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FIELD OF THE INVENTION
The present invention relates in general to electronics (e.g., telecommunications) equipment and components thereof, and is particularly directed to a clip-based fastening arrangement for facilitating aligned ‘blind’ insertion and attachment of a multi-pin communication cable connector, such as, but not limited to a ‘telco’-type multi-pin connector, into a connector-installation aperture of a (rear) panel of an equipment chassis, so that the pins of the connector may readily electrically and mechanically engage corresponding sockets of an associated multi-socket receptacle of a printed circuit board installed in a card slot adjacent to the rear panel of the chassis.
BACKGROUND OF THE INVENTION
A variety of electronics systems, such as telecommunication systems, commonly employ multi-conductor cables to provide electrical connections to system components, such as, but not limited, to circuit components mounted on printed circuit cards installed within respective card slots of an electronics equipment bay. As shown in the diagrammatic side view of FIG. 1 , the respective conductors of such a multi-conductor cable 10 are customarily terminated at pins of a multi-pin connector, such as a ‘telco’-type multi-pin connector, shown generally at 20 , and in detail in the respective front, side, front perspective and rear perspective views of FIGS. 2 , 3 , 4 and 5 , respectively. This type of multi-pin connector is configured to (mechanically and electrically) mate with an associated multi-socket receptacle 30 , such as may be mounted adjacent to a rear edge 42 of a printed circuit card 40 , installed in a respective equipment chassis card slot.
Stable mechanical support for the multi-pin connector 20 is typically provided by way of a rear panel 50 , upper and lower portions of which are affixed to (generally horizontally extending) frame members 60 of the equipment rack proper. The rear panel 50 may have one or more connector-receiving apertures 51 . Such an aperture is sized to allow passage therethrough of a distal end 21 of multi-pin connector 20 , so that the connector's pins may engage corresponding sockets in the distal end 31 of multi-socket receptacle 30 . Where the rear panel contains a plurality of multi-pin connector-receiving apertures, the apertures are normally positioned so as to be alignable with corresponding multi-socket receptacles supported on multiple printed circuit cards, such as a pair of printed circuit cards installed in adjacent card slots, or a motherboard and an adjacent daughterboard mounted thereon by way of associated stand-offs.
In order to enable the multi-pin connector 20 to be stably retained by the rear panel 50 , the rear panel customarily includes a pair of bores 52 and 53 adjacent to opposite (e.g., upper and lower) edges of the connector-receiving aperture 51 . These bores are sized to receive hardware fittings, e.g., screws, that pass through associated bores 22 and 23 in a flange portion 24 of the multi-pin connector 20 on either side of its distal end 21 , and affix the connector 20 to the rear panel 50 .
A shortcoming of this type of connector attachment architecture is the fact that the connector's cable attachment interface 25 that joins the cable 10 with the connector proper overlaps and projects beyond the (lower) connector bore 23 . This is particularly problematic as cable and circuit densities have increased, making access to attachment fittings difficult and cumbersome. As a consequence, in order to attach a fitting to each of the connector bore 23 and its associated rear panel bore 53 , it is often necessary to remove the rear panel from the equipment chassis, so that the fitting can be inserted from the interior or card side of the rear panel through the bore 53 and into the bore 23 of the connector 20 . Then, once the connector 20 has been attached to the rear panel (by way of fittings through each bore pair), the rear panel itself is reaffixed to the equipment rack. Unfortunately, removing the rear panel in order to attach such a connector means that any other printed circuit card, to which another respective connector supported by that rear panel is connected, will necessarily be taken off-line, and thereby disrupt service to its associated telecommunication circuit.
Proposals to avoid removing the rear panel in order to provide attachment to the lower portion of the connector (where the bore 23 is located), have included the use of wire ties, lacing cords, loop-and-hook strap attachments, and the like. Drawbacks of these approaches include their inherent lack of structural rigidity, their inability to ensure blind alignment between the multi-pin connector and its associated multi-socket receptacle on the printed circuit card, and the fact that they are labor intensive, which increases the cost of manufacture.
SUMMARY OF THE INVENTION
In accordance with the present invention, these and other shortcomings of conventional arrangements for attaching a multi-pin connector of a multi-conductor cable, such as but not limited to a multi-conductor telecommunication cable, to an associated multi-socket receptacle on a printed circuit card are effectively obviated by attaching a relatively physically robust (solid, e.g., metallic (aluminum)), rear panel-attachment clip member, or clip, to the multi-pin connector. The attachment clip is configured to allow aligned, ‘blind’ insertion of a standard multi-pin connector, from which the multi-conductor cable extends, into the bottom of a connector-installation aperture of the rear panel.
To this end, the clip includes a notch, or trough-like, region, that allows the lower side of a standard multi-pin connector to be stably captured in the rear panel, simply by placing the notch of the clip onto the bottom edge of the connector installation aperture, thereby confining opposite sides of the rear panel adjacent to the bottom edge of the aperture within the notch. As a result, no hardware fitting attachment bore adjacent to the lower edge of the connector-installation aperture is required. Since a physical connection between the multi-pin connector and such a bore is unnecessary, removal of the rear panel from the equipment chassis (in order to insert a fitting into the lower side of the connector from the interior or card side of the rear panel) is avoided, so that a circuit card in a different card slot terminated by that rear panel will not be taken off-line.
Moreover, being made of a relatively rugged, solid material (e.g., aluminum), in contrast to relatively flimsy prior art attachment devices, such as wire ties, lacing cords, loop-and-hook strap attachments, and the like, referenced above, the connector attachment clip of the invention is structurally robust. As a consequence, when inserted onto the bottom edge of the connector installation aperture, the clip, and thereby the lower portion of the multi-pin connector to which the clip is attached, will be stably and firmly retained within the rear panel.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic side view of the manner of attachment of a multi-pin connector of a multi-conductor telecommunication cable with a multi-socket receptacle mounted on a printed circuit card installed in a card slot of a telecommunication equipment bay;
FIGS. 2 , 3 , 4 and 5 are respective diagrammatic front, side, front perspective and rear perspective views of a standard multi-pin telco-type connector;
FIGS. 6 , 7 and 8 are respective front, front perspective and rear perspective diagrammatic views of the configuration of a rear panel of the multi-pin connector attachment arrangement of the present invention;
FIGS. 9 , 10 , 11 and 12 are respective side, rear, front perspective and rear perspective diagrammatic views of the configuration of a rear panel-attachment clip of the multi-pin connector attachment arrangement of the present invention; and
FIG. 13 is a partially exploded, diagrammatic perspective view of the manner of attachment of a pair of multi-pin connectors and associated rear panel-attachment clips of the invention to respective connector-installation apertures of a rear panel of a telecommunication equipment chassis.
DETAILED DESCRIPTION
Attention is now directed to FIGS. 6 , 7 and 8 , which are respective front, front perspective and rear perspective diagrammatic views of the configuration of a rear panel employed in the multi-pin connector attachment arrangement of the present invention. As shown therein, the rear panel 100 includes a generally planar or flat, rectangular faceplate 110 , from parallel side edges of which extend respective sidewalls 111 and 112 . Upper ends of the sidewalls terminate at respective flange portions 113 and 114 . Extending from a lower edge of the faceplate 110 is a generally L-shaped lower bend portion 115 , having a lower lip portion 116 that is generally coplanar with the longitudinal edges of sidewalls 111 and 112 and includes a slot 117 , that is sized to receive a fitting, such as a screw and the like, for attaching the lower bend portion 115 of the rear panel 100 to a corresponding bore in a generally horizontally extending frame member of a telecommunication equipment rack (such as the frame member 60 of FIG. 1 ).
