device 160 , such as a set-top unit or a personal computer. In one embodiment, for a set-top unit 162 , information is displayed to a user using a television display 170 , while in the case of a computer 180 , information is displayed to a user using a computer monitor 190 .
[0026] A user may be connected to a media server 110 and browse through a selection of content or services. In one embodiment, the connection is over a cable television network. In another embodiment, the connection is over the Internet. Other embodiments may employ different mediums.
[0027] One method for transmitting video is the digital video broadcasting (DVB) protocol or standard. Alternatively, an increasingly popular method of transmitting digital video is IP Television (TV) because of the numerous advantages it provides for network providers to offer video services more efficiently in certain cases. For example, IPTV is suited for programs intended for use by only one subscriber, because a minimum amount of the network is tied up to serve that need. Therefore, the number of channels that can be carried to subscribers can be significantly higher when compared to traditional video delivery systems and depending on the transmission capacity of the network and how much of that capacity is devoted to IPTV. Finally, the same data transmission capacity of a network can be used for all other data traffic.
[0028] In an embodiment employing Internet Protocol Television, the interactive management system delivers digital television service to users using the Internet Protocol over a broadband connection through technologies used for the World Wide Web. IP video signals can be received by customer premise equipment as IP multicast streams delivered from the network. To avoid sending all channel signals simultaneously, each video channel can use a specific IP multicast identification and the customer premise equipment can signal to the network which channel the user is currently viewing or requesting. The signaling information can be carried using Internet Group Management Protocol (IGMP). Therefore, when a user changes the channel, the customer premise equipment can transmit an IGMP “join” message to the network for the new channel, and it can send an IGMP “leave” message for the original channel. The signaling information for the current channel can be transmitted to an IP-enabled set-top box 162 which relays the signal to a television set 170 or to a personal computer 180 .
[0029] In one embodiment, the interactive management system 100 further includes one or more vendor clients 195 . Via the vendor clients 195 , a participating vendor or partner in the interactive management system 100 communicates with the media server 110 to program content that is distributed the users of the system. For example, in one embodiment, a vendor may be a participating restaurant that offers menu choices that are available for sale and may be displayed on a client device 160 of the user. A user may select items to purchase and the selections may be relayed to the vendor client device. Also, item selections or purchases may be tracked by the interactive management service so that appropriate billings may be made via credit card transactions or on monthly billing statements.
[0030] A wireless communication network 196 is coupled to the communications network 120 of the interactive management system 100 . Accordingly, messages may be communicated from the communications network 120 to the wireless network 196 and a wireless device 198 of a user. For example, in one embodiment, a user of the interactive management system 100 may need authorization from another user administering the service, such as a parent (administrative user or administrator), before a purchase is allowed over a television set 170 of the user. Therefore, a message, such as a short message service type of message, may be communicated from the media server 110 to the wireless device 198 of the parent requesting authorization for the purchase. These and other details are further described in the example scenarios below.
[0031] For example, consider a scenario where an eight year-old child comes home from school. Both his parents are working and are not currently at home. The child desires a meal. He turns on the family's television set 170 with the remote control unit for a set-top box 162 connected to the television set 170 and a CATV network 140 . The child presses a “Menu” button on the remote control unit that launches a virtual storefront guide 200 which is displayed on the bottom of the television set 170 , as shown in FIG. 2 . The child navigates the virtual storefront guide using arrow buttons on the remote control. For example, left and right arrow buttons can be used to navigate among the selectable channel “guide” 210 , digital video recorder (DVR) 220 , virtual “fridge” 230 , and “media closet” 240 links or icons. In this scenario, the child highlights and selects the virtual fridge option 230 .
[0032] This causes a prompt to be displayed for the user to enter his or her usercode. For example, a user profile associated with the user maintains a unique usercode associated with the user. By entering the correct usercode, the interactive management service can identify the user and can then apply rules that have been set for the user by an administrative user that established the interactive management service.
[0033] For example, in the present scenario, the user (“John”) enters the code 15933, as shown in FIG. 3 . After providing the usercode, the information is sent to the media server 110 , and the media server 110 either recognizes the usercode as being that of an authorized user or not. If the user is authorized, the media server acknowledges the user with a greeting, such as “Welcome John,” that is displayed on the user's client device 160 . Also, the identified user is presented with current settings or restrictions 410 being imposed during his or her use of the “virtual fridge,” as represented in FIG. 4 .
[0034] The virtual fridge service is a food-ordering service that is facilitated by the interactive management service. Authorized users can not only purchase prepared food items using the interactive management service, but users who have administrative privileges can establish rules for other authorized users (or themselves) as to what items may be purchased, when these items may be purchased, how much purchasing power a user is provided, how many items may be purchased, how a user can receive approval to purchase items or amounts that have not been previously approved by the administrative user, whether promotional material or advertisements are welcomed, etc. Further, such criteria may be customized for different users or set as blanket rules. In the prior examples and the examples that follow, a “virtual fridge” implementation is described. However, the concepts disclosed herein can be extended to other purchasing approaches and items, some of which are expressly disclosed herein.
[0035] Referring back to the previous scenario, John is an authorized user of the interactive management service. However, John is not the administrative user who established the service. His mother is, and John's mother has set rules regarding John's use of the virtual fridge that are maintained in profile information.
[0036] For example, each of the authorized users may have a profile that is maintained by the interactive management service. In the profile, settings, rules, and biographical information may be maintained that allow the interactive management service to know how to invoke the interactive management service to carry out requested services. For example, the address of a user is maintained in his or her profile so that a participating vendor may be provided this information when the vendor is requested to deliver a purchased item to the user.
[0037] In the present case, John's mother has allocated a daily budget of $20 for John to spend on a meal. In this way, John's mother has pre-authorized John to spend $20 so that John does not spend more the mother desires. Further, John's mother may also pre-approve from which vendors John is able to select menu items. For example, John may be allergic to some types of seafood (although he still loves the taste). Therefore, John is not authorized to shop from “SeaFood Express.” When John views the list of participating vendors, unauthorized vendors may be hidden from his view and not displayed. In some embodiments, limits 410 placed on the user may be displayed to the user, as shown in FIG. 4 .
[0038] In the present scenario, John's mother has established a pre-approved set of items that John is allowed to order without any parent intervention. Similarly, John's mother may build a pre-approved set of items for John's sister, Julie. Accordingly, when Julie identifies herself as an authorized user, the media server 110 will present items and information that conforms to requirements established by her mother. For example, Julie's mother authorizes Julie to order pizza once a week in the set of rules established for Julie. However, if Julie ordered pizza yesterday, then the interactive management service may inform Julie that she is unable to purchase pizza, as shown by pointer 510 in FIG. 5 . Further discussion regarding profile information is included in later passages, including the portion accompanying FIG. 6 .
[0039] John and Julie's mother (“Betty”) can set which menu items are available, quantity limits, number of days allowed to select item, time of day allowed to select item, individual price limits, etc. for the users that she has authorized to utilize the interactive management service. To facilitate this scenario, Betty is registered as an administrative user. Accordingly, Betty has a profile that is created by the interactive management service and stored in a database 115 . Betty's profile may also list other users that are authorized to use the service, such as Julie and John, in some embodiments (as shown in FIG. 6 ). As an administrative user, Betty can set rules and settings on other users. In the above example, Betty has established what menu items are available to be selected by Julie and John.
[0040] FIG. 6 shows one embodiment of a guide of the interactive management service for setting up profile information. In the example shown, an administrative user may access the guide over a computer 180 and select checkboxes of items that are preferred by the user by positioning a cursor over the item and using a mouse control to select the appropriate checkbox. The profile information of Betty (the administrative user) indicates a method of payment. In the present example, purchases made through the service may be automatically charged to a credit card of Betty that is stored in the service's records, as shown by pointer 610 . In some embodiments, Betty may have the option of choosing to have service charges billed on a monthly statement that is provided to her, such as her monthly cable bill. In this way, items purchased by John and Julie are automatically billed on behalf of Betty or whomever has authorized for payment.
[0041] In the example shown in FIG. 6 , other profile information indicates that Julie and John are listed as authorized users under Betty's interactive management service (see pointer 620 ). The last usage of the service occurred on Wednesday, June 3rd at 2:45 p.m. (see pointer 630 ). The address or path to send requests for authorizations of purchases is at the telephone number 555-123-3333 (see pointer 640 ), budgetary values should be refreshed on a weekly basis for authorized users (see pointer 650 ), and promotions are allowed to be received by authorized users (see pointer 655 ). To modify a current setting, an Edit link is provided next to each setting that is able to be changed. Also, links are provided for launching an interface to specify limits for Julie and John (see pointer 660 ).
[0042] For example, FIG. 7 shows an embodiment of an interface for specifying purchasing limits for John for the virtual fridge service. Accordingly, Betty may click on checkboxes next to items that she authorizes or approves John to browse and purchase items from. In the example shown, Betty authorizes John to shop from Pizza Barn and Chinese Takeout vendors (see pointer 710 ). Also, in the example shown, Betty has specified a maximum monetary limit of $15 for a food order by John (see pointer 720 ) and John can only order one meal in each order (see pointer 730 ). Further, Betty has specified that John is only able to make purchases on Monday and Tuesday of each week (see pointer 740 ). Also, Betty has not activated automatic ordering (see pointer 750 ). Therefore, if John does not place an order, an order will not automatically be placed for him on Monday and/or Tuesday.
[0043] FIG. 8 shows additional options that may be customized by the administrative user, in one embodiment. For example, an administrative user may choose which items offered for sale by a vendor is available to purchased by an authorized user. In the example shown, Betty is choosing which menu items from Pizza Barn should be made available to John when he browses the offerings of Pizza Barn using the virtual fridge interface. Here, Betty has approved John to possibly purchase an assortment of child size pizzas, dinner salad, breadsticks, small order of wings, and lemonade and water beverages (see pointer 810 ). The items not checked by Betty will not be presented to John when he browses the offerings of Pizza Barn, in some embodiments. While the embodiments illustrated in FIGS. 6-8 utilize a web-based environment to access profile information, some embodiments access profile information over other communication platforms, such as that involving the set-top unit or box 162 .
[0044] In addition to tailoring what options are available to a user, an administrative user may set a time frame for when the virtual fridge service is active and available to a user in some embodiments. For example, a dinner food menu may be available between 6-8 P.M., etc. and/or an administrative user may configure the availability of the dinner food menu to vary by day of the week for a user.
[0045] Also, in some embodiments, an administrative user is able to automatically add items to an order based no established rules. For example, a user may designate items or amounts that can be added to an order by selecting a “Add Favorites” option, for example, where certain items or amounts have been designated as being favorites by the administrative user. Alternatively, or in addition to, rules may be set up by the administrative user such that a six pack of soda always comes with the first order placed for the week, or if a pizza is ordered on a Friday, then a half gallon of ice cream is automatically ordered along with an order for a video rental.
[0046] In summarizing some of the events that have transpired in the present scenario, John has turned on the television set 170 , selected the virtual fridge icon on a virtual storefront guide, and sees the limits imposed by Betty. Certain selected vendors or companies may be shown along with what is allowed to be purchased from the companies, as shown in FIG. 4 . John selects Pizza Barn 410 by scrolling through the available options using the arrow keys of the remote control to the set-top unit 162 . In a next screen, as shown in FIG. 9 , menu items for Pizza Barn are shown that have been pre-approved by Betty. As John selects menu items, such as a child's cheese pizza, by scrolling through the items using the arrow keys of his remote control unit and pressing a “select” key on the remote control unit, the remaining money left in his daily budget is visually updated on the screen, so that John knows how much money he has left to spend (see pointer 910 ). After John finishes choosing items for his meal, John can submit his order for processing by selecting the Submit option 920 . The order is forwarded to a vendor client 195 , such as a computer at Pizza Barn's retail establishment so that it may be received and processed.
[0047] In some embodiments, it may be that John and Julie are able to view special offers or promotions by activating a link 1010 or icon on the virtual fridge interface, as shown in FIG. 10 . For example, Pizza Barn may have a special of 3 child pizzas for $10.00. However, John is only authorized to purchase one child's pizza according to parameters set up by Betty.
[0048] To purchase an item, quantity, price, etc. that has not been pre-approved, a user, such as John, can submit a request for authorization to the administrative user or whomever the administrative user has assigned to answer the request, in some embodiments. Therefore, John may select the request authorization option 1110 using the arrow keys of his remote control and pressing a select button, as represented in FIG. 11 .
[0049] The authorizing user is then sent a message to an address or path of a wireless device 198 (such as a personal digital assistant) identified in the profile record (of FIG. 6 , see pointer 640 ) over the wireless network 196 . For example, a short message service (SMS) message may be sent asking the recipient to reply with a yes or a no to a request to authorize purchase of the 3 child pizzas, as shown in FIG. 12 .
[0050] Previously, it was mentioned that some embodiments hide from view items that are not approved for purchasing by a current user. However, in some other embodiments, an authorized user is allowed to view items that have not been pre-approved by the administrative user. For example, FIG. 13 shows an interface display of menu items with an option 1310 at the bottom of the screen to view non-approved items. By selecting the option 1310 , menu items from the participating vendor are shown that have not been pre-approved by the administrative user, as shown in FIG. 14 . By specifying a quantity for one of the items and selecting the Request Approval link 1410 , a request is sent to the administrative user on to a designated address or path contained in the administrative user's profile, as described with regard to FIG. 12 . Also, if the current user's order exceeds a limit being imposed on the user, the user will be notified of the situation, as shown in FIG. 15 , and may be provided the option 1510 of requesting the administrative user to authorize the transaction.
[0051] When a reply is received by the interactive management service in response to the authorization request, the status of the order will be updated and relayed to the user whenever the user accesses the interactive management service. For example, if the request is approved, then the items will be placed in John's order and the amount of available money he has left to spend will be updated. If the request is not approved, then the items will not be placed in John's order and John will be able to select additional items.
[0052] In some embodiments, an authorized user may select in advance what items he or she would like to receive at a later date. Therefore, a user could select in advance menu items for next week or next month, for example. In some embodiments, this is a feature that may require activation by the administrative user.
[0053] In accordance with the above scenario, the interactive management service may display a reminder 1610 on a television screen or computer screen if a user has neglected to place an order for a scheduled meal and a connection is established with the media server 110 , as represented in FIG. 16 . In this way, the interactive management service can help manage items of interest for the user. Likewise, a display may be shown to remind the user of what purchased items are scheduled to be delivered to the user.
[0054] Also, in some embodiments, the media server 110 may push alerts to a user via the set-top box 162 or a cell phone to prompt the user that it is meal time and the user needs to place an order. Further, in an embodiment, where an alert appears on a television screen, icons may also be displayed to allow for quick navigation to the portion of the storefront guide interface that allows for ordering of the item that is the subject of the alert (e.g., virtual fridge).
[0055] Advantageously, an administrative user, such as a parent, may arrange for a variety of budgetary methods to be used during utilization of the interactive management service by the users authorized to access the interactive management service. For example, the administrative user may limit another user's spending in accordance with a weekly amount. For example, in the above scenario, John may be limited to spending a $100 per week on meals and it is up to John to determine how that money is spent. Therefore, if John only has $5 left on the last day of the current week, than John has likely learned a lesson in budgetary spending and responsibility. Accordingly, an administrative user may set budgetary limits that provide degrees of discretionary or nondiscretionary control (e.g., $100/week versus $10/day). Further, in some embodiments, a hybrid plan may be employed where a user is provided a daily amount for certain items (some discretionary control), such as main course items and a weekly amount for other items (more discretionary control), such as dessert items. In this way, a user may be able to spend $8/week on dessert items, such as ice cream or candy.
[0056] In some embodiments, users may register themselves or other users with certain meal plans. In this way, participating vendors can target packages fitting the plan of the user. For example, if a user is in a kid's meal plan, then meals targeted toward “kids” are offered by participating vendors. Likewise, if a user is in a “diet plan,” then low-calorie meals may be targeted to the user. Also, if a user is in a “budget plan” then low-priced meals may be targeted to the user. One of the benefits for a vendor is that they can market meals (or items in general) to users that have been pre-approved to spend a set budget.
[0057] In this way, an administrative user, such as a parent, can set controls on what items may be purchased, on what limits on purchase amounts are imposed, and on what payment methods are allowed or instituted. Authorized users act as proxies for the administrative user in making purchases on the behalf of the administrative user, and the administrative user institutes control measures on what purchases he or she allows to be made. Likewise, the administrative user may elect to place controls and limits on items that are selected to be purchased by the administrative user himself or herself. Also, in accordance with subscribing to plans of services, an authorized user may upgrade to a plan that allows for additional services or an increased limit on what services are available or downgrade to a plan that has reduced services or a reduced limit on what services are available.
[0058] Referring back to the scenario with John coming home and his parents away at work, Betty may arrange for a meal to be automatically ordered if John neglects to select his meal for the day, in some embodiments. As previously mentioned, this information may be maintained in a profile for John. Therefore, rules may be specified that indicate if John has not provided a menu selection by 5 p.m., the interactive menu service should automatically select a meal for John from one of the available pre-approved menu items, in one embodiment. Alternatively, Betty may specify a default menu item, such as a hamburger (John's favorite food), that is to be automatically ordered.
[0059] Also, an authorized user's pre-approved payment limit or quantities may be automatically set to be refreshed on a periodic basis (e.g., every week, month) or may be set to be refreshed manually. For example, at the end of a week, John may be out of money in his budget that allocated by his mother for use on the virtual fridge. Betty, as administrative user, may specify in John's profile that the budget should be “refreshed” automatically, such that at the beginning of the next week, the budget is returned to its initial value. Alternatively, Betty may specify that the budget amount should be refreshed or modified manually, since she may not want John to regularly make meal purchases using the interactive management service.
[0060] In some embodiments, participating vendors may track which of their items are being ordered by users and then present special packages or offers to users that fit the criteria of a user's current limits, budgets, or plans and ordering trends. Additionally, if a television advertisement for a participating vendor is being shown on the television set 170 for Pizza Barn, a message 1710 may also be displayed on the screen indicating that Pizza Barn is a featured vendor in the user's virtual fridge, as represented in FIG. 17 . In embodiments where a user accesses the virtual storefront guide using a web browser, instead of television commercials or advertisements, Internet advertisements may cause a message to be displayed prompting a user to visit the storefront to view items of a vendor that is also the subject of an Internet advertisement.
[0061] Embodiments of the present disclosure are not limited to only having a virtual fridge and related items being offered by the interactive management service. For example, a “virtual storefront” of items, services, and vendors may be available for browsing and purchasing, as represented in FIG. 2 . In a similar manner as a meal may be purchased by a user, a user may also browse for videos to rent or purchase, music to rent or purchase, games to rent or purchase, shop for tickets to movies, concerts, and other items of interest, which are depicted as being part of the “Media Closet” 240 of the virtual storefront 200 interface or guide. Accordingly, an administrative user may specify in a profile of authorized users, limits or criteria on which items may be purchases and on what amount may be spend on these items. Accordingly, certain categories of items (e.g., music versus meals) may have different rules or limits specified. Also, depending on the type of item, certain limits may be applicable across item type or category or may be applicable to a particular item type or category. For example, limits for music may be selected based on music genre (e.g., rap, rock, pop, etc.) and content ratings (e.g., contains explicit lyrics, does not contain explicit lyrics) that are not applicable to meal items. Further, a video game may be able to be purchased, downloaded to a set-top box 162 (or computer 180 ), but not able to be played until the administrative user gives approval. Approval may then be provided at the set-top box 162 or computer 180 where it is to be played or may be remotely provided by a wireless device in a similar manner, as previously described with regard to selecting a non-approved item in the virtual fridge scenario and subsequently receiving approval or authorization for the administrative user.
[0062] The administrative user may also decide to blanketly or across the board allow or prohibit promotions or advertisements to be received for each service (e.g., meals, music, movies/videos, etc.) offered in the virtual storefront interface, as denoted by pointer 655 in FIG. 6 .
[0063] While many of the examples discussed above have been explained in a context using a television set 170 , it is contemplated that these examples may also be extended to a context utilizing a computer 180 communication via the Internet. For example, a computer 180 may communicate with a media server 110 and purchase and receive items, such as meals, movies/videos, music, etc. that satisfy criteria maintained in a user profile, as described above. It is contemplated that a computer 180 may be employed by a user in a similar manner as a set-top unit 162 and television set 170 , in the examples above, in one or more embodiments.
[0064] Accordingly, FIG. 18 shows an embodiment of a virtual storefront guide that is accessed using a web browser. In this example, John has accessed a video storefront. For the video storefront, John has been pre-approved to order G-rated movies; videos that have been selected for the age range of 7-9 years old; and may order one video per day (see pointer 1810 ). Also, John is restricted from viewing video titles that have been classified as involving sword and sorcery. Accordingly, FIG. 18 shows a portion of the titles that are available to be viewed by John (see pointer 1820 ), in accordance with the viewing and purchasing limits established by the administrative user, his mother. FIG. 19 shows a corresponding representation of the virtual storefront guide being displayed on a television set 170 , in one embodiment.
[0065] Referring now to FIG. 20 , one embodiment of a method for interactive purchasing is described. The method or process is illustrated as a set of operations shown as discrete blocks. The process may be implemented in any suitable hardware, software, firmware, or combination thereof The order in which the operations are described is not to be construed as a limitation. At block 2010 , a first user registers for interactive management service and creates an administrative profile. Information in this profile is used to govern operation of the interactive management service, such as approved payment method, identification of authorized users, designation of approved use of the service (e.g., authorized days and time), designation of whether promotions are allowed to be viewed by authorized users, monetary purchasing limits for authorized users, indication of whether users can request for authorization to purchase non-approved items or amounts, etc. Accordingly, the first user identifies or designates a second user as an authorized user of the service and a profile is created for the second user. For the profile of the second user, the first user specifies limits on the items that can be purchased by the second user, in block 2020 .
[0066] The second user accesses the interactive management service ( 2030 ) and authenticates ( 2040 ) himself or herself as an authorized user. Upon recognition of the second user, the service imposes the limits specified by the first user, as shown in block 2050 . Therefore, when the second user selects an item being offered for sale on the virtual storefront and the item is added to the order of the second user, limits for the order are updated. For example, if the second user is limited to purchasing one item, then this information is met with the addition of the item to the order and is displayed to the second user. Accordingly, authorized limits are tracked ( 2060 ) by the service and displayed to the second user so that the second user knows how he or she stands in regard to complying with these limits. In some embodiments, the second user may request ( 2065 ) authorization from the first user for performing an action that is being prohibited by the prescribed limits. If authorization is granted, then the attempted action is allowed to be performed. Likewise, if authorization is not granted, the attempted action is not allowed to be performed.
[0067] In some embodiments, promotional items are presented to the second user that are in compliance with the prescribed limits. In this way, promotional items may only be delivered to a user if they meet the user's prescribed limits. This is advantageous to both the user and the advertiser, since the advertiser is targeting ads to users who are capable of using the advertisement and the user is being shown advertisements that the user is able to act upon.
[0068] The interactive management service may also provide ( 2070 ) for advance ordering by the second user. Accordingly, the second user browses the available options and places an order with the interactive management service. The interactive management service then provides ( 2075 ) reminders of scheduled services to the second user. Also, the interactive management service may remind ( 2076 ) the second user of unfulfilled scheduled services.
[0069] For example, the second user or the first user on behalf of the second user may schedule for services to be specified by the second user. For instance, the second user may be expected to specify a movie to rent for each month, as part of a movie rental service. Accordingly, at or near the end of a current month, the second user may be reminded that he or she is expected to specify a movie for rent.
[0070] Also in concert with other information being provided by a participating vendor of the interactive management service, prompts may be presented ( 2080 ) to the second user as to items or services that are available for purchase by the second user as part of the interactive management service. Purchased items and services by the second user are billed to the first user.
[0071] Referring back to FIG. 1 , in various embodiments, client devices 160 can be implemented in any number of ways. For example, a client device 160 may be implemented as a personal computer, where the personal computer 180 is coupled to a monitor 190 for presenting interactive management service data received by the client device. Client device 160 may also be coupled to receive data over network 120 and render the received data using associated television 170 and set-top box 162 .
[0072] In some embodiments, a client device runs a virtual storefront guide application that utilizes a data file received from the media server 110 to generate a virtual storefront interface, described above.
[0073] FIG. 21 illustrates selected components of a set-top client device 2110 that is configured to generate a virtual storefront guide or interface. Client device 2110 includes one or more tuners 2120 . Tuners 2120 are representative of one or more tuners (e.g., in-band tuners) that tune to various broadcast or on-demand channels to receive media content. Tuners 2120 are also representative of a tuner (e.g., an out-of-band tuner) that tunes to a channel over which a data file may be received from media server 110 . Alternatively, tuners 2120 may represent an application and/or network connection that enables client device 2110 to receive data over another type of network over which media content can be transmitted, such as an IP based network.
[0074] Client device 2110 also includes one or more processors 2130 and one or more memory components. Examples of possible memory components include a random access memory (RAM) 2140 , a disk drive 2150 , a mass storage component 2160 , and a non-volatile memory 2170 (e.g., ROM, Flash, EPROM, EEPROM, etc.). Alternative implementations of client device 2110 can include a range of processing and memory capabilities, and may include more or fewer types of memory components than those illustrated in FIG. 21 . For example, full-resource clients can be implemented with substantial memory and processing resources, including the disk drive 2150 to store content for replay by the viewer (e.g., a client device that includes a digital video recorder).
[0075] Processor(s) 2130 process various instructions to control the operation of client device 2110 and to communicate with other electronic and computing devices. The memory components (e.g., RAM 2140 , disk drive 2150 , storage media 2160 , and non-volatile memory 2170 ) store various information and/or data such as media content, interactive management data, configuration information for client device 2110 , and/or graphical user interface information.
[0076] An operating system 2180 and one or more application programs 2190 may be stored in non-volatile memory 2170 and executed on processor 2130 to provide a runtime environment. A runtime environment facilitates extensibility of client device 2110 by allowing various interfaces to be defined that, in turn, allow application programs 2190 to interact with client device 2110 . In the illustrated example, a virtual storefront application 2195 is stored in memory 2170 to operate on a received file from the interactive management server to generate a virtual storefront guide.
[0077] Client device 2110 also includes a decoder 2115 to decode a broadcast video signal, such as an NTSC (National Television Signal Committee), PAL (Phase Alternating Line), SECAM (Séquentiel couleur à mémoire or “Color Sequential with Memory”) or other TV system video signal. Client device 2110 further includes a wireless interface 2125 , a network interface 2135 , a serial and/or parallel interface 2145 , and a modem 2155 . Wireless interface 2125 allows client device 2110 to receive input commands and other information from a user-operated input device, such as from a remote control device or from another infrared, Bluetooth, or similar radio frequency (RF) input device.
[0078] Network interface 2135 and serial and/or parallel interface 2145 allow client device 2110 to interact and communicate with other electronic and computing devices via various communication links (e.g., media server 110 via network 120 ). Client device 2110 may also include other types of data communication interfaces to communicate with other devices. Modem 2155 facilitates communication between client device 2110 and other electronic and computing devices via a conventional telephone line.
[0079] Client device 2110 also includes an audio output 2175 and a video output 2185 that provide signals to a television or other display device that processes and/or presents or otherwise renders broadcast or on-demand programs. Although shown separately, some of the components of client device 2110 may be implemented in an application specific integrated circuit (ASIC). Additionally, a system bus (not shown) typically connects the various components within client device 2110 . A system bus can be implemented as one or more of any of several types of bus structures, including a memory bus or memory controller, a peripheral bus, an accelerated graphics port, or a local bus using any of a variety of bus architectures. By way of example, such architectures can include an Industry Standard Architecture (ISA) bus, a Micro Channel Architecture (MCA) bus, an Enhanced ISA (EISA) bus, a Video Electronics Standards Association (VESA) local bus, and a Peripheral Component Interconnects (PCI) bus also known as a Mezzanine bus.
[0080] General reference is made herein to one or more client devices, such as client device 2110 . As used herein, “client device” means any electronic device having data communications, data storage capabilities, and/or functions to process signals, such as broadcast signals, received from any of a number of different sources. In one implementation, functionality of the client device may be distributed such that one device, for example a personal computer 180 , renders the virtual storefront guide or interface.
[0081] Referring now to FIG. 22 , one embodiment of a method for interactive management of storefront purchases is depicted in a flow chart diagram. The flow chart begins with a process of displaying ( 2210 ) a virtual storefront guide—the virtual storefront guide enabling a first user to browse graphical descriptions of items that are offered for sale, the virtual storefront guide further enabled to allow the first user to make purchases of offered items. The method further includes limiting ( 2220 ) which items are displayed to the first user and offered for sale on the virtual storefront guide in accordance with parameters defined by an administrator, the administrator authorizing the first user to participate in activities of the virtual storefront guide; and charging ( 2230 ) payment of purchases made by the first user to the administrator.
[0082] Next, in FIG. 23 , an embodiment of a method for interactive management of storefront purchases is described in a flow chart diagram. Here, an administrative user is enabled ( 2310 ) to designate rules on which items are allowed to be purchased through an interactive storefront system and on which users are allowed to participate in the system. Accordingly, when a user attempts to participate in the system, the system enforces ( 2320 ) the rules set by the administrative user. The method further includes the step of charging ( 2330 ) the administrative user for any purchases made using the system that are in accordance with the rules established by the administrative user.
[0083] As previously discussed, embodiments of the present disclosure can be implemented in hardware, software, firmware, or a combination thereof. System components may be implemented in software or firmware that is stored in a memory and that is executed by a suitable instruction execution system. If implemented in hardware, components can be implemented with any or a combination of the following technologies, which are all well known in the art: a discrete logic circuit(s) having logic gates for implementing logic functions upon data signals, an application specific integrated circuit (ASIC) having appropriate combinational logic gates, a programmable gate array(s) (PGA), a field programmable gate array (FPGA), etc.
[0084] If implemented in software, instructions for implementing logical functions, can be embodied in any computer-readable medium for use by or in connection with an instruction execution system, apparatus, or device, such as a computer-based system, processor-containing system, or other system that can fetch the instructions from the instruction execution system, apparatus, or device and execute the instructions. In the context of this document, a “computer-readable medium” can be any means that can contain, store, communicate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device. The computer readable medium can be, for example but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, or device. More specific examples (a nonexhaustive list) of the computer-readable medium would include the following: an electrical connection (electronic) having one or more wires, a portable computer diskette (magnetic), a random access memory (RAM) (electronic), a read-only memory (ROM) (electronic), an erasable programmable read-only memory (EPROM or Flash memory) (electronic), an optical fiber (optical), and a portable compact disc read-only memory (CDROM) (optical). In addition, the scope of the present disclosure includes embodying the functionality of the embodiments of the present disclosure in logic embodied in hardware or software-configured mediums.
[0085] Any process descriptions or blocks in flow charts should be understood as representing modules, segments, or portions of code which include one or more executable instructions for implementing specific logical functions or steps in the process, and alternate implementations are included within the scope of the preferred embodiment of the present disclosure in which functions may be executed out of order from that shown or discussed, including substantially concurrently or in reverse order, depending on the functionality involved, as would be understood by those reasonably skilled in the art of the present disclosure.
[0086] Conditional language, such as, among others, “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments could include, but do not require, certain features, elements and/or steps. Thus, such conditional language is not generally intended to imply that features, elements and/or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without user input or prompting, whether these features, elements and/or steps are included or are to be performed in any particular embodiment.
[0087] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiments without departing substantially from the spirit and principles of the present disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure. | Electronic commerce is enhanced for customer convenience. When an online order is received, a profile may be checked. A customer may her profile with items that are automatically added to the online order. Food and beverages, for example, may be items that are frequently consumed and thus automatically added to any online order. Electronic commerce may thus be enhanced to restock items that are frequently purchased. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application is a continuation-in-part application of U.S. patent application Ser. No. 10/412,390 and claims priority to U.S. patent application Ser. No. 10/412,390, filed Apr. 14, 2003, now U.S. Pat. No. 6,882,817, in the United States Patent and trademark Office, and Japanese patent applications, Nos. JPAP 2002-110525 filed on Apr. 12, 2002, and JPAP 2003-38211 filed on Feb. 17, 2003, in the Japanese Patent Office. The entire contents of these documents are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to an image forming method and apparatus, and more particularly to an image forming method and apparatus which includes an easy-to-handle large capacity toner container.
Conventionally, an electrophotographic image forming apparatus uses a development mechanism which develops an electrostatic latent image formed on an image carrying member into a visual image. In particular, an electrophotographic image forming apparatus using a two-component developer for the development mechanism adopts a specific structure in which a toner storage such as a toner bottle, a toner cartridge, a toner tank, and the like is arranged close to the development mechanism and toner is transported with a transportation mechanism such as an auger.
In addition, an electrophotographic image forming apparatus provided with a color capability as a recent trend has four development mechanisms with four toner storages for colors of yellow, magenta, cyan, and black.
It is a general requirement for such an image forming apparatus to have a compact size without sacrificing a capacity of the toner storage. However, the toner storage is needed to be arranged close to the development mechanism in an engine of the image forming apparatus and therefore the reduction in size of the engine is constrained. Accordingly, flexibility of a machine design itself is interfered.
Japanese Laid-Open Patent Application Publication, No. 2001-305843, describes an image forming apparatus which has a toner storage arranged in a separate unit from a development mechanism since the toner contained in the toner storage is transported to the development mechanism with a screw pump called a mohno-pump.
Generally, an image forming apparatuses capable of performing functions of copying, printing, and facsimile, for example, has a relatively large machine size and, in such an apparatus, a dead space (i.e., unutilized space) may often be found underneath an operation panel thereof. If a toner storage is placed in this dead space, a large amount of toner can be stocked in the apparatus without the needs of further enlarging the machine size. However, since the top of this dead space is covered by the operation panel, an exchange of the toner storage is not easily performed.
BRIEF SUMMARY OF THE INVENTION
In view of the foregoing, it is an object of the present invention to provide a novel image forming apparatus which can store a large capacity of toner without sacrificing exchangeability of a toner storage.
Another object of the present invention is to provide a novel image forming method which can store a large capacity of toner without sacrificing exchangeability of a toner storage.
To achieve the above-mentioned object, in one example, a novel image forming apparatus includes a development mechanism, a toner storage, and a toner transportation mechanism. The development mechanism is configured to develop an electrostatic latent image formed on an image carrying member into a visual image. The toner storage is detachably installed in the apparatus and is configured to store toner therein. The toner transportation mechanism is configured to transport the toner from the toner storage to the development mechanism. In this apparatus, the toner storage is movable together with at least a part of the toner transportation mechanism between a closed position which is a normal position of the toner storage containing toner and a tilt position at which the toner storage is exchanged with a new toner storage.
The toner transportation mechanism may include a flexible tube for transporting the toner from the toner storage to the development mechanism.
The toner transportation mechanism may include a screw pump including an elastic stator internally having spiral grooves in a two-screw shape and a rotor rotating inside the stator to transport the toner in an axis direction, and the toner is transported to the development mechanism by an action of a negative pressure generated by the screw pump.
The toner storage may be movable between the closed position and the tilt position by a rotational movement.
The flexible tube may be arranged near a rotation shaft of the toner storage.
The flexible tube may include at least two tube portions joined with a connector arranged near the rotation shaft of the toner storage.
At least one of the above-mentioned at least two tube portions included in the flexible tube may be made of a material different from materials of the others.
To achieve the above-mentioned object, in one example, a novel image forming method includes the steps of providing, setting, storing, and transporting. The providing step provides a development mechanism developing an electrostatic latent image into a visual image with toner. The setting step sets a toner transportation mechanism. The storing step stores toner in a detachable toner storage. The transporting step transports the toner with the toner transportation mechanism from the detachable toner storage to the development mechanism. In this method, the detachable toner storage is movable together with at least a part of the toner transportation mechanism between a closed position which is a normal position of the detachable toner storage containing toner and a tilt position at which the detachable toner storage is exchanged with a new detachable toner storage.
The toner transportation mechanism may include a flexible tube for transporting the toner from the detachable toner storage to the development mechanism.
The toner transportation mechanism may include a screw pump including an elastic stator internally having spiral grooves in a two-screw shape and a rotor rotating inside the stator to transport the toner in an axis direction, and the toner is transported to the development mechanism by an action of a negative pressure generated by the screw pump.
The detachable toner storage may be movable between the closed position and the tilt position by a rotational movement.
The flexible tube may be arranged near a rotation shaft of the detachable toner storage.
The flexible tube may include at least two tube portions joined with a connector arranged near the rotation shaft of the detachable toner storage.
At least one of the above-mentioned at least two tube portions included in the flexible tube may be made of a material different from materials of the others.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
A more complete appreciation of the disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
FIG. 1 is a schematic diagram of a color copying apparatus according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic diagram of a major portion of a color copying engine included in the color copying apparatus of FIG. 1 ;
FIG. 3 is a part of the major portion of the color copying engine shown in FIG. 2 with an enlargement;
FIG. 4 is a schematic diagram of a toner replenishing mechanism included in the color copying apparatus of FIG. 1 ;
FIG. 5 is a schematic diagram of a toner replenishing mechanism including a powder pump and a sub-hopper;
FIG. 6 is a top view of an upper chamber of the sub-hopper;
FIG. 7 is a top view of a lower chamber of the sub-hopper;
FIG. 8 is a schematic diagram for showing a tilt position of an enclosure for toner containers in association with the toner replenishing mechanism;
FIG. 9 is a schematic diagram of a jointed toner transportation tube for the toner replenishing mechanism; and
FIG. 10 is a schematic diagram showing an exemplary structure of the enclosure for the toner containers;
FIG. 11 is a diagram of a toner replenishing mechanism for replenishing the development unit of an image forming unit with toner;
FIG. 12 is a diagram of a toner container which includes the toner sack and the toner discharging unit;
FIG. 13 is a schematic diagram showing a toner discharging unit which includes an upper main body and a lower main body;
FIG. 14 is another diagram showing the toner discharging unit which includes the upper main body and lower main body;
FIG. 15 is yet another diagram showing the toner discharging unit which includes the upper main body and lower main body;
FIG. 16 is a schematic diagram showing an image forming apparatus which includes an enclosure to which the toner container having four toner folders is attached;
FIG. 17 is a diagram showing an open and close folder of the enclosure;
FIG. 18 is a diagram showing the enclosure which includes the open and close folder which has the separated toner container;
FIG. 19 is a diagram showing the enclosure which is pulled out with the handle;
FIG. 20 is a diagram showing a nozzle and a slider;
FIG. 21 is a diagram showing another exemplary enclosure;
FIG. 22 is another diagram showing the enclosure shown in FIG. 21 ;
FIG. 23 is a diagram showing yet another exemplary enclosure; and
FIG. 24 is a diagram showing another exemplary toner replenishing mechanism.
DETAILED DESCRIPTION OF THE INVENTION
In describing the exemplary embodiments illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the disclosure of this patent specification is not intended to be limited to the specific terminology so selected and it is to be understood that each specific element includes all technical equivalents that operate in a similar manner.
Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views, particularly to FIG. 1 , a color copying apparatus 1 is explained, which is one example of a color image forming apparatus according to a preferred embodiment of the present invention. The color copying apparatus 1 forms an image using an electrophotographic method and, as shown in FIG. 1 , includes a color copying engine 100 at the middle, a sheet supply station 200 at the bottom, and an image scanner 300 at the top of the color copying apparatus 1 with an automatic document feeder (ADF) 400 on top. In addition, the color copying apparatus 1 is also provided with an operation panel 120 in front of and in an integrated form with the image scanner 300 . Those skilled in the art will recognize that the above components may be located at alternative positions within the apparatus in addition to those mentioned above.
The color copying engine 100 is provided with a tandem mechanism 10 including four image forming units 11 arranged horizontally for black (Bk), cyan (C), magenta (M), and yellow (Y) colors. Each of the four image forming units 11 includes a photosensitive drum 12 which serves as a primary image carrying member for carrying a latent image formed thereon. Around the photosensitive drum 12 , various requisite mechanisms for the electrophotographic process, as explained herein.
Below the tandem mechanism 10 , an intermediate transfer belt 13 is extended under a predetermined tension among a plurality of rollers 14 , 15 , and 16 , and is arranged to contact the four photosensitive drums 12 . The intermediate transfer belt 13 includes a flexible endless belt and serves as a secondary image carrying member for carrying a toner image. One of the rollers 14 , 15 , and 16 is driven to rotate the intermediate transfer belt 13 clockwise, as indicated by an arrow. Other rollers which are not directly driven follow the rotation.
The color copying engine 100 is further provided with four primary image transfer units 17 which contact an inside surface of the intermediate transfer belt 13 at positions to face the respective photosensitive drums 12 via the intermediate transfer belt 13 . Reference numeral 18 denotes a cleaning unit for removing unused toner particles from the intermediate transfer belt 13 .
Above the tandem mechanism 10 , an exposure unit 19 for sequentially irradiating each of the photosensitive drums 12 with an optically-modulated laser beam is provided. The exposure is performed at an area after a charging process and before a development process. Instead of the single exposure unit 19 , four separate exposure units may be provided to be used on a one-to-one basis relative to each of the photosensitive drums 12 . In the exemplary embodiment, the single exposure unit 19 is utilized to decrease cost.
Underneath the intermediate transfer belt 13 , a secondary image transfer unit 22 is provided. The secondary image transfer unit 22 includes a secondary image transfer belt 24 which is an endless belt and is extended between two rollers 23 . The secondary image transfer unit 22 is arranged such that a portion of the secondary image transfer belt 24 close to one of the rollers 23 presses the intermediate transfer belt 13 against the roller 16 . Near the other one of the rollers 23 and below the roller 15 , a fixing unit 25 for fixing a toner image carried by and on a recording sheet is provided.
The secondary image transfer unit 22 further includes a sheet transport mechanism for transporting a recording sheet carrying a toner image thereon to the fixing unit 25 . As an alternative to the secondary image transfer unit 22 , a non-contact charging unit may be used. With such a non-contact charging unit, a mechanism for transporting a recording sheet carrying a toner image thereon to the fixing unit 25 may be installed separately.
The color copying engine 100 is further provided with a pair of sheet ejection rollers 26 for ejecting a recording sheet carrying a toner image fixed thereon and an output tray 27 for storing recording sheets output from the color copying engine 100 .
The color copying engine 100 is further provided with a sheet flipping unit 28 for flipping a recording sheet having a front surface already printed so as to print an image on a back side of the recording sheet in a dual surface copying mode. The sheet flipping unit 28 is arranged under the secondary image transfer unit 22 and the fixing unit 25 .
When a color copying is performed with the color copying apparatus 100 , a set of originals are placed in a face-up orientation on an original input stacker 30 of the ADF 400 . Alternatively, the set of originals can manually be placed sheet by sheet directly on a contact glass 31 of the image scanner 300 . To do this, the ADF 400 is lifted up since it has a shell-like openable structure and, after the placement of the original, the ADF 400 is lowered to a closing position.