In a like manner, extending from an upper edge of the faceplate 110 is a generally L-shaped upper bend portion 118 , having an upper lip portion 119 , that is also generally coplanar with the longitudinal edges of sidewalls 111 and 112 . The upper lip portion 119 includes one or more slots or bores 120 (two being shown in the Figures), that are sized to receive fittings, such as screws and the like, for fixedly attaching the upper bend portion 118 of the rear panel 100 to corresponding bores in a generally horizontally extending frame member of a telecommunication equipment rack. The upper lip 119 of the rear panel cooperates with notches 123 and 124 in the respective flange portions 113 and 114 of the rear panels sidewalls 111 and 112 , so that the rear panel may engage and capture therebetween a lower edge portion of a (generally horizontally extending) frame member of the equipment rack, and thereby be rigidly secured thereto. For this purpose, upper distal ends 125 and 126 of the respective flange portions 113 and 114 of the rear panels sidewalls 111 and 112 of the rear panel preferably have generally curvilinear surfaces, as shown, so as to facilitate pivotal engagement of the rear panel with (and disengagement from) a lower edge portion of equipment rack frame member.
For the non-limiting application of providing a protective closure and cable attachment location for a pair of printed circuit cards installed in mutually adjacent card slots of an equipment rack, the front panel's faceplate 110 is shown as being provided with a pair of parallel, generally rectangularly shaped, multi-pin connector-installation apertures 131 and 132 . Each connector-installation aperture 131 , 132 is sized to accommodate the insertion therein of the distal end of a multi-pin connector of the type shown in FIGS. 2-5 , so that the connector's pins may engage corresponding sockets in the distal end of a multi-socket receptacle mounted on a printed circuit card installed in a respective one of the two mutually adjacent card slots that are closed by the rear panel 100 . Namely, for the illustrated example of a rear panel faceplate 110 having two connector-installation apertures 131 and 132 , these apertures are spaced apart from one another by a distance that provides alignment between multi-pin connectors retained therein with corresponding multi-socket receptacles of a pair of printed circuit cards installed in mutually adjacent card slots of the equipment rack.
Similar to the conventional rear panel 50 shown in FIG. 1 , the rear panel 100 of FIGS. 6 , 7 and 8 includes upper (threaded) bores 141 and 142 adjacent to upper edges 133 and 134 of the connector-receiving apertures 131 and 132 . As in conventional rear panel, these apertures are sized and located to receive hardware fittings, e.g., screws, that pass through associated upper bores 22 in a standard multi-pin connector, such as that shown in FIGS. 2-5 , when a multi-pin connector is inserted into a respective aperture 131 , 132 . However, unlike the conventional rear panel, there are no similar lower bores adjacent lower edges of the apertures for receiving hardware fittings that pass through the lower bores 23 in the multi-pin connector, when that connector is inserted into a respective aperture 131 , 132 .
Instead, the depths of the lower portions of the connector-installation apertures 131 and 132 are increased or extended by means of respective, generally rectangular, connector installation-aperture extension slots 151 and 152 , that terminate at respective lower edges 153 and 154 thereof. Each of these aperture extension slots is sized and shaped to accommodate the insertion therein of a respective rear panel-attachment clip, illustrated diagrammatically in FIGS. 9 , 10 , 11 and 12 . Preferably, the width of each aperture extension slot is slightly wider than the width of a clip, so as to allow for a slight amount of (horizontal) play between the clip and the slot, and thereby accommodate minor offsets in the position of the printed circuit card installed in the card slot that is terminated by the rear panel, and facilitate ‘blind’ engagement of the pins of the multi-pin connector with the sockets of the multi-socket receptacle mounted on the printed circuit card.
As shown in FIGS. 9-12 , a respective rear panel-attachment clip 200 is configured as a generally rectangularly shaped, solid element, made of a relative rugged, robust material such as aluminum, having an upper wall 201 , which has a slightly inclined surface that generally conforms with the inclined shape of the lower edge 26 of the distal end 21 of the multi-pin connector shown in FIGS. 2-5 . This inclination of the surface of upper wall 201 serves as a physical ‘key’, to ensure that the clip 200 will be properly oriented with its rear surface abutting against the multi-pin connector and its tab end down for engagement with a lower edge 153 , 154 of a respective aperture extension slot 151 , 152 , when the clip 200 is installed on the connector 20 , as will be described.
Other than the slightly inclined shape of its upper wall 201 , the remainder of the generally solid, rear panel-attachment clip is generally rectangularly shaped, having a pair of parallel sidewalls 202 and 203 , that extend from upper wall 201 and adjoin a bottom wall 204 . Each of the upper wall 201 , sidewalls 202 and 203 , and bottom wall 204 extends between a generally planar rear surface 205 , that is directly abutable against the multi-pin connector, and a generally planar front surface 206 , that faces the interior of the card slot when the connector, with the clip attached, is inserted into a connector-installation aperture. A hardware fitting bore 207 is formed in the clip's rear surface 205 and passes through a boss region 208 that extends between and is solid with the upper wall 201 and the lower wall 204 . The clip 200 is attached to the multi-pin connector 20 by means of a hardware fitting, such as a screw, inserted through bore 207 in boss regions 208 of clip 200 and into bore 23 of the connector.
The height of the rear surface 205 of the clip is slightly less than the height of its front surface 206 , so as to provide a vertical offset 209 between a lower, generally rectilinear edge 210 of the rear surface 205 , which conforms with the generally rectilinear bottom edge 153 , 154 of a respective connector installation-aperture extension slot 151 , 152 of rear panel 100 , and the bottom wall 204 of the clip. This offset allows one or more tabs, such as the two tabs shown at 211 and 212 , that are solid with the lower portion of the rear surface 205 of the clip, to define a rear panel capture region or notch 213 to be formed between the tabs 211 and 212 and a front face 214 of a lower portion 216 the clip adjacent to its bottom wall 204 . (The generally rectangular holes in the lower position 216 of the clip serve to reduce material only and are otherwise non-directional.) The width of the notch 213 generally corresponds to, but is just slightly wider than, the thickness of the rear panel's faceplate 110 . As a result, as shown in the side view of FIG. 9 a lower edge 153 , 154 of the rear panel faceplate 110 at the bottom of an aperture extension slot 151 , 152 is allowed to enter and be captured by the notch 213 , and thereby stably secure the clip 200 , and thereby the lower portion of the multi-pin connector to which the clip has been attached, to the rear panel.
To this end, the distance between the bore 207 in the boss region 208 and the lower edge 210 of the rear surface 205 of the clip is such that, when the clip 200 is attached to the connector, by means of a hardware fitting passing through the bore 207 in the clip that is coaxial with the bore 23 in the connector, the lower edge 210 of the rear surface 205 of the clip 200 will rest upon or be very slightly vertically offset from a bottom edge 153 , 154 of an aperture extension slot 151 , 152 . In addition, this distance is such that the upper bore 22 of the connector will be aligned with an upper one of the bores 141 and 142 of the rear panel faceplate 110 , so that the connector 20 may be readily affixed to the faceplate 110 by means of a hardware fitting that passes through the upper bore 22 in the connector 20 and its associated aligned bore (one of bores 141 and 142 ) in the faceplate 110 .
This connectivity alignment relationship, that is provided by the configurations and geometries of the panel-attachment clip 200 and a respective aperture extension slot in the rear panel faceplate, is diagrammatically illustrated in the perspective, partially exploded view of FIG. 13 . In particular, FIG. 13 shows a pair of multi-pin connectors 20 - 1 and 20 - 2 , which have respectively associated rear panel-attachment clips 200 - 1 and 200 - 2 . Connector 20 - 1 and its associated rear panel-attachment clip 200 - 1 attached thereto are shown in their installed positions in the connector-installation aperture 132 of the rear panel 100 ; connector 20 - 2 , its associated clip 200 - 2 , and a hardware fitting (screw) 215 - 2 that joins the clip 200 - 2 to the connector 20 - 2 are shown in spaced apart, but aligned relationship with respect to each other and with respect to the connector-installation aperture 131 of rear panel 100 .