Then, upon a depress of a start switch (not shown), when the set of originals are placed on the ADF 400 , an uppermost original of the set of originals is separated and is transported with a sheet transportation mechanism 32 of the ADF 400 to the contact glass 31 of the image scanner 300 and, subsequently, the image scanner 300 is activated. That is, first and second moving units 33 and 34 of the image scanner 300 slide in a predetermined direction. When the original is manually set on the contact glass 31 , the image scanner 300 is immediately activated upon the depress of the start switch. The first moving unit 33 that carries a light source and a mirror (both not shown) causes a light irradiation to move and reflects the light reflected by the original on the contact glass 31 . The second moving unit 34 carrying mirrors (not shown) receives the light reflected by the mirror of the first moving unit 33 and reflects the light to a read sensor 35 via an image forming lens 36 .
Also, upon the depress of the start switch, the image forming units 11 are activated to form mono-color images in black, yellow, magenta, and cyan on the respective photosensitive drums 12 in the tandem mechanism 10 . At the same time, the intermediate transfer belt 13 starts to rotate and sequentially receives the mono-color images at a same position thereof, thereby forming a composite color image.
Further, upon the depress of the start switch, one of sheet supply rollers 42 of the sheet supply station 200 is started to rotate so that a blank recording sheet is moved to a separation roller 45 in a corresponding sheet stocker 44 among a plurality of sheet stockers 44 provided to a sheet bank 43 . The separation roller 45 separates the recording sheet from the following sheets and transfers it to a transportation passage 46 . Then, the recording sheet is moved to a transportation passage 48 provided to the color copying engine 100 by a plurality of transportation rollers 47 . The recording sheet is then stopped by a pair of registration rollers 49 .
When a manual insertion is used, a transportation roller 50 is rotated to move a set of recording sheets placed on a manual insertion tray 51 to a pair of separation rollers 52 . Then, the pair of separation rollers 52 separate an uppermost recording sheet from the rest of the recording sheets and transfers it to the pair of registration rollers 49 through a transportation passage 53 .
After that, the pair of registration rollers 49 are started to rotate in synchronism with the movement of the composite color image carried on the intermediate transfer belt 13 and consequently the recording sheet which is blank is inserted between the intermediate transfer belt 13 and the secondary image transfer unit 22 . The composite color image is transferred at one time from the intermediate transfer belt 13 onto the recording sheet by the action of the secondary image transfer unit 22 .
After the image transfer, the secondary image transfer unit 22 transports the recording sheet having the composite color image to the fixing unit 25 which then fixes the color image to the recording sheet with heat and pressure. Then, the recording sheet passes through an ejection passage selected by a switch pawl 55 and is ejected to the output tray 27 by the pair of sheet ejection rollers 26 . As an alternative, the recording sheet may be headed to the sheet flipping unit 28 by selecting a transportation passage for the dual surface copying mode with the switch pawl 55 . In this case, the recording sheet is flipped by the sheet flipping unit 28 and is then transported again to the pair of registration rollers 49 in a face-down orientation. Then, the recording sheet is caused again to pass through the passage between the intermediate transfer belt 13 and the secondary image transfer unit 25 to receive a composite color image on the back surface thereof. After that, the recording sheet with the front and back sides printed passes through the ejection passage selected by the switch pawl 55 and is ejected to the output tray 27 by the pair of sheet ejection rollers 26 .
After the image transfer, the intermediate transfer belt 13 further moves to undergo a cleaning of unused toner particles by the cleaning unit 18 and to become ready for a next image transfer process.
FIG. 2 shows a major portion of the color copying engine 100 in the color copying apparatus 1 . As indicated in FIG. 2 , in the tandem mechanism 10 , the four image forming units 11 for the colors of Y, M, C, and Bk are arranged in this order in the exemplary embodiment from an upstream side to a downstream side in a moving direction of the intermediate transfer belt 13 in a horizontal area between the rollers 14 and 15 where the four image forming units 11 contact the intermediate transfer belt 13 . With this order, a “first copy time” of a copying operation in black can be shortened by a time period corresponding to a length from the most upstream photosensitive drum 12 for the color Y to the most downstream photosensitive drum 12 for the color Bk.
FIG. 3 enlarges the image forming units 11 for the colors of C and Bk, for example, as a portion of the tandem mechanism 10 . As shown in FIG. 3 , in the image forming unit 11 for the color of C, for example, the photosensitive drum 12 is surrounded by a charging unit 56 , a development unit 60 , the secondary image transfer unit 17 , a cleaning unit 58 , and a discharging unit 59 . A laser light beam L runs to the photosensitive drum 12 between the charging unit 56 and the development unit 60 .
FIG. 4 shows a toner replenishing mechanism for replenishing the development unit 60 of the image forming unit 11 with toner. In FIG. 4 , a toner container 80 contains toner which is transferred to the development unit 60 . This toner container 80 is enclosed by an enclosure 110 (see FIG. 8 ) of the color copying engine 100 . The enclosure 110 is provided with a nozzle 90 which is inserted into the toner container 80 . When the toner container 80 is exchanged and a new one is inserted downwardly into the enclosure 110 , the nozzle 90 is inserted upwardly into the new toner container 80 . The nozzle 90 has a tubular structure and is provided with an upper end 91 in a cone-like shape having a pointed top. The upper end 91 is integrated with the nozzle 90 or is adhered to the nozzle 90 . The nozzle 90 is provided with an opening 92 for exchanging air and taking in the toner at a position below the upper end 91 . The nozzle 90 includes a passage 93 connected to the opening 92 and which is provided with a connection end 94 for connecting a toner transportation tube 85 for transporting toner therethrough. The passage 93 is also provided with an air inlet 95 at a position above the connection end 94 .
In this embodiment, an air pump 96 is connected to the air inlet 95 with an air transportation pipe 97 . When the air pump 96 is in operation, it discharges the air in a confined jet to inside the toner container 80 from the bottom via the air transportation pipe 97 and the passage 93 . The jet air entered inside the toner container 80 agitates the toner and fluidizes the toner in the toner container 80 .
The toner container 80 includes an external case 81 serving as a protection cover and a toner sack 82 stored inside the external case 81 . The toner sack 82 is flexible and exchangeable. The external case 81 is made of a rigid paper material such as a corrugated cardboard or a plastic material, for example, and has an internal space for storing the toner sack 82 . The thus-structured toner container 80 is an easy-to-handle container since the flexible toner sack 82 is protected from an external impact with the external case 81 .
The toner sack 82 is made of at least one flexible sheet material such as a polyester film, a polyethylene film, or the like having a thickness of the order of from about 80 μm to 125 μm. The toner sack 82 has an opening with a ring-shaped portion 83 at a bottom center thereof for discharging the toner. The ring-shaped portion 83 is made of plastic such as polyethylene, nylon, or the like. The opening with the ring-shaped portion 83 is provided with a seal 84 serving as a self-closing valve. The seal 84 includes at least one layer of seal and is made of an elastic material including a sponge foam or the like. The toner sack 82 has a tapered width decreasing as close to the opening with the ring-shaped portion 83 so that the toner cannot remain inside the toner sack 82 .
With the thus-structured toner container 80 , when the toner container 80 is inserted downwardly into the enclosure 110 , the nozzle 90 is inserted upwardly into the toner container 80 .
A mechanical shutter may be provided to the toner container 80 to automatically close the opening with the ring-shaped portion of the toner sack 82 when the toner sack 82 is removed from the toner container 80 .
As shown in FIG. 4 , the development unit 60 is provided with a sub-hopper 61 on the top thereof. The toner discharged from the toner container 80 is temporarily stored in the sub-hopper 61 . The sub-hopper 61 is provided with a powder pump 70 on the top thereof. The powder pump 70 transports the toner discharged from the toner container 80 to the sub-hopper 61 . The powder pump 70 is a pump having a single eccentric screw. The powder pump 70 includes a rotor 71 , a stator 72 , and a holder 73 . The rotor 71 is made of rigid metal and formed in an eccentric screw shape. The stator 72 is made of elastic material such as a rubber and internally has spiral grooves in a two-screw shape. The holder 73 stores the rotor 71 and the stator 72 , and is made of the plastic material same as that used for the passage for transporting the toner. The rotor 71 is stored inside the stator 72 and is connected with a driving gear 74 using a pin connector so that the rotor 71 can be driven for rotation by the driving gear 74 and, as a result, the toner inside the stator 72 is transported to the sub-hopper 61 by an action of a negative pressure generated by the rotation of the rotor 71 in the powder pump 70 . A gear 75 (see FIG. 5 ) integrally formed with the driving gear 74 is connected with a first clutch 76 via an idle gear (not shown). By switching the first clutch 76 between connection and disconnection, the operation of the powder pump 70 is controlled. The first clutch 76 and a second clutch 68 (later explained) are provided to a rotation driving shaft 79 , as shown in FIG. 5 , which is driven by a driving mechanism (not shown).
The holder 73 includes a toner sucking portion 77 at an end thereof, a right end of the holder 73 in FIG. 4 , to which the above-mentioned toner transportation tube 85 is connected. The toner transportation tube 85 preferably is a flexible tube having a diameter of from about 4 mm to 10 mm, for example, and is made of a rubber material having a superior anti-toner characteristic, such as polyurethane, nitrile, EPDM (ethylene-propylene-diene-methylene), silicon, or the like. Such toner transportation tube 85 can be bent easily and arbitrarily in any direction.
When the toner discharging portion of the toner container 80 is positioned lower than a toner receiving portion of the sub-hopper 61 in the vertical direction, the toner can smoothly be transported from the toner container by using the above-mentioned powder pump 70 .
The sub-hopper 61 is divided into an upper chamber 62 and a lower chamber 63 . As shown in FIGS. 6 and 7 , where FIG. 6 is a top view of the upper chamber 62 and FIG. 7 is a top view of the lower chamber 63 , the upper chamber 62 has a larger floor area than the lower chamber 63 and is provided with a pair of upper screws 64 and 65 and a partition 166 having two cut ends, left and right cut ends in FIG. 6 , where the partition 166 is positioned between the pair of upper screws 64 and 65 and the two cut ends are shorter than an internal width of the upper chamber 62 . In FIG. 6 , a position A in the upper chamber 62 indicated by a circular mark with a partly-dotted line is a position to which the toner transported by the powder pump 70 is supplied. The toner supplied at the position A is transported within the upper chamber 62 in a direction P 1 by the rotations of the upper screws 64 and 65 . An opening B in the upper chamber 62 indicated by a square mark with a solid line is an opening connecting inside spaces of the upper chamber 62 and the lower chamber 63 . That is, the toner moved along in the direction P 1 by the upper screws 64 and 65 is transferred to a region around the connecting opening B and drops down to an inside floor of the lower chamber 63 by its weight through the opening B.
As shown in FIG. 7 , the lower chamber 63 is provided with a lower screw 66 . A position B′ in the lower chamber 63 indicated by a square mark with a solid line is a position to which the toner falls from the upper chamber 62 . The toner received at the position B′ is transported within the lower chamber 63 in a direction P 2 by the rotation of the lower screw 66 . An opening C in the lower chamber 63 indicated by a square mark with a solid line is a toner replenishing opening connecting inside spaces of the lower chamber 63 and the development unit 60 . That is, the toner moved along in the direction P 2 by the lower screw 66 is transferred to a region around the opening C and drops down to an inside floor of the lower chamber 63 by its weight through the opening C.
The sub-hopper 61 is thus structured so that the toner transported by the powder pump 70 is temporarily stored and is transferred to the development unit 60 by the upper screws 64 and 65 and the lower screw 66 . That is, these upper screws 64 and 65 and the lower screw 66 serve as a toner transportation mechanism in the sub-hopper 61 . In addition, as shown in FIG. 5 , the upper screws 64 and 65 and the lower screw 66 are provided with gears 64 a, 65 a, and 66 a, respectively, which are connected via a group of idle gears 67 with a second clutch 68 provided to the driving shaft 79 so that the operations of the upper screws 64 and 65 and the lower screw 66 are controlled by the second clutch 68 which turns on and off.
Further, the sub-hopper 61 is provided with a toner sensor 69 for detecting the toner in the upper chamber 62 when an amount of toner exceeds a predetermined value. The toner sensor 69 is located at a position on a wall near the position A of the upper chamber 62 . The toner sensor 69 is a vibration type sensor having a detection surface 69 a , as shown in FIG. 6 , for detecting the toner in the upper chamber 62 when an amount of toner exceeds the predetermined value.
The thus-structured toner replenishing mechanism starts its operation upon a receipt of an instruction signal for replenishing the toner to the development unit 60 from a toner density sensor (not shown), for example. In the toner replenishing operation, the second clutch 68 is turned on to drive the upper screws 64 and 65 and the lower screw 66 so as to supply the toner to the development unit 60 by an amount according to a length of time that the screws are driven. At the same time, the toner sensor 69 monitors the toner amount in the sub-hopper 61 . Upon a detection by the toner sensor 69 that the toner amount decreases under a predetermined amount, the powder pump 70 is activated to transport the toner of the toner container 80 to the sub-hopper 61 . This process can be performed without the needs of a high accuracy in controlling the amount of the toner replenishment to the sup-hopper 61 . Accordingly, the amount of toner to be transported by the powder pump 70 is determined to be greater than an amount of toner to be transferred from the sub-hopper 61 to the development unit 60 by the upper and lower screws.
In addition, if the toner amount detected by the toner sensor 69 maintains under the predetermined amount even with plural times of the toner replenishing operation by the powder pump 70 , the toner container 80 is judged as nearly empty, which is referred to as a toner near-end status. When the toner near-end status is detected, a caution for an exchange of the toner container 80 is displayed on an indication member (not shown), for example, of the operation panel 120 . When the toner container 80 is not exchanged despite the above-mentioned display of the caution, the image forming operation is prohibited after the execution of the image forming operation a predetermined number of times.
Since the color copying apparatus 1 uses the powder pump 70 to replenish the development unit 60 with the toner of the toner container 80 , the placement of the enclosure 110 for the toner container 80 is highly flexible. The enclosure 110 , however, is not preferably placed at a lower part of the color copying engine 100 since a user may need to bow in exchanging the toner container 80 . A top and front part of the color copying engine 100 is a preferable part for the enclosure 110 to be placed. In addition, if the toner container 80 has an insufficient toner capacity, a frequent exchange of the toner container 80 may be required and therefore the toner container 80 preferably has a sufficient capacity of toner.
FIG. 8 shows the enclosure 110 for the toner container 80 which is placed at a position satisfying the above-mentioned requirements. In the exemplary embodiment, the position is located in an upper front part of the color copying engine 100 and underneath the operation panel 120 . At this position, however, the insertion of the toner container into the enclosure 110 is obstructed by the operation panel 120 .
In the color copying apparatus 1 , the toner container 80 is configured to tilt away from the color copying engine 100 , as shown in FIG. 8 , so that the toner container 80 can be removed, in a direction of arrow P 3 , and inserted into the enclosure 110 with being obstructed by the operation panel 120 . More specifically, behind the enclosure 110 , there is provided a housing plate 130 which encloses a unit of the image forming mechanism including the development unit 60 and the toner replenishing mechanism including the powder pump 70 . The enclosure 110 includes a holder 121 for holding the toner container 80 . At a lower part of the holder 121 , the nozzle 90 is mounted vertically. The holder 121 is held on the housing plate 130 for rotation about a rotation shaft 131 , as shown in FIG. 8 , so that the enclosure 110 can be moved to a closed position at which the enclosure 110 is fit underneath the operation panel 120 , where the toner container 80 and associated components are illustrated with dotted lines, and a tilt position at which the toner container 80 can be exchanged without being obstructed by the operation panel 120 , where the toner container 80 and the holder 121 are illustrated with two-dotted-chain lines. The rotation shaft 131 is provided to a position close to the housing plate 130 and in a lower part of the toner container 80 .
In addition, the enclosure 110 is provided with a stopper (not shown) for engaging the enclosure 110 at the closed position and a release button 111 for releasing the engagement of the enclosure 110 at the closed position by the stopper. When the release button 111 is depressed relative to the enclosure 110 staying at the close position, the stopper is released and the enclosure 110 is tilted towards the tilt position by its own weight. Then, the enclosure 110 settles at the tilt position. After an exchange of the toner container 80 , the enclosure 110 can be lifted by manually to the closed position. When the enclosure 110 comes to the closed position, the stopper automatically engages the enclosure 110 at the closed position. The stopper may include a tapered pawl with spring effect for allowing the enclosure 110 to move from the tilt position to the closed position.
Since the enclosure 110 is opposed to the powder pump 70 and the sub-hopper 61 relative to the housing plate 130 , the toner transportation tube 85 has a sufficient length to be flexibly bent and is arranged to pass through a hole (not shown) provided to the housing plate 130 so as to connect the nozzle 90 with the powder pump 70 . When the enclosure 110 moves between the close position and the tilt position, the toner transportation tube 85 follows the movement as it is flexible. Therefore, the toner transportation tube 85 may not cause a problem such as a breakage, a pull-out, and so forth. If the toner transportation tube 85 is excessively long, however, it may be caught on by other components causing damage during a assembly of the mechanism or exchanging the toner container 80 . Therefore, it is preferable to arrange the hole of the housing plate 130 for allowing the toner transportation tube 85 to pass through at a position close to the rotation shaft 131 so that the movement of the toner transportation tube 85 is minimal.
When the toner transportation tube 85 is made of a single tube, it may be damaged by rubbing between an inner circumferential surface and an outer circumferential surface. To avoid this problem, it is preferable that the toner transportation tube 85 is made of plural tubes, as shown in FIG. 9 . That is, a connection pipe 132 is provided to the hole of the housing plate 130 , and first and second tubes 85 a and 85 b are provided. The first tube 85 a connects between the nozzle 90 and the connection pipe 132 , and the second tube 85 b connects between the connection pipe 132 and the powder pump 70 . In this case, the first tube 85 a is caused to move as the enclosure 110 is moved but the second tube 85 b is not caused to move since the powder pump 70 is not moved. Therefore, the first tube 85 a is preferably made of a flexible material to follow the movement of the enclosure 110 and the second tube 85 b is preferably made of a relatively rigid material to avoid breakage.
FIG. 10 shows an exemplary structure of the enclosure 110 , where the holder 121 of the enclosure 110 is divided into first and second holders 121 a and 121 b. The first holder 121 a holds the toner container 80 for the color of Bk, and the second holder 121 b holds the toner containers 80 for the colors of Y, C, and M. As an alternative, it is possible to hold the toner containers 80 for the colors of Y, C, M, and Bk with a single holder, or four individual holders.
In addition, it is possible to install the enclosure 110 with the toner containers 80 therein inside an entire front cover of the color copying apparatus 1 for covering the inside mechanism such as the image forming mechanism, or a partial front cover prepared specifically for the enclosure 110 . In the former case, the image forming operation is prohibited when the entire front cover is open to exchange the toner container 80 , but in the latter case, the image forming operation is not necessarily prohibited when the partial front cover for the enclosure 110 is open to exchange the toner container 80 .
When the above-mentioned partial front cover is applied to the color copying apparatus 1 , the image forming operation can be executed under the conditions that the toner container 80 is in the toner near-end status, because the color copying apparatus 1 has the sub-hopper 61 and can still supply the requisite toner to the image forming operation. Accordingly, the color copying apparatus 1 does not need to stop the image forming operation and can continue the operation even when the toner near-end is detected. When the toner near-end is detected, the color copying apparatus 1 displays an instruction for exchanging the toner container 80 on the operation panel 120 . The enclosure 110 may then be tilted to the tilt position to exchange the toner container 80 . Upon the exchange of the toner container 80 , the transportation of toner from the toner container 80 can be started by the powder pump 70 even with the enclosure 110 at the tilt position. Thus, the color copying apparatus 1 can continue the image forming operation even when the toner near-end is detected.
Further, it becomes possible for the color copying apparatus 1 to check whether the toner container 80 is correctly set to the holder 121 of the enclosure 110 when it is exchanged, by using the above-described feature of the color copying apparatus 1 . That is, since the transportation of toner from the toner container 80 can be started by the powder pump 70 while the enclosure 110 stays at the tilt position, the color copying apparatus 1 can initiates the toner transportation and monitors the result of the toner transportation during the time the enclosure 110 stays at the tilt position after the tone container 80 is exchanged, thereby detecting an inappropriate setting of the toner container 80 .
FIG. 11 shows a toner replenishing mechanism for replenishing the development unit 60 of an image forming unit 18 with toner. The image forming unit 18 utilizes a toner transportation apparatus with a screw pump mechanism. In FIG. 11 , a toner container 80 contains toner which is transferred to the development unit 60 . This toner container 80 is enclosed by an enclosure 99 ( FIG. 16 ) of the color copying engine 100 . The enclosure 99 appears when a front door 100 a ( FIG. 20 ) of the color copying engine 100 is opened and is provided with a nozzle 110 forming a part of the toner replenishing mechanism. When the toner container 80 is placed into the enclosure 99 , the nozzle 110 is inserted into the toner container 80 . The nozzle 110 has a passage 110 a therein. The passage 110 a is connected to one end of the nozzle to communicate with a toner transportation tube 78 for transporting toner therethrough.
The toner container 80 includes a toner sack 81 which is flexible and exchangeable. The toner sack 81 is made of at least one flexible sheet material such as a polyester film, a polyethylene film, or the like having a thickness of the order of from 80 μm to 200 μm. The toner sack 81 has an opening with a single toner discharging unit 183 at a bottom center thereof for discharging the toner. The toner sack 81 also has a tapered width decreasing as close to the opening with the toner discharging unit 183 so that the toner cannot remain inside the toner sack 81 .