As can be seen from FIG. 13 , when a respective clip 200 is placed upon a multi-pin connector 20 in its proper orientation (namely, ‘keyed’ by the inclination of the surface of its upper wall 201 , as described above), and attached to that connector by means of a fitting (e.g., screw) that passes through the clip's bore 207 into an associated lower connector bore (corresponding to the connector bore 23 , described above, but not shown in FIG. 13 ), the lower edge 210 of the rear surface 205 of the clip may be readily placed directly upon, or just slightly vertically offset from, the bottom edge 153 , 154 of the faceplate's aperture extension slot 151 , 152 . In this aperture-inserted position of the clip, the lower edge 153 , 154 of the rear panel faceplate 110 at the bottom of a respective aperture extension slot 151 , 152 is captured within the clip's notch 213 formed between the tabs 211 and 212 and the front face 214 of the lower portion the clip adjacent to its bottom wall 204 , so as to stably secure the clip 200 , and thereby the lower portion of the multi-pin connector to which the clip has been attached, to the rear panel.
With the notch 213 at the bottom of the clip 200 captured at the bottom edge 153 , 154 of the connector installation aperture-extension slot 151 , 152 , the upper bore 22 of the connector 20 will be aligned with an upper bore 141 / 142 of the faceplate 110 , allowing the pins of the multi-pin connector 20 to be inserted into and engage the sockets of a multi-socket receptacle at the rear of the printed circuit card. The connector 20 may now be securely attached to the rear panel by means of a hardware fitting (e.g. screw), that passes through the upper bore 22 and its associated aligned bore 141 / 142 in the rear panel faceplate 110 . Removal of the multi-pin connector from the rear panel is straightforward, requiring only a disengagement of the hardware fitting in the upper bore 22 of the connector from the upper bore 141 / 142 of the faceplate, followed by lifting the connector and its attached clip off the bottom edge of the extension slot.
As pointed out previously, and as will be appreciated from the foregoing description, the rear panel-attachment clip of the invention allows the lower side of a standard multi-pin connector, from which the multi-conductor cable extends, to be readily and stably captured in the rear panel, simply by placing the notch of the clip into engagement with the bottom edge of the connector installation aperture. As a result, the undesirable task of removing the rear panel from the equipment chassis (in order to insert a fitting into the lower side of the connector from the interior or card side of the rear panel) is avoided, so that a circuit card in a different card slot terminated by that rear panel will not be taken off-line. Moreover, because it is made of a relatively rugged, solid material, in contrast to relatively flimsy prior art attachment devices, such as wire ties, lacing cords, loop-and-hook strap attachments, and the like, the attachment clip of the invention is structurally robust, so that, when inserted onto the bottom edge of the connector installation aperture, the clip, and thereby the lower portion of the multi-pin connector to which the clip is attached, will stably engage the rear panel.
While I have shown and described a non-limiting, but preferred, embodiment of the invention, it is to be understood that the same is not limited thereto but is susceptible to numerous changes and modifications as known to a person skilled in the art, and I therefore do not wish to be limited to the details shown and described herein, but intend to cover all such changes and modifications as are obvious to one of ordinary skill in the art.
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A clip is attachable to a flange of a connector terminating an electrical cable, and is configured to mechanically couple one side of the flange to an edge of a connector-installation aperture of a chassis, such that a distal end of the connector may engage a receptacle within the chassis. When the connector, with the clip attached, is placed in the chassis' connector-installation aperture, a notch region of the clip engages the chassis at an edge of its connector-installation aperture, causing a bore on a second side of the flange to be coaxial with a bore in the chassis, so that a hardware fitting therethrough may secure the connector to the chassis.
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FIELD OF THE INVENTION
The present invention generally relates to products and materials in the field of over-molding devices having ferrite cores, powdered metal cores and high energy product magnet cores, and more particularly to the materials and products made by overmolding electronic components incorporating such core materials. The invention has particular applications in the field of electronic identification (“EID”) or radio frequency identification (“RFID”) components and devices manufactured by the overmolding process.
BACKGROUND OF THE INVENTION
Ferrite cores, powdered metal cores and high energy product magnets such as samarium cobalt and neodymium-iron-boron magnets have certain advantageous magnetic and electric field properties making them ideal for use in certain types of electronic components and circuitry. These types of materials are frangible, yet the materials can be fabricated into a variety of shapes and generally exhibit good mechanical characteristics under compression loads. However, these frangible materials are generally weak in tensile strength, tending to crack or fracture when subject to relatively modest tensile loading, binding loads or impact loading. Cracks and fractures within the fabricated frangible materials can substantially decrease the beneficial magnetic and electric field properties, negatively impacting their desirable characteristics. Thus, maximum utilization of these types of frangible materials requires consideration of, and accommodation for, their limiting physical properties.
An exemplary application which can benefit from the use of a ferrite core as part of an electronic circuit is an Electronic Identification (“EID”) or Radio Frequency Identification (“RFID”) transponder circuit used in EID or RFID systems. EID and RFID systems generally include a signal emitter or “reader” which is capable of emitting a high frequency signal in the kilohertz (kHz) frequency band range or an ultra-high frequency signal in the megahertz (MHz) frequency band range. The emitted signal from the reader is received by a “transponder” which is activated in some manner upon detection or receipt of the signal from the reader. In EID and RFID systems, the transponder generates a signal or inductively couples to the reader to allow the reader to obtain identification codes or data from a memory in the transponder.
Generally, the transponder of an EID or RFID system will include signal processing circuitry which is attached to an antenna, such as a coil. For certain applications, the coil may be wrapped about a ferrite, powdered metal, or magnetic core. The signal processing circuitry can include a number of different operational components including integrated circuits, as known in the art, and many if not all of the operational components can be fabricated in a single integrated circuit which is the principal component of the signal processing circuitry of EID and RFID devices.
For example, certain types of “active” RFID transponders may include a power source such as a battery which may also be attached to the circuit board and the integrated circuit. The battery is used to power the signal processing circuit during operation of the transponder. Other types of transponders such as “Half Duplex” (“HDX”) transponders include an element for receiving energy from the reader, such as a coil, and elements for converting and storing the energy, for example a transformer/capacitor circuit. In an HDX system, the emitted signal generated by the reader is cycled on and off, inductively coupling to the coil when in the emitting cycle to charge the capacitor. When the emitted signal from the reader stops, the capacitor discharges to the circuitry of the transponder to power the transponder which then can emit or generate a signal which is received by the reader.
A “Full Duplex” (“FDX”) system, by comparison, includes a transponder which generally does not include either a battery or an element for storing energy. Instead, in an FDX transponder, the energy in the field emitted by the reader is inductively coupled into the antenna or coil of the transponder and passed through a rectifier to obtain power to drive the signal processing circuitry of the transponder and generate a response to the reader concurrently with the emission of the emitted signal from the reader.
Notably, many different circuit designs for active, HDX and FDX transponders are known in the art and have been described in a number of issued patents, and therefore they are not described in greater detail herein. Many of the types of EID and RFID transponders presently in use have particular benefits resulting from their ability to be imbedded or implanted within an object to be identified in a manner whereby they are hidden from visual inspection or detection. For such applications, the entire transponder may preferably be encased in a sealed member, for example to allow implantation into biological items to be identified, or to allow use in submerged, corrosive or abusive environments. Accordingly, various references, including U.S. Pat. Nos. 4,262,632; 5,025,550; 5,211,129; 5,223,851, 5,281,855 and 5,482,008, disclose completely encapsulating the circuitry of various transponders within a ceramic, glass or metallic container.
For an encapsulated transponder, it is generally the practice to assemble the transponder circuitry and then insert the circuitry into the glass, ceramic or metallic cylinder, one end of which is already sealed. The open end of a glass-type cylinder is generally melted closed using a flame, to create a hermetically sealed capsule. Other types of glass, ceramic or metallic containers utilize a cap to seal the open end, with the cap glued or mechanically connected to the open ended cylinder, as discussed for example in U.S. Pat. No. 5,482,008. Furthermore, as discussed in the aforementioned patent, to prevent the transponder circuitry from moving around inside of the capsule, it is also known to use an epoxy material to bond the circuitry of the transponder to the interior surface of the capsule.