As shown in FIG. 12 , the toner container 80 includes the toner sack 81 and the toner discharging unit 183 . The flexible toner sack 81 includes two sheets 81 a and 81 b for the front and back sides, two sheets of 81 c and 81 d for right and left sides, and an upper sheet 81 e attached together. The right and left side sheets 81 c and 81 d have folds 81 f to inwardly fold sidewalls of the container. When the container is filled with toner, the folds 81 f expand to be in a container shape. When the container has no toner, it is folded along the folds 81 f to contact or closely position the front and back side sheets 81 a and 81 b each other.
As shown in FIGS. 13 to 15 , the toner discharging unit 183 includes an upper main body 84 and an lower main body 85 . The upper main body 84 is provided with a container fixing unit 88 which welds the toner sack 81 configured like a boat seen from the top. The lower main body 85 is of generally substantially rectangular shape. In the lower main body 85 , when the left side as shown in FIG. 21 is the front side, the lower main body 85 of the toner discharging unit 183 has a front and back side width Wa wider than both side width Wb. The toner discharging unit 183 is made of resin such as polyethylene, nylon, or the like. The upper main body 84 is formed integral with the lower main body 85 .
The toner discharging unit 183 includes two holes for discharging toner therethrough. One is an internal hole 86 of the toner sack 81 . The other is a shutter hole 87 for communicating with the internal hole 86 and removalby inserting a shutter which is described later. The hole 86 is a longitudinal hole extending in a vertical direction with the toner discharging unit 183 facing downward. The shutter hole 87 is a transverse hole with an axis line generally perpendicular to an axis line of the internal hole 86 . In this example, the shutter hole 87 is a penetrating hole of a circular cross-section through the front side of the lower main body 85 to the back side. The internal hole 86 is a circular cross-sectional hole having the shorter length in diameter inside a boat-shaped container fixing unit 88 with a funnel-shaped constraint 86 a formed therebetween. That is, the internal hole 86 becomes small by the constraint 86 a as it approaches the shutter hole 87 to communicate with an upper portion of the shutter hole 87 . Therefore, the internal hole 86 has a smaller aperture than the shutter hole 87 in the communication between the internal hole 86 and the shutter hole 87 . When a shutter 92 is inserted in the shutter hole 87 , the hole for discharging the toner is securely closed.
In this embodiment, the shutter 92 has an axially circular cross-section with a slightly smaller diameter than the shutter hole 87 . This allows the shutter 92 to be securely inserted in the shutter hole 87 . However, when the shutter 92 has a smaller diameter than the shutter hole 87 , toner and air are leaked between the shutter 92 and the shutter hole 87 . The toner leakage causes toner contamination while the air leakage causes the toner container 80 to be reduced in volume. In order to avoid such a problem, O-rings 89 are provided with the toner discharging unit 183 to seal between the shutter hole 87 and the shutter 92 . Since the shutter hole 87 is a penetrating hole, the O-rings 89 are provided on both sides of the shutter hole 87 . Moreover, providing the O-rings 89 on both sides of the shutter hole 87 require grooves for attachment with adhesion or the like, causing labor intensive for securing the O-rings 89 and a high assembly cost.
Accordingly, the toner discharging unit 183 according to an embodiment shown in FIGS. 13 to 15 is divided into an inner component 195 and an outer component 91 , both components supporting the O-rings 89 . Specifically, the inner component 195 has an engagement groove 93 for engaging the O-rings 89 . The outer component 91 is provided with an attachment 94 for attaching the inner component 195 , the container fixing unit 88 , a retainer 95 for retaining the O-rings 89 engaged by the engagement groove 93 . When the O-rings 89 are engaged within the engagement groove 93 to attach the inner component 195 to the outer component 91 , they are retained by the retainer 95 to thereby prevent the O-rings 89 from slipping out.
The shutter hole 87 is provided across the inner component 195 and the outer component 91 to attach the inner component 195 to the attachment 94 of the outer component 91 and to insert the shutter 92 into the shutter hole 87 so that the inner component 195 is assembled into the outer component 91 . Further, easy operation of extracting the shutter 92 enables the toner discharging unit 183 to be divided into the inner component 195 and the outer component 91 . Therefore, when the shutter 92 is moved widely or extracted with toner container 80 filled with toner, toner is prone to overflow from it so that the shutter 92 provides a diameter of 8 mm at maximum, preferably, 6 mm to avoid moving the shutter 92 with a finger. That is, when the shutter 92 has a diameter of 10 mm, toner frequently leaks with a finger moving the shutter 92 so that the shutter 92 is set within a 8 mm diameter.
On the other hand, as shown in FIGS. 9 and 11 , the development unit 60 for replenishing toner is provided with a sub-hopper 61 for storing toner on the top thereof. The toner discharged from the toner container 80 is temporarily stored in the sub-hopper 61 . The sub-hopper 61 is provided with a powder pump 70 on the top thereof. The powder pump 70 transports the toner discharged from the toner container 80 to the sub-hopper 61 . The powder pump 70 is a pump having a single eccentric screw. The powder pump 70 includes a rotor 71 , a stator 72 , and a holder 73 . The rotor 71 is made of rigid metal and formed in an eccentric screw shape. The stator 72 is made of elastic material such as a rubber and internally has spiral grooves in a two-screw shape. The holder 73 stores the rotor 71 and the stator 72 , and is made of the plastic material same as that used for the passage for transporting the toner. The rotor 71 is stored inside the stator 72 and is connected with a driving gear 74 using a pin connector so that the rotor 71 can be driven for rotation by the driving gear 74 and, as a result, the toner inside the stator 72 is transported to the sub-hopper 61 by an action of a negative pressure generated by the rotation of the rotor 71 in the powder pump 70 . A gear 75 (see FIG. 9 ) integrally formed with the driving gear 74 is connected with a first clutch 76 via an idle gear (not shown). By switching the first clutch 76 between connection and disconnection, the operation of the powder pump 70 is controlled. The first clutch 76 and a second clutch 68 (later explained) are provided to a rotation driving shaft 79 , which is driven by a driving mechanism (not shown).
The holder 73 includes a toner sucking portion 77 at an end thereof, a right end of the holder 73 in FIG. 11 , to which the above-mentioned toner transportation tube 78 is connected. The toner transportation tube 78 preferably is a flexible tube having a diameter of from 4 mm to 10 mm, for example, and is made of a rubber material having a superior anti-toner characteristic, such as polyurethane, nitrile, EPDM (ethylene-propylene-diene-methylene), silicon, or the like. Such toner transportation tube 78 can be bent easily and arbitrarily in any direction.
FIG. 10 is a top view of the upper chamber 62 and FIG. 11 is a tope view of the lower chamber 63 . The sub-hopper 61 is divided into an upper chamber 62 and a lower chamber 63 . The upper chamber 62 has a larger floor area than the lower chamber 63 and is provided with a pair of upper screws 64 and 65 and a partition 66 having two cut ends, left and right cut ends in FIG. 10 , where the partition 66 is positioned between the pair of upper screws 64 and 65 and the two cut ends are shorter than an internal width of the upper chamber 62 . In FIG. 10 , a position A in the upper chamber 62 indicated by a circular mark with a partly-dotted line is a position to which the toner transported by the powder pump 70 is supplied. The toner supplied at the position A is transported within the upper chamber 62 in a direction P 1 by the rotations of the upper screws 64 and 65 . An opening B in the upper chamber 62 indicated by a square mark with a solid line is an opening connecting inside spaces of the upper chamber 62 and the lower chamber 63 .
As shown in FIG. 16 , the image forming apparatus includes the enclosure 99 to which the toner container 80 having four toner folders for four colors is attached. The enclosure 99 with four folders has a substantially identical internal structure for each folder except that one folder having the toner container 80 for black is widen.
As shown in FIGS. 17 and 18 , the enclosure 99 includes an open and close folder 103 which has the separated toner container 80 for each color and is attached to a body frame 101 with a rotation shaft 102 . The open and close folder 103 is pivotally mounted with respect to the body frame 101 between a closed position shown in FIG. 18 and a tilt position shown in FIG. 19 . The open and close folder 103 is provided with a pair of nozzle guide members (not shown) and a guide tube 105 at the bottom thereof. The nozzle guide members slideably support a nozzle 110 . The guide tube 105 is slideably engaged with a slider 106 for returning the inserted nozzle 110 . The open and close folder 103 is provided with a fixed cover 115 on an outside surface thereof. Further, the open and close folder 103 has an open and close handle 125 on the top thereof movably mounted in the vertical direction. The open and close handle 125 includes a stopper 121 for engaging the open and close folder 103 at the closed position when the open and close folder 103 can be lifted by manually to the closed position. The handle 125 is made of resin and integrally forms a resilient arm 122 at the bottom thereof. The resilient arm 122 lifts the handle 125 to its uppermost position at all times. The nozzle 110 is of the same diameter as the shutter 92 .
The nozzle 110 is provided with a slide arm 111 integrally formed at both sides thereof, the slide arm 111 being movably mounted to the nozzle guide members. The slide arm 111 includes a pawl 112 on an end thereof and the pawl 112 is engaged with an end of the nozzle guide members, thus preventing the nozzle 110 from pulling out of the folder 103 . Arranged between the nozzle 110 and the folder 103 is an compression spring 113 which fits loosely to wrap around the nozzle 110 . The spring 113 holds the nozzle 110 with spring effect at a position where the pawl 112 is engaged with an end of the nozzle guide members at all times.
The guide tube 105 expands axially toward the nozzle 110 to form a hole 105 a into which the shutter 92 can be inserted at one end opposite the nozzle 110 . The other end of the nozzle 110 is sealed by the fixed cover 115 . The guide tube 105 encloses the slider 106 and a compression spring 107 , the compression spring 107 pushing the slider 106 to the nozzle 110 . The slider 106 has a cross section in a convex form and is held in the guide tube 105 even when the slider 106 is pushed to the compression spring 107 by a detent 108 which is formed at the nozzle side of the guide tube 105 . The open and close folder 103 is provided with a guide frame 109 for placing the inserted toner container 80 in the set position. The guide frame 109 has a bottom portion where the nozzle 110 is provided so as to form a holder for holding a bottom body 85 of a toner discharging unit 183 of the toner container 80 . The holder includes an opening (not shown) through which the nozzle 110 and the shutter 92 pass.
When the thus-structured enclosure 99 is pulled out with the handle 125 positioning downward, the stopper 121 disengages from an engagement groove 123 of the body frame 101 to pivot the open and close folder 103 about the rotation shaft 102 to the position where the bottom of the folder 103 contacts with the frame 101 as shown in FIG. 19 . The folder 103 then moves to a tilt position, where the nozzle 110 is retracted inward as shown on the left hand side of FIG. 18 . At this position, the toner container 80 is pushed with the toner discharging unit 183 downward so that the shutter 92 of the toner discharging unit 183 is lowered to a position opposed to the nozzle 110 which is held at the position where the pawl 112 contacts with the nozzle guide members by the compression spring 113 .
After the toner container 80 is inserted in a predetermined position, the open and close folder 103 is returned to a closed position shown in FIG. 18 . This operation causes the nozzle 110 to be inserted in the shutter hole 87 and the shutter 92 moves from the hole 105 a to the guide tube 105 . The nozzle 110 includes a toner inlet 114 on a circumference surface near its end. The toner inlet 114 communicates with the lower portion of an inner hole 33 provided to the toner discharging unit 183 so that a path for transporting the toner from the toner container 80 to the development mechanism 60 is opened. The shutter 92 pushed toward the guide tube 105 by an insertion of the nozzle 110 is hold in a position across the shutter hole 87 and the guide tube 105 without completely pulling out of the shutter hole 87 .
When the nozzle 110 is inserted into the shutter hole 87 , the compression spring 113 is compressed against the open and close folder 103 . Further, the compression spring 107 provided in the guide tube 105 is also compressed by the insertion of the shutter 92 through the slider 106 . Thus, when the folder 103 is moved from the closed position to the tilt position, the nozzle 110 returns to its original position with a force of the compression spring 113 and the shutter 92 also returns to its original position with a force of the compression spring 107 . Therefore, the nozzle 110 pulls out of the shutter hole 87 of the toner container 80 and then the shutter 92 is again inserted into the shutter hole 87 .
As previously described, by simply setting the toner container 80 to the color copying apparatus 1 , the container 80 communicates with a toner replenishment path. When the open and close folder 103 is opened, the nozzle 110 pulls out of the shutter hole 87 and then the shutter 92 immediately returns so that a toner does not leak from the toner container 80 . In this embodiment, since the nozzle 110 and the slider 106 move by the same amount toward the same direction at the time of a setup of the toner container 80 , the nozzle 110 and the slider 106 may be integrated as shown in FIG. 20 . This structure eliminates the problems such that the slier 106 does not move even if the nozzle 110 pulls out and the shutter 92 does not seal the shutter hole 87 .
FIGS. 21 and 22 show another example of an enclosure. In this example, the open and close folder 103 slideably moves in the directions of arrows by a linear guide 130 so that the folder 103 is slideably opened and closed to the color copying apparatus 1 .
The open and close folder 103 is attached to the apparatus 1 via the linear guide 130 . As shown in FIG. 22 , at the same time that the folder 103 is drawn from the apparatus 1 , the nozzle 110 moves away from the toner discharging unit 183 so that the toner container 80 can be removed. At this time, when the container 80 is replaced with new one and the open and close folder 103 is inserted into the apparatus 1 , the nozzle 110 is set into the toner discharging unit 183 to replenish toner into the development mechanism.
FIG. 23 shows another example of an enclosure. In this example, the open and close folder 103 is immovable relative to the color copying apparatus 1 . In addition, to insert and remove the toner container 80 , a door 140 is provided on the folder 103 . A nozzle support member 116 for supporting the nozzle 110 is supported by the liner guide (not shown) in the directions of arrows to permit horizontal movement. The nozzle support member 116 is moved in the directions of the arrows by a cam 141 which pivots around a fulcurum 142 . The door 140 pivots around a fulcurum 143 .
Configured in this manner, the cam 141 connects the door 140 by an arm 144 as shown in FIG. 23 . so that the cam 141 rotates in combination with an open and close of the door 140 to insert and remove the nozzle 110 . Therefore, opening the door 140 moves the nozzle 110 away from the toner discharging unit 183 to allow for a replacement and removal of the toner container 80 . Closing the door 140 inserts the nozzle 110 into the toner discharging unit 183 via the arm 144 , the cam 141 and the nozzle supporting member 116 to allow for toner absorption and replenishment.
Referring now to FIG. 24 , another example of a toner replenishing mechanism will be described. In FIG. 24 , a toner replenishing mechanism utilizes the powder pump 70 , which is similar to the embodiment described above, located to near the development unit 60 as a screw pump mechanism. The enclosure 99 of an image forming apparatus body is provided with a nozzle 190 which is inserted into the toner sack 81 . The nozzle 190 has a circular cross section. The toner container 80 is inserted upwardly into the enclosure of the apparatus body to insert the nozzle 190 into a toner discharging unit. The nozzle 190 of the enclosure includes a tubular structure having a passage 191 which is connected to a toner transportation tube 178 at the end thereof. The passage 191 is bent to the right of the drawing above the toner transportation tube 178 to connect to an air pump 194 via an air transportation tube 193 .
When the air pump 194 is in operation, it discharges the air in a confined jet to inside the toner container 80 from the bottom via the air transportation pipe 193 . The jet air entered inside the toner container 80 agitates the toner and fluidizes the toner in the toner container 80 . When the powder pump 70 is in operation, it absorbs the toner and the air in the toner container 80 to replenish the toner into the development unit 60 .
Numerous additional modifications and variations are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the disclosure of this patent specification may be practiced otherwise than as specifically described herein. | An image forming apparatus including a development mechanism for developing an electrostatic latent image formed on an image carrying member into a visual image, a toner storage detachably installed and provided for storing toner therein, a toner transporting mechanism for transporting the toner from the toner storage to the development mechanism, and a supporting device for detachably supporting the toner storage therein and moving between a set position at which the toner storage is engaged with the toner transporting mechanism and a tilt position at which the toner storage is disengaged from the toner transporting mechanism. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a divisional of U.S. patent application Ser. No. 12/828,124, filed Jun. 30, 2010, and currently pending, the entire disclosure of which is hereby incorporated by reference.
BACKGROUND
[0002] 1. Field
[0003] The present disclosure generally relates to systems and methods for dispensing items and, in particular, systems having individually actuated lidded compartments suitable for single-item dispensing of items.
[0004] 2. Description of the Related Art
[0005] Automated dispensing of medications using Automated Dispensing Machines (ADMs) has become common in hospitals around the world. The benefits include a reduction in the amount of pharmacist labor required to dispense the medications as well as enabling nurses to obtain the medications faster as many ADMs are located at the nursing stations. ADMs also provide secure storage of medications, particularly controlled substances, as users must typically identify themselves and the patient to whom the medication will be administered before the ADM will dispense the medication.
[0006] One of the challenges of ADMs is the method of restocking. ADMs that have fixed drawers require the pharmacist to transport medications to the ADM and load the medications, which both consumes pharmacist time and makes the ADM unavailable to the nurses during the loading process. Another challenge is providing the ability to dispense a single dose of medication, particularly controlled substances, without providing access to a larger stock of the same medications. Existing single-dose dispensing products can be complex, unreliable, or inefficient in space usage.
[0007] The technology of ADMs is applicable to a wide range of non-medical applications, such as dispensing of consumable cutting tools in a machine shop or tracking of tools while working on an aircraft engine where it is critical to ensure that no tool has been left in the engine. Applications where inventory control is a concern or where the identity of the user must be authenticated prior to allowing access to the contents of the storage system are candidates for the use of ADM technology.
SUMMARY
[0008] The multi-lidded cartridge and the dispensing system disclosed herein provide an elegant and secure method of dispensing items such as medications. The cartridge may be loaded at a remote location such as a pharmacy and securely transported to the ADM by a non-pharmacist and quickly loaded into the ADM, saving pharmacist time and improving the availability of the ADM to nurses. The cartridges provide single-dose dispense capability in a space-efficient manner.
[0009] A cartridge is disclosed. The cartridge comprises a body having an exterior and a plurality of bins, each bin having an opening. There are a plurality of lids movably attached to the body. Each lid is configured to cover the opening of a bin and each lid has a fastening element. A release mechanism is movably attached to the body. The release mechanism is movable along an axis. A plurality of latches are movably attached to the body. Each of the plurality of latches is configured to engage the respective fastening element of the plurality of lids when in a first position and to release the respective fastening element when in a second position. The latches and release mechanism are configured such that the release mechanism will not cause a latch to move to the second position when the release mechanism is moving along the axis in a first direction and the release mechanism will cause a single latch to move to the second position while leaving the remaining latches in the first position when the release mechanism is moving along the axis in a second direction that is opposite to the first direction.
[0010] A dispensing system is disclosed. The dispensing system comprises a cartridge and a cabinet. The cartridge comprises a body having an exterior and a plurality of bins, with a plurality of lids movably attached to the body, and a connector having contacts exposed on the exterior of the body. The lids have closed positions wherein the lids cover the respective bins. The cartridge is configured such that the lids cannot be opened except by receipt of a command signal by the cartridge through the connector. The cabinet comprises a housing having a docking location configured to accept a cartridge, a docking connector attached to the housing, and a controller coupled to the docking connector. The housing is configured such that the docking connector connects to the cartridge connector when the cartridge is placed on the docking location. The controller is configured to send the command signals to the cartridge via the docking connector to open one of the lids.
[0011] A method of providing access to a single bin of a cartridge having a plurality of bins is disclosed. The method includes the step of moving a latch driver along an axis of motion. The latch driver has an actuation mode and a bypass mode. The latch driver will not actuate a latch while moving in a first direction while in the actuation mode but will actuate the latch to open a lid covering the bin while moving in a second direction while in the actuation mode, the second direction being opposite of the first direction. The latch driver will not actuate the latch when moving in either the first or second direction while in the bypass mode. The method also includes the steps of switching the latch driver to bypass mode upon reaching a first end of a range of motion while moving in the first direction along the axis of motion, moving the latch driver in the second direction over the entire range of motion, switching the latch driver to actuation mode upon reaching a second end of the range of motion while moving in the second direction along the axis of motion, moving the latch driver in the first direction until the latch driver passes the latch, and moving the latch driver in the second direction until the latch driver displaces the latch sufficient to disengage the latch from the lid, allowing the lid to open and allowing access to the bin.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The accompanying drawings, which are included to provide further understanding and are incorporated in and constitute a part of this specification, illustrate disclosed embodiments and together with the description serve to explain the principles of the disclosed embodiments. In the drawings:
[0013] FIG. 1 depicts an ADM used in medical facilities.
[0014] FIG. 2 depicts a dispensing cartridge insertion into an ADM drawer according to certain embodiments of the present disclosure.
[0015] FIG. 3 shows an ADM drawer containing dispensing cartridges according to certain embodiments of the present disclosure.
[0016] FIGS. 4A-4C illustrate an exemplary configuration of a cartridge lid-release system according to certain embodiments of the present disclosure.
[0017] FIGS. 5A-5E illustrate a cartridge lid latch according to certain embodiments of the present disclosure.
[0018] FIGS. 6A-6F illustrate an operational sequence to release a cartridge lid latch according to certain embodiments of the present disclosure.
[0019] FIGS. 7A-7B illustrate an alternate embodiment of a cartridge lid latch and lid-release system according to certain embodiments of the present disclosure.
[0020] FIGS. 8A-8G illustrate an operational sequence for the lid latch configuration of FIGS. 7A-7B according to certain embodiments of the present disclosure.
[0021] FIGS. 9A-9B illustrate an alternate embodiment of the latch release system of a cartridge according to certain embodiments of the present disclosure.
[0022] FIGS. 10A-10H illustrate an operational sequence for the lid latch configuration of FIGS. 9A-9B according to certain embodiments of the present disclosure.
[0023] FIGS. 11A-11D illustrate an alternate embodiment of the latch release system of a cartridge according to certain embodiments of the present disclosure.
[0024] FIGS. 12A-12H illustrate an operational sequence to release a lid for the lid latch configuration of FIGS. 11A-11D according to certain embodiments of the present disclosure.
[0025] FIGS. 13A-13E illustrate an exemplary embodiment of a latch-release system according to certain embodiments of the present disclosure.
[0026] FIG. 14 illustrates an exemplary embodiment of a latch-release system according to certain embodiments of the present disclosure.
DETAILED DESCRIPTION
[0027] Pharmacists are under increasing pressure to manage the medications that are provided to nurses and other caregivers in a medical facility. There is an increasing level of regulation, particularly for controlled substances, related to the handling and tracking of medications. Many of these regulations require a pharmacist to perform certain checks on medications, increasing the workload of a pharmacist. Controlled substances, which may include medications listed on Schedules I-V of the Controlled Substances Act. In addition, many hospitals are finding that they cannot locate pharmacists to fill open positions, placing greater burdens on the pharmacists that are on the hospital staff. There is therefore a need to manage medications with a reduced amount of pharmacist time.
[0028] The disclosed cartridge, system, and method enable a pharmacist to make medications in an ADM available to nurses at a reduced level of pharmacist effort. A cartridge can be filled and verified by a pharmacist in the pharmacy and then securely transported to an ADM and loaded into the ADM by a non-pharmacist employee such as a pharmacy technician. Alternately, the medications can be verified in the pharmacy by a pharmacist and then transported to the ADM by a pharmacy technician who then loads the mediations into the cartridge. As the compartments cannot be opened when the cartridge is not installed in an ADM or equivalent loading station in the pharmacy, the pharmacist does not need to inspect the cartridge again at the ADM.
[0029] Certain exemplary embodiments of the present disclosure include a cartridge having a plurality of bins with individually openable lids. This cartridge is suitable for single-dose dispensing as a single dose of medication may be placed in each compartment. Opening a single lid provides the caregiver with access to that single dose without providing the caregiver access to other doses. This eliminates the need for periodic verification counts of the medications, as the opportunity for undetected removal of the medication from the bins has been eliminated.
[0030] While the discussion of the cartridge, system, and method is directed to the dispensing of medications in a hospital, the disclosed methods and apparatus are applicable to dispensing of medications in other environments as well as the dispensing of other types of items in a variety of fields. For example, machine shops frequently have a tool crib staffed by an individual to provide cutters, drills, and other consumable supplies to the machinists without providing uncontrolled access to the stock of tools and parts. An ADM may be stocked with these consumables and used in place of the tool crib to provide these items to the machinists in a controlled and traceable manner. Similarly, items such as an expensive specialty tool may be removed by an individual for use and returned to the same compartment after use, enabling the tool to be tracked and making a single tool available to multiple people.
[0031] In the following detailed description, numerous specific details are set forth to provide a full understanding of the present disclosure. It will be apparent, however, to one ordinarily skilled in the art that embodiments of the present disclosure may be practiced without some of the specific details. In other instances, well-known structures and techniques have not been shown in detail so as not to obscure the disclosure.
[0032] FIG. 1 is a drawing of an ADM used in medical facilities. This example ADM 10 includes a plurality of drawers 12 , some of which may be configured to receive dispensing cartridges (not shown). This configuration of an ADM can be referred to as a cabinet, which includes the housing 11 , the drawers 12 , a variety of electronics and controls (not shown), and the user interface. The user interface of the ADM 10 includes a display 16 and a keyboard 14 so that a user, such as a nurse, may identify which medication they wish to remove from the ADM.
[0033] FIG. 2 is a drawing showing how a dispensing cartridge 20 fits into an ADM drawer 12 according to certain embodiments of the present disclosure. In this view, a drawer 12 has been removed from the housing 11 of the ADM for clarity. Dispensing cartridges 20 may be provided in a variety of widths. In this example, cartridges 20 are of a width that may be defined as “unit width,” “single width,” or “1×” with a certain number of equal-size compartments 22 . Cartridge 24 is of the same width as cartridge 20 with a reduced number of compartments, such that the compartments are larger and can hold larger items. Cartridge 26 is wider than cartridge 20 and has four large compartments, enabling each compartment to hold a large single item or a larger quantity of a small item. In some embodiments, wider cartridges are provided in incremental widths that are integer multiples of the 1× width. This enables a user to install a variable configuration of cartridges. In the example of FIG. 2 , the drawer 12 has five 1× spaces 28 , with three 1× cartridges 20 and one 2× cartridge 26 installed. Other widths of cartridges may be installed up to, in this example, a single 5× cartridge.
[0034] FIG. 3 is a drawing of an ADM drawer 12 containing dispensing cartridges according to certain embodiments of the present disclosure. In FIG. 3 , the drawer 12 of FIG. 2 is installed in housing 11 and is shown in a state after a user has requested a medication that was contained in one of the cartridges placed in drawer 12 . One compartment of cartridge 20 has been opened by the ADM controller (not shown), revealing lid 30 that covered bin 32 of the compartment containing the desired medication. In this example, lid 30 is attached by a hinge to the body of cartridge 20 . The lid 30 has a hook or other fastening element (not shown in FIG. 3 ) that enables a latch or other mechanism (not shown in FIG. 3 ) within the cartridge to retain the lid 30 in the closed position. The remaining lids 30 remain closed and locked, preventing access to the contents of the other compartments.
[0035] FIGS. 4A-4C illustrate an exemplary configuration of a cartridge lid-release system according to certain embodiments of the present disclosure. FIG. 4A shows a dispensing cartridge 20 having a plurality of lids 30 attached to a body 34 . FIG. 4B shows a side view of cartridge 20 where a side panel has been removed from body 34 to show the release mechanism 36 and latches 38 . Distal and proximal directions are herein defined relative to the cartridge 20 for discussion of operation in later sections. FIG. 4C is an enlarged view of a section of FIG. 4B . Lid 30 is shown in FIG. 4C in the closed position and has an attached hook 38 as an example fastening element. Latch 40 is engaged with hook 38 and retains lid 30 in the closed position. The details of the construction and operation of this example latch 40 are discussed below. This embodiment of release mechanism 36 includes an endless belt 42 passing over a pulley 44 at each end of the cartridge body 34 , as shown in FIG. 4C . FIG. 4C is shown with a split across the body between pulley 44 and latch 40 to indicate that this same configuration of lid 30 and latch 40 are repeated at each lid along the cartridge 20 . The endless belt 42 has an attached latch driver 46 that is discussed in more detail below. The endless belt 42 has an upper or first path 42 A and a lower or second path 42 B, and the latch driver 46 may travel the full circumference of the endless belt, traveling along either first path 42 A or second path 42 B in either the proximal or distal direction. In this example, the endless belt 42 is moved in either direction by rotation of one of the pulleys 44 as driven by a motor (not shown).
[0036] FIGS. 5A-5E illustrate the construction of a cartridge lid latch 40 according to certain embodiments of the present disclosure. FIG. 5A is a side view of the latch 40 showing the upper latch arm 52 and lower latch arm 54 , both of which pivot about an axle 53 . Axle 53 may be a part of the body to which the latch 40 is attached or may be a separate item. The distal and proximal directions of FIG. 4B are repeated for the example embodiment shown herein. FIG. 5B is a perspective and exploded view of latch 40 , wherein a stop bar 55 of upper latch arm 54 is visible. In operation, a biasing element (not shown), such as a torsional spring, urges the upper latch arm 52 to rotate counterclockwise about axle 53 to the position shown in FIG. 5A . Similarly, a biasing element (not shown) urges lower latch arm 54 to rotate clockwise about axle 53 to the position shown in FIG. 5A . In some embodiments, a single biasing element may provide both functions while multiple biasing elements may be used in alternate embodiments.
[0037] FIG. 5C shows one degree of freedom of motion of latch 40 , wherein upper latch arm 52 rotates clockwise about axle 53 while lower latch arm 54 remains in its original position. FIG. 5D shows a second degree of freedom of motion of latch 40 wherein lower latch arm 54 rotates counterclockwise while the upper latch arm 52 remains in its original position. FIG. 5E shows another degree of freedom wherein lower latch arm 54 rotates clockwise and stop bar 55 engages the upper latch arm 52 , causing upper latch arm 52 to also rotate clockwise. It can be seen that the motions of FIGS. 5C-5E are all opposed by the action of the respective biasing elements, so that each element will return to the position of FIG. 5A in the absence of an applied force. The points where these motions occur during operation of release mechanism 36 will be discussed below.
[0038] FIGS. 6A-6F illustrate an operational sequence to release a cartridge lid latch according to certain embodiments of the present disclosure. FIG. 6A shows a starting position wherein latch 40 is in a stable configuration and engaged with hook 38 . Latch driver 46 is attached to endless belt 42 and is positioned on the distal side of latch 40 . It can be seen that latch driver 46 and latch 40 have matching inclined surfaces. In FIG. 6B , latch driver 46 is moving in the proximal direction, as indicated by the arrow, forcing lower latch arm 54 to rotate counterclockwise. It can be seen that this motion does not release hook 38 . FIG. 6C shows latch driver 46 as having passed lower latch arm 54 and stopped on the proximal side of latch 40 , wherein lower latch arm 54 has returned to the position of FIG. 6A . In FIG. 6D , belt 42 has reversed direction and latch driver 46 is moving in the distal direction and is forcing lower latch arm 54 to rotate clockwise, which causes upper latch arm 52 to also rotate clockwise. Clockwise rotation of upper latch arm 52 releases hook 38 . In this example, there is a biasing element (not shown) urging the lid to which hook 38 is attached to open, whereupon hook 38 moves upward and out of engagement position for upper latch arm 52 . In FIG. 6E , latch driver 46 has again moved to the proximal side of latch 40 and allowed latch 40 to return to the position of FIG. 6A . FIG. 6F shows how hook 38 moves downward and engages upper latch arm 52 as the lid (not shown) is closed, as upper latch arm 52 rotates clockwise to allow hook 38 to pass the engagement feature of upper latch arm 52 and move to the engagement position of FIG. 6A , whereupon upper latch arm 52 will rotate counterclockwise under the urging of the biasing element (not shown) and the system will return to the configuration of FIG. 6A .
[0039] FIGS. 7A-7B illustrate an alternate embodiment of a cartridge lid latch and lid-release system according to certain embodiments of the present disclosure. FIG. 7A shows a dispensing cartridge 60 having the same release mechanism 36 as shown in FIGS. 4A-B , with a different latch (not shown). FIG. 7B shows an enlarged view of the distal end of cartridge 60 , wherein two latches 62 are visible. The proximal latch 62 is shown engaged with hook 38 of lid 30 . It can be seen that latch 62 does not rotate about a fixed axle and, instead, slides and rotates within a partial cavity 64 formed in the body 34 . A biasing element 66 , which is a spring in this example, applies force to latch 62 in the downward and proximal direction.
[0040] FIGS. 8A-8G illustrate the operations sequence for the lid latch configuration of FIGS. 7A-B according to certain embodiments of the present disclosure. FIG. 8A depicts a starting position where latch 62 is in the fully down position and engaged with hook 38 with latch driver 46 positioned to the distal side of latch 62 . FIG. 8B shows latch driver 46 pushing latch 62 upwards as it passes under the latch 62 , with latch 62 remaining engaged with hook 38 . FIG. 8C shows latch driver 46 stopped on the proximal side of latch 62 that has returned to its fully down position. In FIG. 8D , latch driver 46 is moving in the distal direction and forcing latch 62 in the distal direction as well, causing latch 62 to disengage from hook 38 . FIG. 8E shows the lid 30 fully opened by its biasing element (not shown). FIG. 8F shows latch driver 46 moved distally out of the way of the open lid 30 and associated latch 62 , which has returned to its fully down position. Hook 38 is visible as close to but not yet in contact with latch 62 . It can be seen that there are mating inclined surfaces on both hook 38 and latch 62 that will force latch 62 to move distally as the hook 38 descends. FIG. 8G shows the lid 30 fully closed and hook 38 engaged with latch 62 , which has returned to the original position of FIG. 8A .
[0041] FIGS. 9A-9B illustrate an alternate embodiment of the latch release system of a cartridge according to certain embodiments of the present disclosure. Cartridge 70 is similar to the cartridges 20 and 40 of FIGS. 4A and 7A , respectively, except that the release mechanisms have been replaced by release mechanism 72 . FIG. 9B shows an enlarged side view of the distal end of two components of release mechanism 72 , inner slide 74 and outer slide 76 . Inner slide 74 has an attached post 78 that protrudes towards the outer slide 76 and fits through the shaped hole 80 . The shaped hole 80 has detent positions 82 and 84 at the distal and proximal ends, respectively, with a centerline path 86 connecting the two detent positions. The two slides 74 , 76 are positioned adjacent to each other when installed in cartridge 70 , with post 78 protruding through shaped hole 80 . Inner slide 74 may move parallel to outer slide 76 along a path defined by the motion of post 78 along centerline path 86 . Inner slide 74 also includes latch driver 46 as a shaped element that is an integral part of the slide. The equivalence of this shaped element to the latch driver of previous embodiments is discussed below.
[0042] FIGS. 10A-10H illustrate the operational sequence for the lid latch configuration of FIGS. 9A-9B according to certain embodiments of the present disclosure. FIG. 10A shows a starting position where post 78 is located in detent 82 . In this configuration, inner slide 74 is at it lowest position relative to outer slide 76 and it can be seen that the tip of latch driver 46 is lower than the lowest part of latch 86 and will pass under without touching latch 86 . This is a “bypass mode” of this embodiment. Latch 86 again is a sliding latch with a biasing element 64 forcing it down and in a proximal direction. In FIG. 10B , outer slide 76 has been moved distally until the end of inner slide 74 comes into contact with distal travel stop 88 . FIG. 10C shows outer slide 76 continuing to move in a distal direction, forcing post 78 to move out of detent 82 and follow the shaped path upwards, which forces inner slide 74 to move upwards as well. FIG. 10D shows that outer slide 76 has moved distally far enough that post 78 has reached detent 84 , stopping the motion of outer slide 76 . As detent 84 is higher than detent 82 , latch driver 46 is now higher relative to latch 86 and can be seen to be high enough to engage latch 86 as it passes under latch 86 .
[0043] In FIG. 10E , outer slide 76 is moving in the proximal direction. Latch driver 46 is forcing latch 86 upwards as latch driver 46 passes under latch 86 without causing latch 86 to disengage hook 38 . Outer slide 76 could continue to move proximally and latch driver 46 could pass under additional latches 86 such that a single latch driver could selectively open any of a plurality of latches. In FIG. 10F , outer slide 76 has moved further proximally such that latch driver is now on the proximal side of latch 86 . FIG. 10G shows how outer slide 76 again moves in a distal direction. Latch driver 46 is now in its “actuation mode”, i.e. in the higher position of shaped hole 80 , and so latch driver 46 pushes latch 86 in the distal direction, which causes latch 86 to disengage from hook 38 . FIG. 10H shows lid 30 fully open. This embodiment will re-engage upon closure of lid 30 in much the same way as shown in FIGS. 8F-8G for the prior embodiment.
[0044] FIGS. 11A-11D illustrate an alternate embodiment of the latch release system of a cartridge according to certain embodiments of the present disclosure. FIG. 11A shows a dispensing cartridge 90 having a different latch and release mechanism than the previous cartridge embodiments. FIG. 11B is a close-up view of the distal end of cartridge 90 , showing a latch 94 and a sliding carrier 96 having flexible arms 98 . Latch 94 and sliding carrier 96 are shown at an even larger scale in FIG. 11C and FIG. 11D , respectively. In FIG. 11C , it can be seen that latch 94 has a shaped cavity 100 and a diverter path 102 , the function of which will be discussed below. In FIG. 11D , it can be seen that flexible arms 98 have tips 104 .
[0045] FIGS. 12A-12H illustrate the operations sequence to release a lid for the lid latch configuration of FIGS. 11A-11D according to certain embodiments of the present disclosure. FIG. 12A shows the sliding carrier 96 in an initial position where tip 104 is not in contact with latch 94 . This embodiment of latch 94 moves only along a distal-proximal axis and engages hook 38 at the distal end of travel, as shown in FIG. 12A . Biasing element 64 , which is a spring in this embodiment, can be seen to be urging latch 94 to move in a distal direction. In FIG. 12B , sliding carrier 96 has moved distally such that tip 104 is in contact with the outer surface of latch 94 , forcing the flexible arm 98 to bend outward. FIG. 12C shows the sliding carrier as having moved further distally such that tip 104 is now in contact with shaped cavity 100 . The shaped cavity 100 has a sloped surface on the distal side such that, if sliding carrier 96 continues to move in distal direction then tip 104 will ride up and out of shaped cavity 100 . Shaped cavity 100 has a straight or undercut edge on the proximal side such that tip 104 will not ride out of the shaped cavity 100 but will, instead, engage the edge. FIG. 12D shows this situation, where sliding carrier 96 has reversed direction such that tip 104 has reached the proximal edge of shaped cavity 100 and engaged, or snagged, the proximal edge of shaped cavity 100 . As sliding carrier 96 continues to move proximally, tip 104 will pull latch 94 in the proximal direction, releasing the hook 38 as shown in FIG. 12D .
[0046] FIG. 12E continues from the configuration of FIG. 12C where the tip 104 is in contact with the shaped cavity 100 . The shaped cavity 100 has a sloped surface on the distal side such that, if sliding carrier 96 continues to move in distal direction then tip 104 will ride up and out of shaped cavity 100 . FIG. 12E shows tip 104 riding on the outer surface of latch 94 on the distal side of shaped cavity 100 , having followed the sloped surface up out of shaped cavity 100 . FIG. 12F shows the configuration after the sliding carrier 96 has moved further distally such that tip 104 is not in contact with latch 94 . In FIG. 12G , sliding carrier 96 has reversed direction and is traveling in a proximal direction. As tip 104 comes into contact with the outer surface of latch 94 , approaching from the distal side of the latch 94 , tip 104 follows diverter path 102 . As tip 104 follows diverter path 102 , flexible arm 98 bends upwards. Diverter path 102 continues around shaped cavity 100 and tip 104 will not engage latch 94 . FIG. 12H shows the configuration after tip 104 is no longer in contact with the outer surface of latch 94 , which is identical to FIG. 12A .
[0047] FIGS. 13A-13E illustrate an exemplary embodiment of a latch-release system according to certain embodiments of the present disclosure. FIG. 13A shows a distal portion of inner slide 74 of the release mechanism of FIGS. 11A-11D and five identical, evenly spaced latches 86 A- 86 E at the distal end of a cartridge 70 . Inner slide 74 includes three latch drivers 46 A- 46 C within the portion of inner slide 74 shown in FIG. 13A . The latch drivers 46 A- 46 C are spaced at an interval slightly less than twice the interval of the latches. In FIG. 13A , latch driver 46 A is touching the proximal edge of latch 86 A such that a slight distal movement of inner slide 74 will cause latch 86 A to release its respective hook 38 . At the same time, latch drivers 46 B and 46 C are pushing latches 86 C and 86 E, respectively, upward and the distal movement of inner slide 74 will not cause either latch 86 C or 86 E to release their respective hooks 38 . Thus, inner slide 74 is positioned such that a small distal movement, i.e. a movement that is a fraction of the interval between latches, of inner slide 74 will release the lid over latch 86 A while not releasing the other four lids over latches 86 B- 86 E.
[0048] In FIG. 13B , inner slide 74 has moved proximally to a position where latch driver 46 B is in contact with latch 86 C such that a small distal movement of inner slide 74 will cause latch 86 C to release its respective hook. At the same time latch driver 46 C is pushing latch 86 E upwards and a distal movement of inner slide 74 will not cause latch 86 E to release its respective hook. Thus, inner slide 74 is positioned such that a small distal movement of inner slide 74 will release the lid over latch 86 C while not releasing the other four lids over latches 86 A- 86 B and 86 D- 86 E.
[0049] Similarly, it can be seen that in FIG. 13C , inner slide 74 is positioned to release latch 86 E without releasing the other latches. FIG. 13D shows inner slide 74 positioned to release latch 86 B and FIG. 13E shows inner slide 74 positioned to release latch 86 D. FIGS. 13A-13E collectively show how a release mechanism, embodied as inner slide 74 in this example, can selectively release one of a plurality of lids without releasing the remaining lids by selection of a spacing, or pitch, between latch drivers that is less than an integral multiple of the spacing of the latches. This same approach may be applied to the flexible arms 98 and tips 104 of the embodiment of FIGS. 11A-11D .
[0050] FIG. 14 illustrates an exemplary embodiment of a latch-release system according to certain embodiments of the present disclosure. In this embodiment, inner slide 74 has a plurality of latch drivers 46 that can each release two latches when operated according to the procedure illustrated in FIGS. 13A-13E . The separation, or pitch, of adjacent latch drivers 46 A and 46 B is slight less than the separation of latches 86 A and 86 C. In this example, latch drivers 46 A and 46 B are separated by 72.950 millimeters whereas latches 86 A and 86 C are separated by 78.339 millimeters.
[0051] It can be seen that the disclosed embodiments of the multi-lidded dispensing cartridge enable the dispensing of one or more items from a single compartment without allowing access to the contents of other compartments. If a single item is placed in each compartment, this enables single-item dispensing of items such as high-value medications or supplies and controlled substances. The use of a single release mechanism to selectively release all the lids of a cartridge allows a simpler and less expensive system. Cartridges may be provided in a variety of widths, enabling a user to easily configure a drawer to provide a variety of compartment sizes such that large items may be handled in some compartments while the remaining compartment may be efficiently used to dispense smaller items.