As shown for example in U.S. Pat. No. 4,262,632 (hereby incorporated by reference), the potential advantages of utilizing EID and RFID devices in biological applications, such as the identification of livestock, have been under investigation for several years. As discussed in the U.S. Pat. No. 4,262,632, studies show that an EID “bolus” transponder suitable for placement in the reticulum of a ruminant animal will remain in the reticulum for an indefinite time if the specific gravity of the bolus transponder is two or greater, and/or the total weight of the bolus transponder exceeds sixty grams. Accordingly, for such applications, the bolus transponder generally requires a weight element as the EID circuitry can generally be very small and lightweight, requiring merely the integrated circuit and antenna and few other components. It has therefore been disclosed, for example in the U.S. Pat. No. 4,262,632 to incorporate a ferrite weight element within an encapsulant which also contains an EID transponder.
The design of a bolus transponder suitable for use in a ruminant animal may be also benefit from the appropriate use of a magnet or a ferrite core to enhance the signal transmission characteristics of the transponder while also providing the necessary weight to maintain the specific gravity of the bolus transponder at two or greater, and/or to have the total weight of the bolus transponder exceed sixty grams. In order to obtain widespread acceptance and use of the EID bolus transponder devices for ruminant animals, however, the devices must also be designed and fabricated with an understanding of the physical and economic requirements of the livestock application. Thus, while ceramic encapsulated bolus transponders suited to the reticulum environment are being investigated, the cost and fragile physical characteristics of the ceramics impact their commercial acceptance. Thus, an encapsulant for fabricating the capsule or casing for EID transponders which does not have the limitations of ceramic, glass or metallic encapsulants, particularly for bolus transponders, would be highly beneficial.
SUMMARY OF THE INVENTION
The present invention contemplates a method and apparatus for overmolding ferrite, powdered metal and magnet core materials and associated circuitry, for example circuitry for an EID or RFID transponder, whereby the encapsulant is a plastic, polymer or elastomer or other injection molded material compatible with the intended application environment. According to the invention, the encapsulant material applied in an injection molding or extrusion molding process to overmold the core and electronic circuitry of the transponder.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional side view of a transponder including an overmolded core fabricated according to the present invention;
FIG. 2 is a cross-sectional view of the transponder of FIG. 1;
FIG. 3 depicts a perspective view of the mold tooling utilized for the overmolding process to fabricate the transponder of FIG. 1;
FIG. 4 depicts a cross-sectional view through the mold tooling of FIG. 3 during the initial stage of the injection of molding material into the mold tooling;
FIG. 5 depicts a second cross-sectional view of the mold tooling of FIG. 3 showing a later stage in the molding process;
FIG. 6 depicts another cross-sectional view of the tooling of FIG. 3 showing a further stage in the molding process;
FIG. 7 depicts another cross-sectional view of the tooling of FIG. 3 showing the molding process wherein the pins are being retracted into the tooling;
FIG. 8 depicts a side view of an alternative configuration for a transponder which has not yet been coated with molding material;
FIG. 9 depicts the front view of the transponder of FIG. 8;
FIG. 10 depicts the transponder of FIGS. 8 and 9 placed within the mold tooling of FIG. 3 during the injection molding process at the same stage as depicted in FIG. 6;
FIG. 11 depicts a frangible core element placed within the tooling of FIG. 3 during the overmolding injection process at the same stage as the step depicted in FIG. 6;
FIG. 12 depicts a cross sectional view of a frangible core overmolded with an overmolding material according to the process of the present invention;
FIG. 13 depicts a perspective view of a transponder within an alternative design for the mold tooling, and positioned therein by one or more centering elements during the overmolding process;
FIG. 14 depicts a perspective view of a centering element as shown in FIG. 13 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 depicts a cross-sectional side view of a transponder 10 made according to the present invention. FIG. 2 depicts an end view of the transponder 10 of FIG. 1 . The transponder 10 includes signal processing circuitry such as an integrated circuit 12 mounted on a circuit board 14 together with other circuit elements such as a capacitor 16 . The signal processing circuitry may be an active, Half Duplex (HDX) or Full Duplex (FDX) transponder circuit.
The integrated circuit 12 and capacitor 16 are affixed to the circuit board 14 and electrically coupled to a wire 18 formed into a coil 20 , at the leads or ends 22 and 24 of the wire 18 . In the embodiment illustrated in FIGS. 1 and 2, the coil 20 is wrapped about a bobbin 26 and then positioned over a core 30 , with the circuit board 14 affixed to an end of the core 30 to form a transponder assembly 10 a. As discussed below, the transponder assembly 10 a may preferably be over-molded within an injection molding material 32 , which may be a plastic, polymeric or epoxy material to form the completed transponder 10 .
The relative axial location of the coil 20 about the core 30 may be important to the optimal operation of the transponder 10 . Specifically, the transponder 10 preferably includes a tuned coil 20 and capacitor 16 combination. Generally, in a transponder, tuning is accomplished by matching the length of the wire 18 forming coil 20 to the capacitance of capacitor 16 . However, when the wire 18 has to be wrapped around the bobbin 26 and installed over the core 30 , the exact length of wire 18 , as well as its inductance, cannot be as advantageously controlled during design and fabrication so as to allow matching of the inductance of the coil 20 to the capacitance of the capacitor 16 in order to tune the circuit of the transponder 10 . It should be appreciated that if the transponder is not properly tuned, the reading and data transfer capabilities of the transponder may be diminished.
It has been found, however, that by the proper axial placement of the core 30 within the coil 20 , the transponder 10 can be tuned even without optimizing the length of the wire 18 , as the inductance of the coil 20 changes due to the axial positioning of the ferrite core 30 . For a given set of design parameters for a ferrite core 30 and coil 20 combination, including the core's circumference and length as well as the length of the wire 18 and the capacitance of the capacitor 16 , a tuned transponder assembly 10 a can be fabricated by moving the coil 20 axially along the long axis of the ferrite core 30 until a tuned inductor/capacitor system is established and then securing the bobbin 26 with coil 20 to the ferrite core 30 during the manufacturing process.
Following assembly of the circuitry of the transponder assembly 10 a, the transponder assembly 10 a is transferred to an injection molding machine, Specifically, the transponder assembly 10 a is placed within the mold tooling 40 , 42 illustrated in FIGS. 3-7. FIG. 3 depicts a perspective view of the mold tooling 40 , 42 without the transponder assembly 10 a installed therein. The mold tooling 40 , 42 , when closed, defines a cavity 44 sized to receive the transponder 10 a in preparation for over-molding with the plastic, polymeric or epoxy injection molding material 32 . It should be noted, however, that while depicted as cylindrical, the interior walls of the mold tooling 40 , 42 can have surface features to define a variety of shapes or patterns on the outer surface of the completed transponder 10 , as may be beneficial to particular applications. The potential variations for the design of the exterior shape of the completed transponder, thus, for example, may be cylindrical, bullet shaped, tapered at opposite ends or a flattened oval, and the outer walls may be smooth, rough or bumpy, depending on the intended application.
As depicted in FIG. 3, the mold tooling 40 , 42 includes inwardly projecting pins 46 , 48 which serve to position and secure the transponder assembly 10 a within the tooling 40 , 42 during the injection process. The pins 46 , 48 are configured to be retracted by pressure response pin retractors 50 , 52 into the mold tooling 40 , 42 near the end of the injection cycle. At one end of the mold tooling 40 , 42 is a sprue 56 through which the injection molding material 32 is injected by an injection molding machine (not shown). As also shown in the perspective view of FIG. 3, the mold tooling 40 , 42 may include guide pins 60 on tooling 42 which align with and engage guide pin receiving holes 62 on tooling 40 when the mold tooling is closed, to maintain the alignment of the mold tooling 40 , 42 during the injection cycle.
FIGS. 4-7 depict cross-sectional views of the mold tooling 40 , 42 , and a transponder assembly 10 a positioned therein, illustrating in sequential the advance of the plasticized molding material 32 during the injection molding process. As depicted, the pins 46 , 48 act to co-axially position and center the transponder assembly 10 a within the mold cavity 44 . When the heated and plasticized molding material 32 is injected under pressure by the injection molding machine, the plasticized molding material 32 flows in through the sprue 56 and impinges upon the end 64 of the core 30 as shown by arrow 70 , and axially compresses the core 30 against pins 48 which are positioned to contact the opposite end 66 of the transponder assembly 10 a.