[0052] The previous description is provided to enable any person skilled in the art to practice the various aspects described herein. While the foregoing has described what are considered to be the best mode and/or other examples, it is understood that various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects. Thus, the claims are not intended to be limited to the aspects shown herein, but is to be accorded the full scope consistent with the language claims, wherein reference to an element in the singular is not intended to mean “one and only one” unless specifically so stated, but rather “one or more.” Unless specifically stated otherwise, the terms “a set” and “some” refer to one or more. Pronouns in the masculine (e.g., his) include the feminine and neuter gender (e.g., her and its) and vice versa. Headings and subheadings, if any, are used for convenience only and do not limit the invention.
[0053] It is understood that the specific order or hierarchy of steps in the processes disclosed is an illustration of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the processes may be rearranged. Some of the steps may be performed simultaneously. The accompanying method claims present elements of the various steps in a sample order, and are not meant to be limited to the specific order or hierarchy presented.
[0054] Terms such as “top,” “bottom,” “front,” “rear” and the like as used in this disclosure should be understood as referring to an arbitrary frame of reference, rather than to the ordinary gravitational frame of reference. Thus, a top surface, a bottom surface, a front surface, and a rear surface may extend upwardly, downwardly, diagonally, or horizontally in a gravitational frame of reference.
[0055] A phrase such as an “aspect” does not imply that such aspect is essential to the subject technology or that such aspect applies to all configurations of the subject technology. A disclosure relating to an aspect may apply to all configurations, or one or more configurations. A phrase such as an aspect may refer to one or more aspects and vice versa. A phrase such as an “embodiment” does not imply that such embodiment is essential to the subject technology or that such embodiment applies to all configurations of the subject technology. A disclosure relating to an embodiment may apply to all embodiments, or one or more embodiments. A phrase such an embodiment may refer to one or more embodiments and vice versa.
[0056] The word “exemplary” is used herein to mean “serving as an example or illustration.” Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs.
[0057] All structural and functional equivalents to the elements of the various aspects described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. No claim element is to be construed under the provisions of 35 U.S.C. §112, sixth paragraph, unless the element is expressly recited using the phrase “means for” or, in the case of a method claim, the element is recited using the phrase “step for.” Furthermore, to the extent that the term “include,” “have,” or the like is used in the description or the claims, such term is intended to be inclusive in a manner similar to the term “comprise” as “comprise” is interpreted when employed as a transitional word in a claim. | A dispensing system has a cartridge with a body having a plurality of bins and a plurality of attached lids that cover the respective bins when the lids are closed. The body has an external connector and the lids are opened by receipt of a command signal through the connector. The system also includes a cabinet with a docking location configured to accept a cartridge. The cabinet has a docking connector that connects to the cartridge connector when the cartridge is placed on the docking location. The cabinet also has a controller that sends the command signal through the docking connector to the cartridge to open one or more of the lids. | 6 |
FIELD
[0001] This disclosure relates generally to fencing systems. More particularly, this disclosure relates to a picket fence system including singular blow-molded pickets.
BACKGROUND
[0002] The present disclosure relates to fence systems. Traditional wood picket fences have a desirable planar picket surface. When polymer or similar materials have been used to make construct similar fences due to, inter alia, the lighter and more robust characteristics of such materials and manufacturing techniques (e.g., extruding and/or blow-molding), a consistent problem encountered in the art has been the inability to achieve a traditional planar picket surface using polymer-based materials and related techniques. This problem is based at least in part on the external appearance of functional features in such polymer-based fences wherein such appearance does not correspond with the traditional look of similar fences made of wood. In particular, the pickets included in traditional picket fence designs have substantially planar surfaces of various widths and thicknesses, and often a particular repeating feature on the top of each picket. Picket fences made using blow molding techniques and/or extrusion have not been able to reproduce such a look and often require multiple parts per picket that must be attached together.
[0003] What is needed therefore is a simplified picket fence system that provides a picket fence with a traditional picket fence look but wherein the parts of the fence are minimal and are made using blow molding and extrusion technologies.
SUMMARY
[0004] The disclosure relates to a fencing system having a first singular blow-molded picket, a first substantially hollow rail, and a second substantially hollow rail.
[0005] The first singular blow-molded picket includes a plurality of interference members defined along a first face of the first picket and at least one interference member defined along a second face of the first picket. The first picket is shaped according to a first predefined blow-molding pattern. The first substantially hollow rail includes a first aperture and a second aperture aligned on a common axis on opposing sides of the first rail and configured to tightly receive the first picket therethrough. A first interference member is located directly adjacent a lower rim of the first aperture. The second substantially hollow rail includes a third aperture and a fourth aperture aligned on a common axis on opposing sides of the second rail and configured to tightly receive the first picket therethrough. A second interference member is located directly adjacent a lower rim of the third aperture. A third interference member is located directly adjacent an upper rim of the second aperture or an internal upper rim of the fourth aperture.
[0006] In some examples, the first interference member is located directly adjacent an internal lower rim of the first aperture, the second interference member is located directly adjacent an internal lower rim of the third aperture, and the third interference member is located directly adjacent an internal upper rim of the second aperture or an internal upper rim of the fourth aperture.
[0007] In other examples, the first interference member is defined along the first face of the first picket and the second interference member is defined along the second face of the first picket. Additionally, a fourth interference member is defined along the second face of the first picket, directly across from the first interference member, located directly adjacent an internal lower rim of the first aperture. Also, a fifth interference member is defined along the first face of the first picket, directly across from the second interference member, located directly adjacent an internal lower rim of the third aperture.
[0008] In still other examples, the first interference member is defined along the first face of the first picket and the second interference member is defined along the first face of the first picket. Additionally, a fourth interference member is defined along the second face of the first picket, directly across from the first interference member, located directly adjacent an internal lower rim of the first aperture. Lastly, a fifth interference member is defined along the second face of the first picket, directly across from the second interference member, located directly adjacent an internal lower rim of the third aperture.
[0009] In certain other examples, a second singular blow-molded picket including a second plurality of interference members is defined along a first face of the second picket. Also, at least one interference member is defined along a second face of the second picket, wherein the second picket is shaped according to a second predefined blow-molding pattern. Additionally, the first substantially hollow rail includes a fifth aperture and a sixth aperture that are aligned on a common axis on opposing sides of the first rail and are configured to tightly receive the second picket. A fourth interference member is located directly adjacent an internal lower rim of the fifth aperture. Also, the second substantially hollow rail includes a seventh aperture and an eighth aperture that are aligned on a common axis on opposing sides of the second rail and are configured to tightly receive the second picket. A fifth interference member is located directly adjacent an internal lower rim of the seventh aperture. Lastly, a sixth interference member is located directly adjacent an internal upper rim of the sixth aperture or an internal upper rim of the eighth aperture.
[0010] In certain other examples, each of the interference members of the plurality of interference members includes a bulge. Each bulge includes at least one sloped edge.
[0011] In other embodiments, a sixth interference member is defined along the second face of the first picket, directly across from the third interference member and is located directly adjacent an internal upper rim of the second aperture. Also, a seventh interference member is defined along the second face of the first picket and is located directly adjacent an internal upper rim of the fourth aperture. Lastly, an eighth interference member is defined along the first face of the first picket, directly across from the seventh interference member and is located directly adjacent an internal upper rim of the fourth aperture.
[0012] In some examples, the first pre-defined blow-molding pattern is the same as the second pre-defined blow-molding pattern.
[0013] In some examples, the first pre-defined blow molding pattern has an average picket width of X and the second pre-defined blow molding pattern has an average picket width of X×Y, wherein X and Y are variables representing different numbers with each number provided in units of length.
[0014] In some examples, the first pre-defined blow molding pattern has an average picket depth of X and the second pre-defined blow molding pattern has an average picket depth of X×Y, wherein X and Y are variables representing different numbers with each number provided in units of length.
[0015] In some examples, the first pre-defined blow molding pattern has an average picket length of X and the second pre-defined blow molding pattern has an average picket length of X×Y, wherein X and Y are variables representing different numbers with each number provided in units of length.
[0016] In a second set of examples, the disclosure relates to a kit of picket fence parts including a plurality of singular blow-molded pickets, a first substantially hollow rail and a second substantially hollow rail. Each picket includes a plurality of interference members defined along a first face of each picket. Also, each picket includes at least one interference member defined along a second face of each picket. At least a first portion of the plurality of pickets are shaped according to a first predefined blow-molding pattern. The first substantially hollow rail includes a first plurality of apertures spaced in a repeating pattern along a first edge of the first rail and a second plurality of apertures spaced in the repeating pattern along a second edge of the first rail. The second edge of the first rail is disposed opposite the first edge of the first rail such that the first rail includes repeating first pairs of apertures. Each pair of apertures is configured for tightly receiving one of the plurality of pickets therethrough. The second substantially hollow rail includes a third plurality of apertures spaced in the repeating pattern along a first edge of the second rail and a fourth plurality of apertures spaced in the repeating pattern along a second edge of the second rail. The second edge of the second rail is disposed opposite the first edge of the second rail such that the second rail includes repeating second pairs of apertures. Each pair of apertures is configured for tightly receiving one of the plurality of pickets therethrough.
[0017] Additionally, the pickets are configured to be fixedly attached to the first rail by sliding each of the plurality of pickets partially through the first pairs of apertures along the first rail such that at least one interference member per picket is located directly adjacent a respective lower rim of a respective aperture of the first rail. Additionally, the pickets are configured to be fixedly attached to the second rail by sliding each of the plurality of pickets partially through the second pairs of apertures along the second rail such that at least one interference member per picket is located directly adjacent a respective lower rim of a respective aperture of the second rail. Sliding each of the plurality of pickets partially through the first pairs of apertures along the first rail and partially through the second pairs of apertures along the second rail also causes at least one interference member per picket to be located directly adjacent a respective upper rim of a respective aperture of either the first rail or the second rail.
[0018] In some embodiments, the pickets are configured to be fixedly attached to the first rail and the second rail by first sliding each of the plurality of pickets partially through the first pairs of apertures along the first rail such that at least one interference member per picket is located directly adjacent a respective internal lower rim of a respective aperture of the first rail. Additionally, the pickets are configured to be fixedly attached to the first rail and the second rail such that the pickets are provided load-bearing support along each respective lower rim. Lastly, the pickets are configured to be fixedly attached to the first rail and the second rail by sliding each of the plurality of pickets partially through the second pairs of apertures along the second rail such that at least one interference member per picket is located directly adjacent a respective internal lower rim of a respective aperture of the second rail, providing load bearing support for each respective picket along each respective lower rim.
[0019] In certain other embodiments, each picket of the plurality of singular blow-molded pickets includes a plurality of interference members defined along a first face of each picket and at least one interference member defined along a second face of each picket. At least a second portion of the plurality of pickets are shaped according to a second predefined blow-molding pattern.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Further advantages of the disclosure are apparent by reference to the detailed description in conjunction with the figures, wherein elements are not to scale so as to more clearly show the details, wherein like reference numbers indicate like elements throughout the several views, and wherein:
[0021] FIG. 1A is a perspective view of a fence section according to a fence system described in the disclosure; FIG. 1B is an exploded view thereof; and FIG. 1C is a cross-sectional side view thereof.
[0022] FIGS. 2A-2C are perspective views of a rail component of the system of FIGS. 1A-1C .
[0023] FIG. 3 is a perspective view of picket components of the system of FIGS. 1A-1C .
[0024] FIGS. 4A-4C and 5 A- 5 C show picket components of the system of FIGS. 1A-1C .
[0025] FIG. 6A is a perspective view of a fence section according to another embodiment of the fence system described in the disclosure, and FIG. 6B is an exploded view thereof.
[0026] FIG. 7A is a perspective view of a fence section according to yet another embodiment of the fence system described in the disclosure, and FIG. 7B is an exploded view thereof.
[0027] FIG. 8A is a perspective view of a fence section according to a still further embodiment of the fence system described in the disclosure; FIG. 8B is a cross-sectional side view thereof; and FIGS. 8C and 8D are exploded views thereof
[0028] FIGS. 9A-9C are perspective views of a rail component of the system of FIGS. 8A-8D .
[0029] FIGS. 10A-10C show a picket component of the system of FIGS. 8A-8D .
[0030] FIG. 11 shows an interference fit of a picket and a rail according to the disclosure.
[0031] FIG. 12 shows relative dimensions of components of a picket and a rail according to the disclosure.
[0032] FIG. 13 shows an exemplary partial cut-away side view of a picket and rails engaged with the picket.
[0033] FIG. 14 shows another exemplary partial cut-away side view of a picket and rails engaged with the picket.
[0034] FIG. 15 shows yet another exemplary partial cut-away side view of a picket and rails engaged with the picket.
[0035] FIG. 16 shows still another exemplary partial cut-away side view of a picket and rails engaged with the picket.
DETAILED DESCRIPTION
[0036] Referring to the FIGS. 1-16 , the disclosure relates to a fencing system including, for example, a fence section 10 including a plurality of pickets 12 , a first rail 14 , and a second rail 16 . Each of the pickets 12 are formed as a single (or “singular”) piece by blow molding in a single molding step and are, therefore, formed based on one or more predefined blow-molding patterns. The first rail 14 is preferably substantially hollow and includes a plurality of first apertures 18 along two opposing sides of the first rail 14 , forming a pattern of pairs of first apertures 18 along the first rail 14 . Each pair of the first apertures 18 is configured to tightly receive one of the pickets 12 therethrough. Similarly, the second rail 16 is also preferably substantially hollow and includes a plurality of second apertures 20 along two opposing sides of the second rail 16 , forming a pattern of pairs of second apertures 20 along the second rail 16 . Each pair of the second apertures 20 is configured to tightly receive one of the pickets 12 therethrough.
[0037] With reference to FIGS. 13-16 , each of the pickets 12 includes a plurality of interference members 22 defined thereon. At least two of the interference members ( 22 A and 22 C) for each picket are defined along a first face 24 of each picket as well as at least one interference member ( 22 B) defined along a second face 26 of each picket. For each picket, at least one interference member ( 22 B) is located directly adjacent a lower rim 28 of one of the first apertures 18 , at least one interference member ( 22 C) is located directly adjacent a lower rim 30 of one of the second apertures 20 , and at least one interference member ( 22 A) is located directly adjacent either an upper rim 32 of one of the first apertures 18 or an upper rim 34 of one of the second apertures 20 .
[0038] The interference member 22 B is preferably located as shown in FIG. 13 directly adjacent a lower rim 28 of one of the first apertures 18 from an internal position (internal of the first rail 14 ), thereby providing load bearing support function for the applicable picket. Similarly, the interference member 22 C is preferably located directly adjacent a lower rim 30 of one of the second apertures 20 from an internal position (internal of the second rail 16 ), thereby providing load bearing support function for the applicable picket. Preferably, each picket includes at least four interference members 22 at every rail interface 36 as shown in FIG. 14 wherein the internal height “H” of each rail ( 14 , 16 ) is approximately the same as the distance “D” between outer edges 38 of the interference members 22 located on the same face of a picket between a rail.
[0039] FIG. 15 shows an example of a picket that includes three interference members 22 per rail interface 36 . FIG. 16 shows an example of a picket wherein some of the interference members 22 are located at locations external from the first rail 14 and the second rail 16 . However, internal location of interference members is preferred so as to preserve the look of a traditional picket fence with pickets made of wood or otherwise having substantially smooth and flat, panel-like exterior surfaces.
[0040] As shown by comparing FIG. 1A , FIG. 6C , FIG. 7A , and FIG. 8A , the style of picket can vary, which, in turn, can vary the size and/or shape of apertures in the various rail designs to accommodate for the different sizes of the variously styled pickets. FIG. 1A through FIG. 3 show an example of a picket fence section 40 wherein the style of picket varies according to a repeating pattern along the fence section 40 . Because the style and size of picket varies according to a particular pattern, the size of the respective apertures 18 in the first rail 14 and the size of the respective apertures 20 in the second rail 16 also vary accordingly as shown, for example, in FIGS. 2A-2C .
[0041] FIGS. 6A-6B show another example of a fence section 42 including pickets 44 all made from a first predefined blow-molding pattern along with an upper rail 46 and a lower rail 48 , wherein both rails include apertures 50 configured for receiving the pickets 44 . FIGS. 7A-7B show yet another example of a fence section 52 including pickets 54 made from a second predefined blow-molding pattern along with an upper rail 56 and a lower rail 58 , wherein both rails include apertures 60 configured for receiving the pickets 54 . A plurality of interference members 62 are defined along widthwise surfaces 64 of the pickets 54 in this example. FIGS. 8A-10C show a third example of a fence section 66 including pickets 68 all made from a third predefined blow-molding pattern along with an upper rail 70 and a lower rail 72 , wherein both rails include apertures 74 configured for receiving the pickets 68 . A plurality of interference members 76 are defined along the depthwise surfaces 78 of the pickets 68 in this example.
[0042] The size of various components of the fence system described herein can vary based on various factors including, for example, customer need, although traditional fence picket heights, widths, and lengths are often preferable. The plurality of fence pickets and associated rails are preferably made of polyvinyl chloride (PVC), high density polyethylene, polypropylene or other similar polymer, copolymer, and/or combinations thereof The rails are preferably made using an extrusion process. Fences are preferably formed in sections (e.g., the fence section 10 shown in FIG. 1A ) prior to shipment to dealers or customers. However, kits of picket fence components are also contemplated wherein the fence components are shipped unattached. FIG. 8C shows an example of a fence kit 80 including the plurality of pickets 68 , the upper rail 70 , and the lower rail 72 used to form the fence section 66 shown in FIG. 8A . End posts may be included in fence kits wherein the upper rail 70 and the lower rail 72 are attached to the end posts in any manner known to person having ordinary skill in the art.
[0043] The previously described examples of the present disclosure have many advantages, including providing traditionally styled picket fence sections made from recyclable and/or recycled material, the whole of which is lighter than wood and more impervious to the elements than traditional wood picket fences. Another advantage is the traditional appearance of painted wooden picket fence pickets with substantially planar surfaces with little or no functional features appearing on the outside surfaces of the various parts of each fence section.
[0044] The foregoing descriptions of preferred embodiments for this disclosure have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the disclosure to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiments are chosen and described in an effort to provide the best illustrations of the principles of the disclosure and its practical application, and to thereby enable one of ordinary skill in the art to utilize the disclosure in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the disclosure as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled. | A fence system including fence sections including singular blow-molded pickets that engage with fence rails using no additional parts and wherein the pickets show no external signs of functional engagement between the pickets and fence rails (e.g., pickets having substantially planar surfaces common to traditional wooden picket fence designs). | 4 |
BACKGROUND OF THE INVENTION
[0001] Hip surgery requires the implantation of a femoral stem and an acetabular cup. The femoral stem has a spherical head that attaches to the neck of the stem and is free to articulate within a bearing insert that is fitted into the shell of an acetabular cup. Should the stem and cup not be positioned/aligned accurately, the neck of the stem may impinge on the lip of the insert resulting in a levering action that could allow the femoral head to cam out of the insert resulting in a permanent dislocation of the head. The impingement can also lead to excessive component wear and possibly failure.
[0002] In addition, a malpositioned cup can result in excessive liner wear even without impingement. A shell with a high abduction (inclination) angle can have joint forces concentrated near the cup liner rim, thereby increasing the wear rate due to concentrated forces.
[0003] Reducing or eliminating the chance for neck/insert impingement and high inclination angles is critical to eliminating dislocation and wear, which can ultimately result in a revision surgery to correct compound alignment (abduction and anteversion).
[0004] A recent study by H. Malchau et al., Clin. Orthop. Relat. Res. (2011) 469; 319-329 reviewed the implanted acetabular cup position post implantation in relation to the pelvic anatomy. The study of 1823 patients revealed that the cup position varied widely in reference to their described target zone.
[0005] One main reason for such variation is that the exact position of the patient's pelvis is not known in relation to the operating room (OR) table. Surgeons must rely on their experience to know how to position the cup, however the cup may not be implanted in the intended orientation. This is especially true with respect to less experienced surgeons.
[0006] Alignment of an acetabular cup can be achieved with an alignment guide that attaches to an insertion rod for facilitating the insertion of the acetabular cup into the acetabulum. The alignment guide preferably references the surgical table on which the patient rests. Conventionally, it is assumed that the patient's pelvis is parallel to the table, and that the surgical tables is parallel to the floor. Based on such assumptions, the ordinary position (in most patients) for the acetabular cup is 45° of inclination (abduction) and 20° of anteversion. For a discussion of angles of anteversion and also inclination or abduction of the acetabular cup when installed in the acetabulum, see, for example, U.S. Pat. No. 6,395,005, the disclosure of which is incorporated by reference herein in its entirety.
[0007] It has been found based on post-operative x-rays, however, that despite the alignment guide being parallel to the floor during insertion, of the acetabular cup, the resultant inclination or anteversion of the acetabulum in relation to the alignment guide is often different than expected and, thus, the acetabular cup has been installed at a less than ideal position. The pelvic position changes in relation to the operating room table which is not recognized during the procedure for example.
[0008] Presently most orthopedic companies offer instrumentation to direct reaming for acetabular cups and cup impaction which is an antenna-like device that attaches to either the reamer shaft or the cup impaction tool. Such cup alignment instruments are shown in, for example, U.S. Pat. Nos. 5,037,424, 5,571,111 and 6,395,005. When an x-shaped “antenna” is used a cup impactor that is oriented 45 degrees to the floor and 20 degrees to the long axis of the patient. The ‘X’ shape on the antenna is set parallel to the floor, and one leg of the ‘X’ set in line with the long axis of the body. One leg is for a left leg operation, and the other for a right leg operation.
[0009] Some of the drawbacks of this type of instrument are that the pelvis usually shifts when the patient is laid on the operating room table. If the pelvis does not shift, and the surgeon wants a 45/20 cup position, then the surgeon could use the instrument as is and get the perfect 45/20 alignment within the bone. However, most times the pelvis does shift in three possible planes: tilt, obliquity, and rotation. The surgeon does not know in which direction or by how much and therefore must use his experience or intuition to apply a correction factor to the direction of cup impaction. The actual cup orientation after impaction is not usually known until after the operation is complete and a post-operative x-ray is taken, and the patient is in recovery, and therefore at a time when changes to cup orientation are not possible without reoperation.
[0010] Another drawback is that the current antenna/impactor combination is set at set angles. For example a 45/20 degree abduction/anteversion orientation. If the surgeon determines that orientation of 40° to the floor and 15° to the long axis of the patient's femur is best for the patient, the set angles are of little use, or again the surgeon has to estimate a correct alignment. The orientation of the antenna/impactor combination in practice is set visually. The antenna shaft is set vertically, with the antenna ‘X’ cross bars parallel to the floor. The 20 degree orientation to the patient long axis is visual as well. Many surgeons do not use the antenna at all.
[0011] Some major prosthetic hip joint companies offer a navigation option to surgeons. This system uses cameras in the operating room and optical trackers on instrumentation. From a clinical perspective, the major drawbacks for navigation are that the technique involves placing invasive pins having the tracker thereon in the patient pelvis and femur. The pins are placed in the pelvis and the femur, through the skin and screwed into the bone. Using pins results in multiple separate wounds and increases the possibility of infection. This technique is also time intensive. Pins must be placed and pointers with trackers on them are used multiple times to register anatomy. This technique has a learning curve. The software and technique require extensive training and practical experience. Some systems require a pre-op CT scan which is costly.
[0012] A more recent development is digital imaging which produces an x-ray like image on a digital receiver. Once digitized, the digital image can be used to identify points in order for the system to calculate lengths and angles which could be used by the surgeon to help to identify how the pelvis is oriented to the operating room table. The surgeon can take pre-operative and intra-operative x-rays and pick points on the screen to calculate lengths and angles. This is a relatively new technology with a relatively small amount of users.
[0013] The x-rays can be visually observed for comparison. The system can aid the user by allowing the user to plan by designating the desired cup inclination and version angles pre-operatively as well as taking dimensions that will help to designate leg length and femoral stem offset corrections. Taking dimensions that will measure the cup inclination and version angles of the actual implanted cup intra-operatively as well as taking dimensions that show that actual leg length and offset of the trials or implants.
[0014] However, they do not aid the user by figuring out how the pelvis has shifted on the table as there is no algorithm to do this. A pelvis may have tilted by 15 degrees, yet the cup angle measurement only measures the cup angle at the plane that the x-ray is taken. If the pelvis has tilted by 15 degrees, then the correct cup placement would not be 45°/20° to the intra-op x-ray image, but should be adjusted to account for the tilt.
[0015] These current digital imaging systems do not have an algorithm that tries to compare pre-operative and intra-operative images to calculate how the intra-operative pelvic position changes in orientation to a pre-operative image. Furtheremore, the current digital systems don't calculate the cup impaction angles that would account for these changes. Instead the cup needs to be first impacted into the bone prior to taking the image, and reoriented if not in the desired position. Reorienting the shell could compromise the fit and security of the cup to the acetabular bone cavity. Multiple reorientations could possibly compromise the fit to the point that a secure fit is no longer achieved. In this situation, the surgeon may have to remove the shell, ream up to the next size shell, and start over. The removal of further acetabular bone is not ideal as this could compromise the overall strength of the remaining bone, and reduce the amount of bone for any future revisions. Current digital imaging techniques require successive intra-operative images, exposing the patient and the surgical team to higher levels of radiation than with a single image.
BRIEF SUMMARY OF THE INVENTION
[0016] The present invention, in the preferred embodiment, uses a combination of digital imaging and orientation technology to improve upon the limitations described above, along with an algorithm that determines the amount of pelvic movement in the three planes (obliquity, tilt, rotation) that is used as input for the orientation technology. The preferred embodiment to calculate pelvic tilt obliquity and rotation inoperatively which no other system does. Most pre-operative x-ray images are taken lying down, and hence placing the pelvis in an unnatural position. A standing x-ray is the gold standard as the amount of pelvic tilt when standing is what is right for that individual. This invention serves to recreate the natural standing x-ray tilt and, if desired, obliquity and rotation amount intra-operatively by adjusting the orientation of reaming and cup impaction, and performing these functions at the pre-op plan angles determined by the user (e.g. at 40° inclination and 15° anteversion).
[0017] The connection uses a method for aligning an acetabular cup including: taking a pre-operative preferably standing anterior/posterior view digital x-ray image and a lateral view standing digital x-ray image of the pelvis of a patient. A desired cup abduction and anteversion angle is determined based on two standing x-ray images. At least three points on the digital anterior/posterior digital x-ray image and at least two points on the lateral digital x-ray image are identified. The lengths and angles between each of the points on both the anterior/posterior digital image and the lateral digital image are calculated. A patient is positioned on an operating table in an operating room. The preferred operating table has a reference element thereon. In the preferred embodiment, the operating room has a navigation system therein, the preferred operating table has a navigation tracker mounted in a known position with respect to the operating table. Alternately, the reference system could reference the floor or other fixed point including the operating room table. At least one pelvic digital x-ray image of the patient positioned on the operating table is taken with the x-rays including the reference element. At least three points are identified on the intra-operative x-ray image. In the preferred embodiment, the points corresponding to the points on the pre-operative x-ray image. The lengths and angles between each of the at least three points on the intra-operative digital images are then calculated. An intra-operative angular deviation of the acetabular cup insertion instrument from the desired abduction and anteversion angle i.e. calculated by comparing the dimensional differences between the points on the pre-operative standing x-ray images and the at least one intra-operative x-ray image. The insertion instrument is then aligned to a calculated angular position, based on the intra-operative deviation, using the navigation camera and a navigation tracker mounted on the insertion instrument.
[0018] The at least three points on the anterior/posterior pre-operative and intra-operative images are preferably the right and left promontory points and the pubic symphysis. The at least two points on the intra-operative lateral image are preferably the left or right promontory and the public symphysis. However, other points can be used. Additional points may be selected from the group consisting of acetabular teardrops, the obturator foramen and the base of the left and right ischial rings, the points being identified on the pre-operative and intra-operative images. The angle between a line connecting the ischial ring points and the reference element indicates any obliquely change between the pre-operative, preferably standing pelvic anterior/posterior x-ray image and the at least one intra-operative x-rays. The reference element may be a radiolucent bar extending parallel to the operating table surface, the radiolucent bar having two radiopaque markers thereon. Alternately, the radiolucent bar has three radiopaque markers, each marker located at an apex of a triangle. The pre-operative determination of the desired cup abduction and anteversion angles based on the standing x-ray are about 40 to 45 degrees and 15 to 20 degrees respectively. The calculations are performed by a computer using digital image analysis software receiving input from a digital x-ray machine and an operating room navigation tracking system. A pubic tilt may be is calculated by comparing the distance between the promontory points and the pubic symphysis on both the pre-operative standing x-rays and the at least one intra-operative x-ray.
[0019] As used herein when referring to bones or other parts of the body, the term “proximal” means close to the heart and the term “distal” means more distant from the heart. The term “inferior” means toward the feet and the term “superior” means toward the head. The term “anterior” means toward the front part or the face and the term “posterior” means toward the back of the body. The term “medial” means toward the midline of the body and the term “lateral” means away from the midline of the body
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIGS. 1A to 1C are reference diagrams showing pelvic obliquity, pelvic rotation and pelvic tilt which three axial movements typically occur when moving from a standing position to a prone position;
[0021] FIG. 2 shows nine possible anatomic landmarks on a pelvic anterior/posterior x-ray;
[0022] FIG. 3 shows three points on a pelvic anterior/posterior x-ray including the right and left promontory points and the pubic symphysis;
[0023] FIG. 3A shows a lateral view of a lateral x-ray showing a left promontory point and the pubic symphysis;
[0024] FIG. 4 shows an artist's rendition of an anterior/posterior standing x-ray showing the three points of FIG. 3 and dimensions A, B and C;
[0025] FIG. 5 shows an artist's rendition of a lateral x-ray showing the anatomic points shown in FIG. 3A including the dimensions D, E and F therebetween;
[0026] FIG. 6 shows a reference system mounted on an operating table including a radiolucent guide bar and two radiopaque markers;
[0027] FIG. 7 shows a pelvis area of a patient located on an operating table showing the right and left promontory points, pubic symphysis and the base points of the right and left ischial rings;
[0028] FIG. 8 is a anterior/posterior x-ray showing the anatomic landmark points on the pelvis;
[0029] FIG. 8A is an artist's rendition of a pelvis of a patient oriented on an operating table having a reference element mounted thereon with the pelvis in a first orientation having a pelvic tilt;
[0030] FIG. 8B is an artist's rendition of the pelvis of 8 A showing the various components for a reaming operation including the chosen landmarks.
[0031] FIG. 8C is a lateral x-ray of the patient's pelvis of FIGS. 8 to 8B ;
[0032] FIG. 8D is a picture of the anterior pelvic x-ray showing the promontory points and the symphysis;
[0033] FIG. 8E shows three views of a pelvis, in an idealized position on an operating table on three standing image planes with an acetabular impactor at 45% version.
[0034] FIGS. 9 and 9A are an artist's rendition of an intra-operative x-ray image taken in the anterior/posterior and lateral views of a pelvis on an operating table in a second position;
[0035] FIG. 10 shows an example of pelvis shift in the standing plan x-ray when a patient is placed on an operating table.
[0036] FIGS. 10A and 10B are anterior and posterior intra-operative views of a pelvis on an operating table showing 45° inclination and 20° anteversion;
[0037] FIGS. 11 through 11D show the reorientation of the acetabular cup impactor/reamer from a pre-operative plan based on a standing x-ray to an intra-operative plan accounting for movement of the pelvis with 10° tilt;
[0038] FIGS. 12 through 12L show the repositioning of an acetabular cup impactor/reamer from an inter-operative plan of 45° inclination and 20° anteversion with 8° rotation of the pelvis when placed on an operating table as set forth in example 4 of the present application;
[0039] FIGS. 13 through 13G shows the repositioning of an acetabular cup impactor or reamer from a pre-operative plan based on a standing x-ray with 45° inclination and 20° anteversion desired based on the standing x-ray with the pelvis being rotated in 10° of obliquity as set forth in example 5 of the present application;
[0040] FIGS. 14 through 14E shows the repositioning of an acetabular cup impactor/reamer where the desired orientation is 45° inclination and 20° anteversion based on a standing x-ray with 10° of obliquity imparted to the pelvis when being placed on an operating table as set forth in example 6 of the present application;
[0041] FIGS. 15 through 15D of the present application show the repositioning of an acetabular cup impactor from a desired 45° inclination and 20° anteversion based on a standing x-ray to a pelvis oriented on an operating table with 10° tilt, 8° rotation and 10° obliquity change from the standing x-ray as set forth in example 7, with FIGS. 15 and 15A showing the standing x-ray anterior/posterior plane, the central plane and a rotational plane of the pelvis along with the x, y and z vectors lying on each of the planes; and
[0042] FIG. 16 shows a preoperative image showing an individual with one leg shorter than the other (non-zero pelvic tilt in the x-ray).
DETAILED DESCRIPTION
[0043] The method for aligning an insertion instrument for an acetabular cup of the present invention will now be described. Such an insertion instrument may be a reamer or impactor. For definitional purposes, pelvic obliquity and tilt rotation are shown respectively in FIGS. 1A , 1 B and 1 C. Initially a pre-operative digital standing A/P (anterior/posterior)( FIGS. 2 and 3 ) and lateral view x-ray ( FIG. 3A ) images of a pelvis 10 are taken. A magnification marker (not shown) may be included in these two x-rays.
[0044] The goal of the invention is that a pre-operative x-rays ( FIGS. 2 and 4 ) are taken and a plan established for the best acetabular cup position (inclination and version) relative to right and left acetabulum pelvis 10 for the individual patient. The pre-operative A/P plane is reestablished the calculations relative to the intra-op pelvis position ( FIG. 3 ).
[0045] The pre-operative cup position plan for inclination and version is then applied to the reestablished plane. In order to do this, at least some of the changes that took place in tilt, obliquity and rotation from their pre-operative position (angular changes) are determined and then used with the acetabular cup impactor. This can be done without placing any pins or other elements in contact with the body.
[0046] In the preferred embodiment, the x-ray images are taken with the patient standing. A standing image naturally orients the pelvis to the individual patients natural pelvic tilt, obliquity and rotation.
[0047] Referring to FIG. 2 to FIG. 5 , the surgeon identifies at least five or more specific points on the images (three on A/P x-ray and two on lateral x-ray). The three points on the A/P x-ray are preferably the left and right promontory 20 , 22 and pubic symphysis 24 . The two points on the lateral x-ray are the lateral promontory point 22 and the pubic symphysis 24 . Other possible pelvic anatomy points are shown in FIG. 2 as the bases of the left and right ischial rings 30 , 32 , the left and right inside obturator foramen 34 , 36 and the left and right acetabular teardrops 37 and 39 . It may not be necessary to compare every pre and intra-operative dimension to calculate tilt, rotation and obliquity changes.
[0048] Computer software may be used to calculate lengths and angles between these five points and retains the calculated dimensions to compare to a future correlated intra-operative dimension on intra-operative x-rays. For example, FIG. 4 shows lengths A, B C and D based on points 20 , 22 and 24 and FIG. 5 shows lengths D, E and F based on points 22 and 24 and a point 25 at the origin of a right triangle formed by points 22 , 24 .
[0049] Referring to FIGS. 6 and 7 , the intra-operative routine starts with the patient being placed on an operating 46 table usually on the side opposite the hip being replaced. The surgeon performs the operation up to the point of reaming the acetabulum for acetabular cup. Prior to taking an intra-operative image, a reference plane is established. The reference plane is used to translate the angular changes to angular dimensions for a single measurement system, such as a navigation system, to use to direct the reamer and acetabular cup placement. Referring to FIGS. 6 and 7 , preferably a radiolucent reference system 38 generally denotes as (system 38 ) with two or three system 38 1 of FIG. 7 , radiopaque markers 44 , 45 and 47 , is attached to the table. Reference system 38 , 38 1 needs to be located so it is able to be included in the intra-operative x-ray image. Reference system 38 , 38 1 have a horizontal bar 40 which and can be mounted on a post 42 vertically mounted on operating table. The reference element could also be just the post with radiopaque markers, and the post could be a patient positioning post for a peg board. The reference systems 38 , 38 1 could conceivably be the actual operating room table 46 . Preferably a navigation system tracker 50 is then placed on the reference bar 40 . Magnification markers could be included in or on reference bar 40 . Bar 40 could be made out of radiolucent material with at least one magnification marker imbedded in the bar. The markers could be spherical in shape and the points taken could be the centers of the markers.
[0050] As shown in FIGS. 8A to 8E , at least one intra-operative digital x-ray image (preferably an A/P image FIG. 8 ) is taken making sure the reference bar 40 is within the image (see FIGS. 8A to 8E ). The surgeon identifies at least 5 specific points on the intraoperative A/P image. The preferred embodiment has the surgeon identifying seven points. The promontory points 20 , 22 and pubic symphysis point 24 are similar to the pre-operative image. The two ischial ring points 30 , 32 are used to detect obliquity change. (Note: Other points that are meant be symmetrical about the pelvic anatomy can be chosen. Examples are: inside left and right obturator foramen 34 , 36 , and left and right acetabular teardrops 37 , 39 . The two ischial points or other symmetrical points are chosen to make calculating the obliquity easier. The line between the two promontory points could also be used, negating the need for two other symmetrical points.)
[0051] Software is used to calculate key lengths and angles between points on intraoperative image. Note that the specific points are at the center of the pubic symphysis 24 , the two promontory points 20 , 22 , a point 35 at the center between the promontory points, and a point 49 that is 90° to the line between the promontory points. By determining the angular changes in tilt obliquity and rotation of the pelvis, the software can recreate a virtual standing image in reference to the pelvic position on the table ( FIG. 8E ). FIG. 8E shows the pelvis in a perfect prone position where there is no tilt rotation or obliquity and impactor is done at 45° inclination and 0° anteversion relative to table 46 . The standing image plane is shown as 37 and is a frontal or coronal plane.
[0052] The software identifies abduction and anteversion angles relative to the reference in order to achieve the pre-operative desired cup position as shown in FIGS. 3 and 4 . Referring to FIGS. 5 , 6 , 7 , 8 and 9 , the preferred embodiment uses commercially available navigation system is used to determine the position of the cup impaction angle versus the reference bar 40 . A tracker 50 is placed on bar 40 and a tracker 52 is placed on an cup impactor 54 . Impactor 54 includes shaft 56 extending along axis 59 which engages the inside of an acetabular cup shell or reamer 5 located in acetabulum 11 , 13 . The impactor is adjusted to the angles α and β calculated by a computer program while looking at a monitor. Preferably, the same monitor as the digital image monitor. Alternate embodiments could obtain the desired angles via manual goniometers or protractors, or via electronic means suh as with an inclinometer. Software for the required calculation is commercially available.
[0053] The surgeon then reams the acetabulum at indicated calculated angles with a standard acetabular reamer. If the surgeon suspects that the pelvis has moved prior to cup impaction, then an x-ray of the at least five points can be retaken. The surgeon impacts cup at the calculated angles α and β.
[0054] The following examples show calculations and workflow of various possible intraoperative pelvic orientations.
Example 1
[0055] This example shows how the cup impactor is positioned relative to reference bar 40 to obtain the desired inclination and anteversion. The pelvis is shown in a perfect orientation similar to FIG. 8D .
[0056] Referring to FIGS. 9 and 9A there is shown a “perfect” pelvic orientation on table 46 . Also shown is the acetabular cup impactor 54 with shaft 56 shown at a 45° inclination 0° anteversion and zero tilt, rotation and obliquity with respect to reamer or impactor 57 .
[0057] As shown in FIGS. 9 and 9A pelvis 10 did not alter position from the A/P image (pelvis in a perfect position) when placed on table 46 . The basic pelvis orientation is exactly 90° to the standing x-ray. The plane is normal to the table. This is shown by the 0° alignment between the planes of the two x-rays (pre-standing and intraoperative prone). The plane that the standing x-ray was taken at is shown with the line 59 of FIG. 9 . The plane through line 59 is normal to the table. The impactor is placed in the reamed acetabulum and rotated up to 45° in relation to the reference bar 40 . In general, the plane that the standing x-ray was taken at is first found, and then impactor 54 is angled for inclination along that plane, and then anteversion is placed normal to the plane by pivoting in the acetabulum (in example 1 this is 0°). The bar 40 defines the plane normal to the intra-operative x-ray view and parallel to the front edge of the table. It is perpendicular to the cross-table x-ray image taken in the operating room. The front edge of the operating room table could also be used as a reference, however, the size of the x-ray image may not be able to capture both the table and the anatomy required in the same shot. Having a reference bar 40 attached to the table allows it to be moved to a position that is within the image and not blocking the anatomic points needed for the calculations. The navigation tracker 50 is attached to whatever the reference is, whether it be the bar or the table itself.
[0058] Referring to FIG. 10 , the navigation system first recreates the standing x-ray plane 37 , defines a central plane 39 then calculates the amount the pelvis has moved off that reference plane. A rotational plane 35 is also shown. Reference bar 40 defines plane normal to x-ray view and parallel to table.
Example 2
[0059] Referring to FIGS. 10A and 10B , similar “perfect” pelvic orientation on the OR table as with Example 1. Standing x-ray plane is normal to the table shown with acetabular cup impactor at a now desired 45° inclination ( FIG. 10A ) and 20° anteversion ( FIG. 10B ). The cup impactor 54 would be oriented 45° from the reference bar 40 and 20° off the reference bar 40 . The two navigation trackers 50 , 52 , one of the reference bar, and one on the impactor helps facilitate finding these angles for the impactor. The orientation is now 45 DEG INCLINATION, 20 ANTEVERSION, 0 TILT, 0 ROTATION and 0 OBLIQUITY.
Example 3
[0060] Here the cup impactor orientation is 45° INCLINATION, 20° ANTEVERSION, AND THE PELVIC ORIENTATION IS 10° TILT (to be confirmed below), 0° ROTATION and 0° OBLIQUITY. Dimensions for calculations for determining amount of tilt are pre-op images are shown in FIGS. 11 , 11 A and 11 B. Intra-op image: A/P image shown in FIG. 11A : May have tilt. This is to be verified by the calculation outlined below. A Pre-op A/P, preferably standing image is taken and shown in FIG. 11 . An Intra-operative A/P image is taken and shown in FIG. 11A . The 3.179 dimension between points 24 and 35 is compared to the pre-op dimension of 2.599 between points 24 and 49 . Since the 3.179 is greater than 2.599, it indicates that the pelvis has tilted forward (positive tilt) by a certain amount. Dimensions for calculations for determining amount of tilt: A pre-operative lateral image is shown in FIG. 11B with lengths B, C, and E and angle D.
[0000] Table 1 refers to the dimensions of FIGS. 11A and 11B .