The molding material 32 then flows radially outward along the end 64 of the ferrite core 30 as depicted by arrows 72 in FIGS. 4 and 5. When enough molding material 32 has been injected to fill up the end of the cavity 44 , the advancing face of the molding material 32 proceeds longitudinally along the radially outer surface 68 of the transponder assembly 10 a, as shown by arrows 74 in FIG. 6 . This over-molding injection process only subjects the core 30 to compressive loads, and does not subject the core 30 to tensile loading at any time during the entire injection cycle. Thus, by the over-molding injection process of the present invention the core 30 will not be damaged in a manner which would diminish the electrical or magnetic properties of the core.
When the mold cavity 44 is completely filled with the plasticized molding material 32 , the internal pressure within the cavity 44 increases. The pins 46 , 48 , which position the transponder assembly 10 a within the cavity 44 , are connected to pin retractors 50 , 52 , which are pressure sensitive. When the pressure in the mold cavity reaches a predetermined level, the pins 46 , 48 retract into the mold cavity wall as shown by arrows 76 , 78 , and the space vacated by the pins 46 , 48 is filled by the molding material 32 as shown in FIG. 7 . Since the molding material 32 has already encased the transponder 10 , however, the molding material 32 will hold the transponder 10 in place during the curing or hardening stage of the injection over-molding cycle. Upon completion of the over-molding process, the mold tooling 40 , 42 is opened and the completed transponder 10 is ejected.
FIGS. 8 and 9 depict a side view and a front view, respectively, of an alternative embodiment of a transponder 80 which does not include the core 30 of the transponder 10 of FIG. 1 . Instead, for the transponder 80 , the wire 18 forming the coil 20 is wrapped about the circuitboard 14 upon which the integrated circuit 12 and capacitor 16 are mounted. The coil 20 is interconnected to the circuitboard 14 and the integrated circuit 12 thereon, via leads 22 and 24 generally as discussed above with respect to FIG. 1 . The transponder 80 of FIGS. 8 and 9 is generally much smaller than the assembly of FIG. 1, in that it particularly does not include the core 30 and the added weight and size attendant to the use of the core 30 as depicted in FIG. 1 . The transponder 80 of FIGS. 8 and 9, however, can also be over-molded in a process similar to the process described with respect to FIGS. 4-7.
To briefly illustrate this process, the transponder 80 is depicted within the assembled mold tooling as shown in FIG. 10, which is comparable to mold tooling 40 and 42 discussed above with respect to FIGS. 3-7. In the illustration of FIG. 10, the injection of the plastisized molding material 32 has progressed to essentially the same stage as shown in FIG. 6, in that the advancing face of the molding material 32 is proceeding longitudinally up the outer surface of the transponder 80 and the pins 46 and 48 are centrally positioning the transponder 80 within the mold tooling 40 , 42 . Again, the exterior configuration of the resulting overmolded transponder assembly 60 may be any desired shape which is limited only by the moldability of the shape. It should be noted that transponder 80 may be encased in glass prior to the overmolding process, however, the glass capsule is not shown.
FIG. 11 illustrates another application for the overmolding process according to the present invention in which a frangible core 110 is placed within the mold tooling 40 and 42 of FIG. 3 and positioned by pins 46 and 48 during the over-molding process. The over-molding process proceeds generally in the same manner as discussed above with respect to FIGS. 4-7. FIG. 11 thus illustrates the stage generally corresponding to FIG. 6, wherein the advancing face of the plasticized molding material 32 is proceeding longitudinally along the outer radial surface of the frangible core 110 . Following completion of the over-molding process, the encapsulated frangible core 110 is ejected from the mold tooling. The completed assembly 100 , as shown in the cross-sectional view of FIG. 12, is a frangible core 110 encased within an overmolding material 112 . In this embodiment, the frangible core may be formed from ferrite, powdered metals or high energy product magnets such as samarium cobalt and neodymium-iron-boron materials.
FIG. 13 depicts a cross-sectional view of a transponder within an alternative design for the mold tooling, and positioned therein by one or more centering elements 120 during the overmolding process to fabricate the transponder like that of FIG. 1 . The centering elements 120 are designed with a center portion such as a sleeve 122 , designed to fit around the core 30 . The centering elements 120 may also include radially outwardly projecting fins or pins 124 , which will center the transponder within the tooling during the overmolding process, and thereby eliminate the need for the retractable pins illustrated and described above.
The over-molding process of the present invention encapsulates the frangible core 110 in a protective shell, which allows the frangible core materials to be used in applications which the frangible physical property of such materials would not otherwise allow. For example, samarium cobalt and neodymium-iron-boron magnets encased in a relatively thin coating of plastic or polymeric materials by the over-molding process could be used in objects subject to shock, impact or vibrational loads which would otherwise lead to the cracking, fracturing or other physical and magnetic degradation of the magnetic core.
FIG. 14 depicts a perspective view of the centering element 120 , showing the sleeve 122 and the radial projecting fins or pins 124 . The centering element 120 may be formed from plastic, or from the same type of material used to overmold the transponder. It is also contemplated that the centering element may simply be a part of, or connected, to the bobbin 26 of FIG. 1, wherein the pins 124 simply extend radially outward from one end or both ends of the bobbin.
The material selected for over-molding of the transponder assembly 10 a, transponder 10 or frangible core 110 , depends in part upon the specific application for the completed component. Various types of thermoplastic materials are available for injection molding such components. As used herein, thermoplastic is to be construed broadly, including for example linear polymers and straight-chain or branch-chained macromolecules that soften or plasticize when exposed to heat and return to a hardened state when cooled to ambient temperatures. The term polymer is to be understood broadly as including any type of polymer such as random polymers, block polymers, and graft polymers.
A large number of thermoplastic polymeric materials are contemplated as being useful in the overmolding of transponders and frangible cores of the present invention. The thermoplastic materials may be employed alone or in blends. Suitable thermoplastic materials include, but are not limited to, rubber modified polyolefins, mettallocene, polyether-ester block copolymers, polyether-amide block copolymers, thermoplastic based urethanes, copolymers of ethylene with butene and maleic anhydride, hydrogenated maleic anhydride, polyester polycaprolactone, polyester polyadipate, polytetramethylene glycol ether, thermoplastic elastomer, polypropylene, vinyl, chlorinated polyether, polybutylene terephalate, ploymethylpentene, silicone, polyvinyl chloride, thermoplastic polyurethane, polycarbonate, polyurethane, polyamide, polybutylene, polyethylene and blends thereof.
Preferred thermoplastic materials include rubber modified polyolefins, metallocenes, polyether-amide block copolymers and polyether-ester block copolymers. Preferred rubber modified polyolefins are commercially available under the tradenames of VISTAFLEX™ from Advanced Elastomer Systems Corporation, KRATON™ from Shell Corporation, HIFAX™ from Montell Corporation, X1019-28™ from M. A. Hanna, SARLINK™ from DSM Corporation, and SANTOPRENE™ from Advanced Elastomer Systems Corporation. Preferred metallocenes are available from Dow Corporation under the tradenames ENGAGE™ and AFFINITY™. Preferred polyether-amide block copolymers are available under the tradename PEBAX™ from EIG Auto-Chem. Preferred polyether-ester block copolymers are commercially available from DuPont under the tradename HYTREL™.
The thermoplastic overmolded casings of the present invention may also include a suitable filler or weighting material in order to adjust the properties of the finished casing and/or transponder. For example, the specific gravity or density of the overmolded casing may be adjusted by the addition of a suitable material, such as barium sulfate, zinc oxide, calcium carbonate, titanium dioxide, carbon black, kaolin, magnesium aluminum silicate, silica, iron oxide, glass spheres and wollastonite. The filler or weighting material may be present in an amount that will adjust the specific gravity of the overmolded casing and the resulting transponder. Thus, the weighting material may be added in a range from about 5 percent by weight to about 70 percent by weight. Additionally, the over-molding material for the casings of the present invention may also include a suitable plasticizer or other additives, in order to improve the processability and physical properties, such as the flow properties and ejectability of the over-molding material. The plasticizer may be present in an amount that will adjust the flow properties during the injection molding process as necessary for various applications.