[0000] TABLE 1 Feature length/ Letter Name Given angle Pre-op Intra-op A Promontory Between 4.173 4.173 Line Promontory points B Normal Line On A/P Image: 2.599 3.179 (90 deg) between Prom Line and Pub Sym. On Lateral Image: vertical distance between Prom pts and Lat Image Horizontal Line C Lateral Image Promontory to 4.412 N/A as no Hypotenuse Pub Sym lat image taken but 4.412 remains the same D Lateral Image Angle between 36.094 To be Tilt Angle Hypotenuse and deg calculated line parallel to floor E Horizontal Pre-op line Not N/A Line parallel to important the floor or as no OR table rotation Tilt Angle Relative change in pelvic tilt from the pre- op angle D to the intra-op angle D
From FIGS. 11A and 11B : Sin angle D=3.179/4.412
Angle=46.098 deg (intra-op angle D)
Tilt angle=angle of intra-op image minus angle of standing image
Tilt angle=46.098-36.094
Tilt angle˜10 degrees
FIGS. 11C and 11D show what angles the navigation would set the impaction at.
Inclination=45 deg (remains unchanged)
Version=20 deg anteversion minus 10 deg positive tilt=10 deg as shown
Example 4
[0061] The cue orientation pelvic orientation in this example is 45 DEG INCLINATION, 20° ANTEVERSION, and the intra-operative pelvic orientation is 0° TILT, 8° ROTATION (to be confirmed below) and 0° OBLIQUITY. FIGS. 12 and 12A show an inter-operative top view ( FIG. 12 ) and front view ( FIG. 12A ) of what a pelvis at 8 deg of Rotation looks like. FIG. 12 shows standing x-ray plane 37 and rotational plane 140 . Calculations for determining amount of rotation: Previously (similar to FIGS. 11 and 11C ) taken pre-operative images are shown in FIGS. 12B and 12C . FIGS. 12D and 12E are A/P Intra-operative images which show the pelvis may have rotated. This is to be verified. The following table 2 refers to the dimensions in FIGS. 12B to 12E .
[0000]
TABLE 2
Feature length/
Letter
Name Given
angle
Pre-op
Intra-op
A
Promontory
Between
4.173
4.133
Line
Promontory
points
B
Normal Line
On A/P Image:
2.599
2.599
(90 deg)
between Prom
Line and Pub
Sym.
On Lateral
Image: vertical
distance
between Prom
pts and Lat
Image
Horizontal Line
C
Lateral Image
Promontory to
4.412
N/A as no
Hypotenuse
Pub Sym
lat image
taken but
remains
the same
D
Lateral Image
Angle between
36.094 deg
N/A as no
Tilt Angle
Hypotenuse and
lat image
line parallel
taken but
to floor
remains
the same
E
Horizontal
Pre-op line
Not
To be
Line
parallel to the
important
calculated
floor or OR
table
F
Midpoint Line
Line between
Not
Not
Prom Line
important
important
Midpoint and
Pub Sym
G
Rotational
Distance
0
0.496
Offset
between Normal
Distance
Line and
Midpoint Line
on Promontory
Line
H
Rotational
Angle of Pelvic
0
To be
Angle
Rotation of
calculated
Intra-op
relative to
Pre-op
Rotational Angle
[0062] Referring to FIG. 12E to find the Rotation Angle (H), first find length E.
B 2 +E 2 =C 2
E 2 =C 2 −B 2
E 2 =(4.412) 2 −(2.599) 2
E=3.565
[0063] The Lateral Image Horizontal Line dimension E found above, 3.565″, is now used to help calculate the amount of intra-operative pelvic rotation. The Rotational Offset Distance (0.496″), FIG. 12D , was found on the intra-op digital image device. Using these two numbers, the Rotational Angle can be found.
Sin H=0.496/3.565
Rotational Angle H=7.997 deg
[0064] The pelvis has rotated nominally 8 degrees
Note:
[0065] A less optimal way of determining the degree of rotation would be to compare the pre-op Promontory Line distance (4.173) to the intra-op distance (4.133). The 4.133 distance is a projection of the 4.173 distance at the rotation angle.
[0000] Cos rotation angle=4.133/4.173
Rotation angle=7.939 degrees
[0066] FIG. 12F shows what 8 degrees of rotation looks like from a side view with sanding x-ray plane 37 and rotation plane 137 .
[0067] Calculations for finding the impactor angles to be used by Navigation are shown in FIGS. 12G to 12J .
[0000] Step 1: Project the impactor angle position (45/20) onto the plane of angle change. In this case it is the Rotation Plane shown in FIG. 12G .
[0000]
TAN
45
°
=
h
R
SIN
45
°
=
h
L
COS
45
°
=
R
L
SIN
20
°
=
B
R
F
=
SIN
20
°
R
F
=
(
SIN
20
°
)
(
COS
45
°
)
L
TAN
α
=
h
F
TAN
α
=
sin
45
°L
(
sin
20
°
)
(
cos
45
°
)
L
α
=
71.118
°
[0000] Step 2: Rotate 8° as shown in FIG. 12 H)(71.118-8°.
[0000]
cos
71.118
°
=
F
L
R
cos
63.118
°
=
(
F
+
f
)
L
R
F
cos
71.118
°
=
(
F
+
f
)
cos
63.118
°
F
.3236
=
F
.4521
+
f
.4521
F
=
.7157
F
+
.7157
f
.2843
F
=
.7157
f
f
=
.3973
F
[0000] Step 3: As shown in FIG. 12I .
[0000]
From
Before
:
F
=
(
cos
70
°
)
(
cos
45
°
)
L
f
=
.3973
F
F
+
f
=
(
cos
70
°
)
(
cos
45
°
)
L
+
.3973
(
cos
70
°
)
(
cos
45
°
)
L
F
+
f
=
.3378
L
TAN
70
°
=
D
R
F
TAN
ω
=
D
R
F
+
f
TAN
ω
=
TAN
70
°
F
.
.3378
L
TAN
ω
=
(
TAN
70
°
)
(
COS
70
°
)
L
(
COS
45
°
)
L
.3378
L
TAN
ω
=
1.9670
ω
=
63.052
°
=
90
°
-
63.052
°
=
26.947
°
[0000] Step 4: Find cup impactor inclination angle as shown in FIG. 12J .
[0000]
TAN
63.118
°
=
h
R
(
F
+
f
)
From
Before
:
F
+
f
=
.3378
L
SIN
γ
=
h
R
L
SIN
γ
=
(
TAN
63.118
°
)
(
.3378
)
L
L
SIN
γ
=
.6663
γ
=
41.786
°
[0000] The following angular values are used for the navigation system to effectively impact a cup at a desired standing position of 45°/20° (inclination/anteversion) and are shown in FIGS. 12K and 12L . FIG. 12L shows standing plane 37 and rotated plane 140 .
Navigation version angle=26.947 deg
Navigation inclination angle=41.786 deg
Example 5
Here the cup impactor orientation is
[0068] 45° INCLINATION, 20° ANTEVERSION, AND THE PELVIC ORIENTATION IS 0° TILT, 0° ROTATION, and 10° OBLIQUITY (to be confirmed below). FIGS. 13 and 13A show a top view and front view of what a pelvis at 10 deg of Obliquity looks like. To find obliquity changes, two points are identified on the intra-op pelvis (refer to FIG. 9 ) to determine the angle of obliquity. The pelvis obliquity has changed by 10 degrees from the perfect position of 90 degrees.
[0069] Calculations for finding the impactor angles to be used by Navigation:
[0070] Step 1: As shown in FIG. 13B , project pre angle change impactor inclination angle onto plane of angle change. In this case it is the Standing Image Plane 37 shown in FIG. 13 . Calculation angles are shown in plane of standing x-ray in FIG. 13C .
[0071] Referring to FIG. 13C , project onto plane 37 (standing x-ray) that the change in angle will take place.
[0000]
COS
45
°
=
R
L
R
=
COS
45
°
L
COS
20
°
=
A
R
A
=
(
COS
20
°
)
(
COS
45
°
)
L
SIN
45
°
=
H
L
H
=
SIN
45
°
L
TAN
γ
=
H
A
=
SIN
45
°
(
COS
20
°
)
(
COS
45
°
L
)
γ
=
46.7808
°
[0072] Step 2: Rotate 10 deg of Obliquity in plane of rotation (Standing Image Plane).
[0073] Step 3: Calculate impactor version angle as shown in FIG. 13D .
[0000]
COS
46.7808
°
=
A
L
1
L
1
=
A
COS
46.7808
°
COS
36.7808
°
=
(
A
+
a
)
L
1
L
1
=
(
A
+
a
)
COS
36.7808
°
A
.6848
=
A
.8009
+
a
.8009
A
=
.8550
A
+
.8550
a
.1450
A
=
.8550
a
.
a
=
.1695
A
From
Before
:
a
=
(
COS
20
°
)
(
COS
45
°
)
L
a
=
.1126
L
s
o
:
A
=
.6644
L
A
+
a
=
.7771
L
Solve
for
σ
Tan
σ
=
d
.7771
L
Tan
20
°
=
d
.6644
L
d
=
.2418
L
Tan
σ
=
.2418
L
.7771
L
σ
=
17.283
°
[0074] The new position of the impactor handle is 17.286 degrees off the reference. This is one of the input angles needed for navigation and is shown in FIG. 13E .
[0075] Now calculate the inclination angle of the impactor as shown in FIG. 13F .
[0000]
TAN
36.7808
°
=
H
(
A
+
a
)
From
Before
:
(
A
+
a
)
=
.7771
L
SIN
δ
=
H
L
SIN
δ
=
(
TAN
36.7808
°
)
.7771
L
)
L
δ
=
35.5166
°
shown
in
FIG
13
G
.
[0076] The following angular values are used for the navigation system to effectively impact a cup at 45/20. Navigation version angle=17.283 deg; Navigation inclination angle=35.520 deg.
Example 6
[0077] Here the cup impactor orientation is 45 DEG INCLINATION, 20° ANTEVERSION, AND THE PELVIC ORIENTATION IS 0° TILT, 8° ROTATION (to be confirmed below) and 10° OBLIQUITY (to be confirmed below). Calculations for determining amount of Obliquity and Rotation: Use the method in Example 4 to calculate the amount of Rotation, and use the method in Example 5 to calculate the amount of Obliquity. Calculations for finding the impactor angles to be used by Navigation:
Step 1:
[0078] Use the method in Example 5 to find the following angles for the cup impactor for 10 deg Obliquity:
Cup impactor version=17.283 deg
Cup impactor inclination=35.516 deg
Step 2:
[0079] Now project these onto the plane for rotation, rotate 8 deg, and project back to plane that impactor is on (See FIG. 14 ).
FIG. 14 shows the cup impactor position prior to rotating 8 degrees
[0000]
COS
35.516
=
A
L
A
=
(
COS
35.516
)
L
SIN
35.516
=
h
L
h
=
(
SIN
35.516
)
L
COS
(
90
°
-
17.283
°
)
=
B
A
(
COS
72.717
)
(
COS
35.516
)
L
=
B
.2418
L
=
B
TAN
ω
=
h
B
=
(
SIN
35.516
)
L
(
COS
72.717
)
(
COS
35.516
)
L
ω
=
67.400
°
[0080] Now rotate 8 degrees as shown in FIG. 14A
[0000] σ=ω−8°
[0000] σ=67.400−8°
[0000] σ=59.400°
[0081] Now project back to plane of impactor as shown in FIGS. 14A , 14 B and 14 C.
[0000]
TAN
72.717
=
m
B
TAN
δ
=
m
(
B
+
b
)
TAN
(
72.717
)
B
=
TAN
δ
(
B
+
b
)
COS
67.400
=
B
L
1
L
1
=
B
COS
67.400
COS
59.400
=
B
+
b
L
1
L
1
=
(
B
+
b
)
COS
59.400
B
COS
67.400
=
(
B
+
b
)
COS
59.400
B
.3843
=
B
.5090
+
b
.5090
B
=
.7549
+
.7549
b
.2451
B
=
.7549
b
b
=
.3246
B
TAN
δ
=
m
(
B
+
b
)
TAN
72.717
=
m
B
TAN
(
72.717
)
B
=
TAN
δ
(
B
+
b
)
TAN
(
72.717
)
B
=
TAN
δ
(
B
+
.3246
B
)
3.2139
B
=
TAN
δ
(
1.3246
B
)
2.4263
=
TAN
δ
δ
=
67.601
°
Navigated
impactor
version
90
°
-
64.601
°
=
22.399
°
[0082] Find impactor inclination (shown in FIG. 14D ).
[0000]
TAN
59.400
=
h
1
(
B
+
b
)
SIN
α
=
TAN
59.400
(
B
+
b
)
L
From
Before
:
.2418
L
=
B
and
b
=
.3246
B
b
=
.3216
(
.2418
)
L
b
=
.0785
L
B
+
b
=
.2418
L
+
0.0785
L
=
.3203
L
SIN
α
=
TAN
59.400
(
.323
)
L
L
α
=
32.798
°
[0083] The following angular values are used for the navigation system to effectively impact a cup at 45 / 20 . Navigation version angle=22.399 deg ( FIG. 14C ) Navigation inclination angle=32.798 deg ( FIG. 14E )
Example 7
[0084] Here the cup impactor orientation is 45° INCLINATION, 20° ANTEVERSION, AND THE PELVIC ORIENTATION IS 10° TILT (to be confirmed below), 8° ROTATION (to be confirmed below) and 10° OBLIQUITY (to be confirmed below). Calculations for determining amount of Obliquity and Rotation: Use the method in Example 3 to calculate the amount of Tilt Use the method in Example 4 to calculate the amount of Rotation
[0000] Use the method in Example 5 to calculate the amount of Obliquity
Calculations for Finding the Impactor Angles to be Used by Navigation:
Step 1:
[0085] Use the methods in Example 6 to find the impactor angles to be used for Navigation after applying 8 deg of Rotation and 10 deg of Obliquity.
Cup impactor version=22.399 deg
Cup impactor inclination=32.798 deg
Step 2:
Apply 10 deg of Tilt.
[0086] FIG. 15 shows the three basic x, y and z directions that angle changes can take place: Tilt, Obliquity, and Rotation. The three directions are along the three basic vector directions of a coordinate system. In Example 6, Rotation and Obliquity were applied 90 degrees to each other. Following this approach, Tilt would be rotated around the third vector Y (perpendicular to the page) of the coordinate system. In FIG. 15 , Tilt changes would take place in the Central Plane 39 by rotating on the axis perpendicular (normal) to the Central Plane. The practical issue with this is that the pelvis would be lifting off the OR table in doing this. FIG. 15A illustrates the extreme example of the pelvis with the same Rotation and Obliquity as FIG. 15 , but with 180 deg of Tilt applied.
[0087] The pelvis is no longer laying on the operating room table with the legs resting along the plane of the table. In this position, the portion of the legs near the pelvis would be lifted off the table. This is not a realistic situation as the patient, no matter what the pelvic tilt, is laying flat on the table. Although this example is extreme, it demonstrates that any pelvic tilt angle applied to the coordinate system would lift the legs up off the table. Calculations could be performed to project the cup inclination and version angles found in Example 6 along the Central Plane 39 , rotate the Tilt amount in this plane, and reproject as per the above examples. However, a more practical method would be to perform the calculations as per Example 6, and simply rotate these results by the Tilt angle amount found as per Example 3.
[0088] Method to apply 10 deg of Tilt:
Step 1:
[0089] Find the amount of Tilt as per Example 3.
Step 2:
[0090] Perform calculations as per Example 6 for Rotation and Obliquity. Navigation angles found in Example 6 are shown in FIGS. 15B and 15C .
[0091] To apply 10 degrees of positive Tilt, simply subtract 10 degrees from 22.402 deg to yield 12.402 degrees. The cup impactor inclination angle of 32.798 deg remains the same.
[0092] This example uses the apparent obliquity change when looking across the reference from the front of the OR table. In reality, the pelvis has obliquely changed in the direction of the pelvic tilt. In this example, the obliquity would be 10 degrees off the front of table plane. The calculations below show what the actual obliquity would be (see FIG. 15D ).
[0000]
TAN
10
°
=
d
h
COS
10
°
=
d
L
TAN
δ
=
L
h
TAN
δ
=
TAN
10
°
COS
10
°
δ
=
10.15
[0093] The plane defined by the front of the table would be a plane thru d and h of FIG. 15D . The plane defined by the tilt plane in the direction of the standing xray image plane would be defined by L and h. The actual obliquity would be 10.15 degrees not 10 degrees. However, the difference of 0.15 degrees is inconsequential in practice for cup positioning in hip surgery and that using 10 degrees for the calculations would be acceptable. Either method could be used.
[0094] The pre-operative image may show a leg shortening that needs correction as shown in FIG. 16 . Note that the pelvis is in the pre-operative x-ray shown in FIG. 16 is not parallel to the floor (the line joining points 30 and 32 is not parallel). A line through points 30 and 32 is angled at 5° from horizontal. The surgeon may want to correct for this. If a check for obliquity is taken in this image, it would show that the pelvis is 5 degrees off. The method of measurements set forth above allows for correcting this. To correct for the 5 degrees, a measurement for obliquity as shown in FIG. 20 would be taken. But suppose the surgeon wants to keep the 5 degrees of obliquity, then the extra 5 degrees is added/subtracted from the intra-operative obliquity measurement and used to calculate the impactor inclination angle.
[0095] It is assumed that the intra-operative image is taken perpendicular (normal) to reference bar 40 . Normally, this is a good assumption, but in practice, it may be a few degrees off from being perpendicular. This could be accounted for in two ways:
[0096] The two or more radiopaque points in the reference bar could be at precise distance apart from each other. Any angular differences in the image would result in a difference in measurement between the points which can be calculated in the computer.
[0097] The preferred reference bar is radiolucent, and has two radiopague spheres ( 44 , 45 ) embedded in reference bar 40 3 inches apart. Any angular differences in the image would result in a difference in measurement between spheres 44 and 45 . An image that is taken perpendicular to bar 40 would show a 3 inch measurement between the radiopaque spheres. However, an image at a 10 degree angle to the bar would show a distance of 2.954 inches long. So in practice, an image would be taken and the actual distance on the image compared against the known distance of 3 inches. It would be discovered that the image is being taken at an angle to the reference at that time. The x-ray direction could then be changed to account for it, or the calculated 10 degree angle could be used as a modifier to the follow-up dimensions to be used for obliquity, tilt, and rotation.
[0098] If for some reason it is suspected that the x-ray emitter is also taken at an angle to the floor, as in pointing more to the floor or away, another option would be to include a third radiopaque marker in the reference bar that could be used for angular corrections.
[0099] Using the above methodology to determine the pelvis location intra-operatively can have benefits beyond cup placement. Another use would be for drilling along a certain direction in times where it is desirable to place a screw in the area having the most bone. An example of this would be in a severe revision situation whereas bone erosion can comprise desirable areas to have fixation.
[0100] Alternately, a navigation tracker could be placed on the x-ray emitter itself and used to make automatic corrections. If for some reason it is suspected that the x-ray emitter is also taken at an angle to the floor, as in pointing more to the floor or away, another option would be to include a third radiopaque marker in the reference that could be used for angular corrections. The navigation tracker could be used for this as well.
[0101] This invention describes the benefits of taking a pre-operative standing image vs. a pre-operative supine image. A standing image takes into account the normal pelvic position for each individual patient as opposed to a laying down/supine image which can alter the pelvis position similar to laying down on the operating table.
[0102] However, the invention does not exclude supine images, both pre-operative and intra-operative. For example, for the direct anterior surgical approach, the patient is supine on the table. It could be argued that the pelvis may have similar angular changes for the supine pre-operative x-ray image to the intra-operative supine position on the table, and therefore, in a way, recreating a natural standing pelvic position due to the similar angular changes.
[0103] At a minimum, the two A/P promontory points and the public symphysis point needs to be taken. If only these three points are taken, the line between he promontory points could help dictate the obliquity angle, and an assumption could be made that the x-ray emitter is parallel to the operating table and floor, and therefore, any line parallel to the floor on the image could be the reference. This also assumes that the image detector is parallel to the operating table and/or floor.
[0104] A common operating room table can be adjusted in two ways: trendelenburg (about the long axis of the table) and lateral tilt (about the short axis of the table). It is conceivable that the table could be adjusted to account for pelvic obliquity and rotation prior to an intro-operative image to account for any angular changes. This would be an attempt to adjust the table in order to place the pelvis at the “perfect” position 90° to the floor as described above, and therefore a surgeon could simply use the impactor at the 45°/20° position to the floor. There are two major issues with this that this invention addresses. First, there are only two adjustments with the table, not three. There is not an adjustment for tilt and therefore the surgeon would need to somehow adjust for this. Second, multiple intra-operative images would have to be taken in order to get the exact position needed for the pelvis. For instance, the table would have to be tilted to remove any intra-operative pelvic rotation. An image would be taken, and a guess as to how much the table would be adjusted to remove rotation. Another image taken, and further adjustment until the pubic symphysis is directly positioned over the sacrum. This would be a visual positioning, as well as adjusting for obliquity with trendelenburg table adjustments.
[0105] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | An alignment system for aligning an acetabular cup insertion instrument utilizes pre-operative preferably standing x-rays and intra-operative x-rays to allow the surgeon to compensate for the position of a patient on an operating room table. The system uses a programmable computer connected to a digital x-ray system and an navigation tracking system to provide input for calculating the inclination and anteversion angles of an acetabular cup impactor based on a pre-operative plan developed from the standing x-rays. The system calculates changes in lengths and angles between anatomic landmarks on the pelvis to alter the intra-operative orientation of the acetabular reaming and impacting instruments to produce the desired inclination and anteversion angles when the pelvis is reoriented as the patient is placed on an operating table. | 0 |
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