Notably, for many of the foregoing types of injection molding materials, particularly those whose density is increased by the addition of a densifier, the material in its plasticized state for the injection process has a low viscosity. Thus, injection molding such materials requires high injection pressures in turn leading to high stress forces being imposed on the core materials during the injection process. For these reasons, minimizing or eliminating any loading other than compressive loading on the frangible cores during the injection process is highly preferred.
The over-molded casing of the present invention preferably have a wall thickness of between about 0.010 inches to over one inch, however, for most applications the wall thickness will preferable be less than 0.5 inches. Depending on the desired exterior shape of the completed assembly and the shape of the core, the wall thickness of the casing may be uniform or may vary significantly at various locations about the core.
For a bolus transponder 10 intended for use within ruminant animals, it is necessary to have specific physical properties for the over-molded casing material. Thus, the over-molded casing material must be able to withstand the acidic environment in the digestive tract of a ruminant animal, it must be impervious to the microbes and enzymes which are active within the digestive tract of the ruminant animal, and it should preferably have certain physical properties to allow ease in shipping and handling of the bolus transponder 10 prior to administration to the ruminant animal. In addition, it is preferable that the bolus transponder 10 have a specific gravity of at least 1.7 and preferably at least 2. Thus, it is generally desirable to use a weighting material to increase the bulk density or specific gravity of the over-molding material, so that the over-molding material has a specific gravity which assists in maintaining the specific gravity of the fabricated bolus transponder 10 in the desired range.
For a bolus transponder 10 , therefore, it has been determined that a preferred combination of a thermoplastic polyester elastomer sold by DuPont under the trade name HYTREL 3078™, combined with barium sulfate as a densifier provides an acceptable combination for use as the over-molding material for a bolus, and, in appropriate ratios, provides an injection molding material with a specific gravity in the range of between 1.7 and 2. Such a material may be introduced by DuPont and available under the trade name HYTREL 8388.™
By way of providing a specific example, an acceptable over-molding material can be made from a blend of HYTREL 3078™, or a similar thermoplastic polyester elastomer (TPE), mixed with barium sulfate in a ratio of between about 20 to 90% TPE and 80% to 10% barium sulfate. This blend provides a suitable over-molding material to form the casing for the bolus transponder 10 . Purified USP grade barium sulfate or barite fines are preferred as the densifying agents, as these materials have previously been blended with a carnauba wax and a medicant to form boluses for ruminant animals, as described for example, in U.S. Pat. No. 5,322,692 issued to American Cyanamid Company.
The advantages of the foregoing method for use in fabricating boluses have been found to be significant. First, eliminating the necessity of the ceramic encapsulate has resulted in a substantial reduction in material costs as compared to the costs of fabricating a ceramic encapsulated bolus. In addition, the fabrication costs, i.e. the costs of manufacturing the bolus separate and distinct from the component costs, are substantially decreased due to the efficiency and automation associated with the injection molding process. Accordingly, the overall costs savings over the equivalent costs of fabricating bolus transponder encased in a ceramic material may exceed 50%. While the ceramic encased boluses have been found to be relatively fragile such that they can be damaged if they are dropped or even rattled together during shipping, the boluses encased with the HYTREL 8388™—barium sulfate over-molding material has demonstrated physical characteristics which have eliminated these problems. In addition, the bolus transponder 10 of the present invention can be packaged in bulk with minimal packing material because vibrations during shipping between respective boluses does not cause breakage. Finally, the HYTREL 8388™; TPE-barium sulfate combination provides the physical characteristics required for utilization in the stomach of a ruminant animal. The blend is not effected by the acidic conditions, is neutral to the biologic fuana, microbes and enzymes, and it has a preferred specific gravity so as to maintain retention within the stomach of a ruminant animal.
For the transponder 80 of FIGS. 8-10 which is intended for implantation applications, it may be preferable to use a class 6 medical grade epoxy. Alternatively, the transponder 80 may be encased in a glass material by known methods, and then overmolded with the plastic or polymeric materials discussed herein to provide added strength, impact resistance and toughness, which properties are lacking in the glass encased transponders.
It will be appreciated by those skilled in the art that, upon review of the foregoing description of the present invention, other alternatives and variations of the present invention will become apparent. Accordingly, the scope of the protection afforded is to be limited only by the appended claims.
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A method of fabricating, a composition and overmolded components fabricated by the method and with the composition such as an overmolded transponder circuitry for a radio frequency identification device.
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FIELD OF THE INVENTION
[0001] The invention relates to luminaires and in particular to decorative elements, for example to provide a user with an easily changeable decorative element.
BACKGROUND OF THE INVENTION
[0002] To reduce harsh and glaring light emitted by a luminaire a decorative element may be used. The decorative element may shield part or all of the luminaire to reduce glare. The decorative element may also serve an aesthetic purpose too.
[0003] US2011170294 discloses a luminaire having a base, the base includes a heat sink and a primary LED module. There is one of a plurality of interchangeable decorative elements disposed against the luminaire base. The decorative element is fixed in place with one of a plurality of interchangeable collar assemblies.
SUMMARY OF THE INVENTION
[0004] It would be advantageous to achieve a luminaire having a decorative element that is easy to change. It would also be desirable to provide a user with a range of optical structures to suit a particular decorative element. To better address one or more of these concerns, in a first aspect of the invention, there is provided a luminaire, comprising:
[0005] a LED light engine for emitting light,
[0006] an optical structure positioned to receive the light emitted, and
[0007] a decorative element,
[0000] wherein said decorative element is removably located proximate to said light engine by said optical structure and said decorative element is changeable by a user to provide configurable light output characteristics.
[0008] This arrangement enables the light emitted by the light engine to be configured by a user to suit their particular application. In one embodiment the optical structure may be arranged to provide a narrow spot type beam pattern and a different optical structure may be arranged to provide a wide flood type beam pattern. In another embodiment the decorative element may be changed in order to optimize the beam pattern, for example, a narrow angle decorative element to suit an optical structure that provides a spot type beam pattern and a wider angle decorative element to suit an optical structure that provides a flood type beam. Such optical elements are well known in the field, the trend within LED luminaires is to manufacture a product that by virtue of the longevity of the LEDs within need not be user serviceable. Indeed on a frequent basis luminaires are seen that have LED light engines that are overmolded with the optical elements. This means that if the user changes the functionality of part of their room, for example, from a sitting area to a dining area the lighting requirements may well be different for the two uses and the luminaire and more specifically the optical element or structure may well be unsuited for the new lighting requirements.
[0009] It would be advantageous to offer the user a luminaire in which the optical structure can be changed to suit a new lighting requirement and that the optical structure removably locates a decorative element. The decorative element may be changed by a user when the decor of the room is changed or again, to suit a new lighting requirement. A narrow angle decorative element or taken to an extreme, cylindrical decorative element with a light engine at one end will produce a concentrated spot of light on the object that is illuminated. This is because the shape of the decorative element will reflect light internally that is emitted at an angle greater than the angle of the sides of the decorative element relative to the light engine. That is to say, if the decorative element chosen by the user is, for example, a cylinder with the light engine located at one end emitting light into the cylinder then the light emitted by the light engine at angles greater than substantially parallel to the normal of the light engine will impinge on the internal wall of the cylinder and be reflected. This effect can be tailored in multiple ways, the first and most simple way is to adjust the length of the cylinder. A short cylinder will have less light rays impinge upon it than a long cylinder, a greater range of angularly emitted light will exit then in a longer cylinder where a narrower angular range of light emitted does not impinge on the inside of the cylinder.
[0010] It can also be seen that a wider angle decorative element may not have an effect on the angular range of the light emitted by the luminaire if the optical structure is designed to narrow or collimate the light emitted by the light engine. It can be seen that all combinations are possible but in most cases it is probable that a user would wish to tailor both the decorative element and the optical structure to the desired light output requirements.
[0011] The invention also provides a method of installing a luminaire, the method comprising:
[0012] installing a base component of a fixing in the desired location,
[0013] installing one portion of at least one connector to the electrical supply located at the desired location,
[0014] selecting a decorative element that provides configurable light output characteristics,
[0015] locating said decorative element proximate to a light engine,
[0016] securing said decorative element proximate to said light engine using a removably attachable optical structure,
[0017] connecting at least one mechanical and electrical connection at the desired location,
[0018] covering the at least one connection with a decorative cover.
[0000] These and other aspects of the invention will be apparent from and elucidated with reference to the embodiment(s) described hereinafter, the sequence of the steps disclosed is not essential.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Examples of the invention will now be described in detail with reference to the accompanying drawings, in which:
[0020] FIG. 1 shows a luminaire in accordance with an embodiment of the invention,
[0021] FIG. 2 shows a light engine and optical structure in accordance with an embodiment of the invention.
[0022] FIG. 3 shows a cut away view of a light engine and optical structure in accordance with an embodiment of the invention,
[0023] FIG. 4 shows a view of a light engine, a fixing and a decorative cover in accordance with an embodiment of the invention,
[0024] FIG. 5 shows a view of an external structure of an optical structure according to an embodiment of the invention,
[0025] FIG. 6 shows a view of an internal structure of an optical structure according to an embodiment of the invention,
[0026] FIG. 7 shows a simulated view of the luminance generated by a 26 LED array without an optical structure according to an embodiment of the invention,
[0027] FIG. 8 shows a simulated view of the luminance generated by a 26 LED array with an optical structure according to an embodiment of the invention,
[0028] FIG. 9 shows a polar diagram of a light output generated by a light engine and emitted through an optical structure in accordance with an embodiment of the invention,
[0029] FIG. 10 shows a view of a decorative element according to an embodiment of the invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0030] The invention provides a luminaire. A decorative element may be secured in a position proximate to a light engine by an optical structure.
[0031] FIG. 1 shows a luminaire comprising a light engine 1 , an optical structure 2 , a decorative element 3 , a decorative cover 4 , and an electrical wire 5 .
[0032] The light engine 1 comprises at least one LED, in the example shown an electrical driver and the at least one LED are mounted on a common circuit board.
[0033] The optical structure 2 provides optical management of the light emitted by the LED light engine and secures the decorative element 3 in a position proximate to the light engine 1 .
[0034] A decorative cover 4 may be provided; this cover may conceal the electrical and/or mechanical connections between the light engine 1 and the desired fixing location of the luminaire.
[0035] In the example shown the light engine 1 is located at a remote location from the decorative cover 4 and an electrical wire 5 is provided to provide an electrical path between the electrical connection concealed by the decorative cover 4 and the light engine 1 .
[0036] FIG. 2 shows a light engine 1 and an optical structure 2 . In the example shown, the LEDs 6 are mounted on a Printed circuit board (PCB) 7 . Also mounted on this PCB 7 is the electrical driver 8 . The advantage of mounting the driver 8 and the LEDs 6 on a common PCB 7 is that this sub assembly has a small form factor and can be incorporated in smaller LED light engines 1 .
[0037] The light engine 1 is designed to be a standardized part, that is to say that it is a single design that can be utilized in a range of luminaires. The optical structure 2 may be changed for another optical structure that offers different optical management properties. This allow the user to modify the light output characteristics of his luminaire by simply removing the optical structure 2 from the light engine 1 and replacing with a different optical structure 2 . In the example shown the light engine 1 does not have any additional cooling mechanisms such as, for example a heat sink as the PCB 7 radiates the heat generated by the LEDs 6 and the electrical driver 8 via the optical structure 2 .
[0038] FIG. 3 shows a cut away view of a light engine 1 according to an embodiment of the invention. In this example, the optical structure 2 is dished in order to homogeneously spread the light emitted by the LEDs 6 over a wide viewing angle. This optical structure 2 has the advantage of creating multiple secondary light source images; this will give the viewer the impression of a more or less uniform light source behind the optical structure 2 . The optical structure 2 could also be a diffuser; such a diffuser would also create the visual impression of a more or less homogenous light source, furthermore, the optical structure 2 may be a lens and/or a reflector.
[0039] The LED(s) 6 are mounted on a common PCB 7 with the electrical driver 8 . In this example, the PCB 7 is attached to the housing 12 by a mechanical fastener, e.g. a screw 11 . The light engine 1 is also attached in this example to the electrical wire 5 by a mechanical fastener, e.g. a grub screw 13 .
[0040] In the embodiment shown in FIG. 3 , the optical structure 2 has a protruding, annular portion 9 extending around its circumference. The purpose of this annular portion 9 is to support the decorative element 3 . The decorative element could be manufactured with a circular hole that is designed to cooperate with the light engine 1 , i.e. the circular hole may have a diameter larger than the diameter of the housing 12 but smaller than the diameter of the annular portion 9 , this would mean that if the decorative element was located above the annular portion that it would be free to move in a upwards vertical direction but it would not be able to move in a downwards vertical direction.
[0041] The optical structure 2 as shown in FIG. 3 has a fixing 10 , in this example this fixing 10 may comprise a screw thread designed to cooperate with a matching screw thread in the housing 12 . It is also possible to complete the attachment of the optical structure 2 to the housing 12 in other ways, for example, a snap fitting wherein the fixing 10 is of a slightly larger diameter than the internal diameter of the housing 12 . The fixing 10 of the optical structure 2 or the housing 12 may be made of a resilient but deformable medium such as a plastic. This will allow the deformable part to return to its original diameter once the external force has been removed. This is known as plastic deformation. A small residual force may be exerted and this will keep the deformable part in the plastic deformation zone and may result in a more secure snap fit as the both parts exert a small force upon each other. These types of snap fits may allow a secure fit that is still easy for the user to assemble and disassemble with no need for additional tooling, they are also designed to be assembled and disassembled frequently with no noticeable degradation in fit quality.
[0042] The fixing 10 of the optical structure 2 to the housing 12 could be achieved with the use of magnets; these could either be of the permanent magnet type or the electromagnetic type. If a permanent type magnet is used, it may be advantageous to insert ferritic elements in the other cooperating part, for example if magnets were used in the fixing 10 of the optical structure 2 it may be advantageous to insert ferric elements in the housing 12 so that the two parts were magnetically attracted to each other. An electromagnetic fastening may function in a broadly similar way to that of the permanent magnet type of fixing however when power is no longer supplied to the electromagnet the attraction will be removed thus enabling the optical structure 2 to be removed from the housing 12 .
[0043] FIG. 4 shows an embodiment of the invention, in this example the decorative cover 4 is shown in the final position, i.e. the edge 16 may rest against the surface of the desired fixing location, this may be a ceiling, the underside surface of a horizontal surface, for example a shelf etc. The purpose of the decorative cover 4 is to provide a more aesthetic finish to the overall luminaire by concealing the fixing. In this example both a mechanical connection 14 and electrical connection 15 is provided. In other embodiments (not shown) only the electrical connection 14 is provided, mechanical support is achieved by the electrical connection 15 and the electrical wire 5 . In the example shown, a mechanical connection 14 is an eyelet that cooperates with a hook type fixing at the desired location. Other examples of the mechanical connection 14 include, but are not limited to snap fittings, a slideable bolt and hasp or any other type of two or more piece fittings. It is advantageous to use at least a two part mechanical connection 14 as this allows the user to removably attach the luminaire in the desired location.
[0044] In the example shown in FIG. 4 , the decorative cover 4 has a smaller diameter than the annular portion 17 of the housing 12 . The annular portion 17 is part of the housing 12 in this embodiment and not part of the optical structure 2 . This embodiment allows the user to move the decorative cover 4 in a downwards direction along the electrical cable 5 , this will provide access to the mechanical connection 14 and the electrical connection 15 . Advantageously, the electrical connection 15 is a Mate-N-Lok® connector allowing the swift and safe disconnection of the power supply to the luminaire. Alternatively a screw terminal block may be used.
[0045] Once the electrical wire 5 is disconnected from the power the mechanical connection 14 can be disconnected allowing the luminaire to be lowered from the fixing location. The decorative element 3 (not shown) can be maneuvered past the decorative cover 4 , the electrical connection 15 and the mechanical connection 14 . Once the decorative element 3 is clear of the luminaire it may be changed by the user for a different decorative element 3 . The decorative element 3 to be fitted is maneuvered past the mechanical connection 14 , the electrical connection 15 and the decorative cover 4 . The decorative element 3 may have a circular through hole that is larger in diameter than the small diameter 18 of the housing 12 but smaller than the diameter of the annular portion 17 of the housing 12 . The decorative element 3 will be supported in position by the annular portion 17 of the housing 12 . The user then connects the electrical connection 15 and the mechanical connection 14 and conceals the connections with the decorative cover 4 .
[0046] This allows the user to select an optical structure 2 that offers a different light distribution and to fit this optical structure 2 to his existing light engine 1 to obtain the desired light distribution characteristics without having to change the entire luminaire. This brings time and financial benefits to the user and environmental benefits to society as a whole as large parts of the luminaire are not discarded when a different light distribution is desired by the user.
[0047] FIG. 5 shows an embodiment of an optical structure 2 . In this example, the external surface 19 comprises a series of concentric ridges extending in an axial direction. The protruding annular portion 9 for supporting the decorative element 3 (not shown) is also visible.
[0048] FIG. 6 shows an embodiment of an optical structure 2 . In this example, the internal surface 20 of the optical structure 2 comprises a series of radial ridges extending outwards towards the protruding annular portion 9 from a central point. The fixing 10 of the optical structure 2 is shown, this fixing secures the optical structure 2 to the housing 12 of the light engine 1 .
[0049] FIG. 7 shows a simulated view of the luminance generated by an array of 26 LEDs 6 according to an embodiment of the invention. In this example, the light emitted by the LEDs 6 does not pass through an optical structure. The individual point sources of light are high luminance that can be clearly seen and may be perceived as irritating by an observer.
[0050] FIG. 8 shows a simulated view of the luminance generated by an array of 26 LEDs 6 according to an embodiment of the invention. In this example, the light emitted by the array of LEDs 6 passes through the optical structure 2 shown in detail in FIGS. 5 and 6 . It can be seen that the optical structure 2 comprising a combination of axial lenses and radial lenses results in an optical structure that multiplies the LED 6 images and therefore an observer will have the visual impression that there is an equalized luminance distribution across the surface 19 of the optical structure 2 . This equalized distribution will reduce the irritation to the observer as they are no longer able to see the individual high luminance point sources of light.
[0051] FIG. 9 shows a polar plot of the light distribution of the light emitted by the LEDs 6 after passing through the optical structure 2 shown in FIGS. 5 and 6 according to an embodiment of the invention. This shows that the light output is more concentrated in the middle of the optical structure 2 and as such is suitable for overall lighting with a good light distribution for task lighting underneath the luminaire. Other optical structures 2 may be utilized for different light distributions that are desired by the user.
[0052] FIG. 10 shows an embodiment of the decorative element 3 . The decorative element 3 can serve a functional purpose as well as an aesthetic purpose. This can be achieved in a variety of ways. If the decorative element 3 is opaque then the light emitted by the light engine 1 that passes through the optical structure 2 and impinges on the inner surface of the decorative element 3 will be reflected and will exit the decorative element 3 by the exit window 21 .
[0053] The decorative element 3 can be manufactured with a specular or diffuse inner reflectance, a diffuse reflectance may improve the mixing of the light and so if the decorative element has a wide angle (with respect to the normal of the decorative element 3 ) and a large exit window 21 then the light emitted by the luminaire will be homogenous.
[0054] The decorative element 3 may be transparent and it may also have a micro structure on the inner surface. This micro structure may be designed to reflect the light emitted by the light engine 1 that has passed through the optical structure 2 and is impinging on the decorative element 3 ; this is known as total internal reflection (TIR).
[0055] In another embodiment of the invention, the decorative element 3 may be tailored to the optical structure 2 , e.g. the consumer can purchase a decorative element 3 and optical structure 2 that provides a desired light output characteristic from the luminaire. The consumer may wish to purchase an optical structure 2 and decorative element 3 that provide a narrow spot type beam pattern for focused task lighting or they may wish to purchase an optical structure 2 and decorative element 3 that provide a flood type beam pattern for general illumination.
[0056] The decorative element may be manufactured from any material that provides the desired optical or aesthetic characteristics. This can include, for example but not limited to, plastics, ceramics, glass or metals. These can be formed by conventional manufacturing techniques, for example, injection molding, cast molding, lost wax casting, drawing, spinning, machining, turning, glass blowing, or they may be manufactured using additive manufacturing, that is to say 3D printing. Additive manufacturing offers numerous benefits when the decorative element 3 is complex or a consumer wishes to purchase a unique or low volume luminaire.
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A luminaire is provided, the luminaire is fitted with a decorative element ( 3 ) that is simple to exchange for a user without the need for additional tooling. Further, a range of optical structures ( 2 ) are provided that enable the user to easily tailor the light distribution generated by his luminaire without having to purchase an entire new luminaire.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention generally relates to tubular connectors. In particular, the present invention relates to an apparatus for connecting tubulars in such a way that the connection is prevented from becoming unmade in response to expansion of the tubulars in a wellbore. More particularly, the present invention provides a tubular connection using a thread insert to maintain sealing and mechanical integrity in a tubular connection during and after expansion.
[0003] 2. Description of the Related Art
[0004] In order to access hydrocarbons in subsurface formations, it is typically necessary to drill a bore into the earth. The process of drilling a borehole and of subsequently completing the borehole in order to form a wellbore requires the use of various tubular strings. These tubulars are typically run downhole where the mechanical and seal integrity of the jointed connections are critically important in the original make-up of the tubulars, during expansion of the tubulars, and after expansion of the tubulars.
[0005] Typically threaded connections are used to connect multiple tubular members end-to-end. This is usually accomplished by providing tubulars that have a simple male to female threaded connection. The male end is generally referred to as a pin, and the female end as a box. The tubulars are connected, or “made-up,” by transmitting torque against one of the tubulars while the other tubular is typically held stationary. Torque is transmitted in a single direction in accordance with the direction corresponding with connection make-up. Any torque applied to the joint in the make-up direction will have the effect of continuing to tighten the threaded joint.
[0006] When running tubulars there is sometimes a requirement to run jointed tubulars that will later be expanded by various types of expansion mechanisms. In some instances, tubulars are expanded by the use of a cone-shaped mandrel. In this manner, the tubular is expanded by forcibly moving the cone through the expandable tubular, deforming the steel beyond its elastic limit while keeping the stresses below the ultimate yield. Alternatively, another recent method of expanding tubulars relies on rotary expander tools that have been developed to operate in response to hydraulic forces. The rotary expander tool typically includes radially expandable members that are urged outwardly, through fluid pressure, from a body of the expander tool and into contact with a tubular therearound. As sufficient pressure is generated on a piston surface behind these expansion members, the tubular being acted upon by the expander tool is expanded past its point of elastic deformation. In this manner, the inner and outer diameter of the tubular is increased in the wellbore. By rotating the expander tool and by moving the expander tool axially in the wellbore with the expansion members actuated, a tubular can be expanded into plastic deformation along a predetermined length.
[0007] Tubulars to be later expanded are typically run downhole where the mechanical and seal integrity of the connections, or joint, are critically important both in the original and expanded state of the tubular. The current method of making-up expandable tubulars is by the design of modified threaded connections which can be applied and handled in the same way as conventional oil-field tubulars, i.e., stabbed into each other and screwed together by right hand or left hand rotation and finally torqued to establish the seal integrity. This method of connecting tubulars, though a reliable means of connecting non-expanding tubulars, is proving to be problematic when these tubulars are expanded. The reasons for this being mainly due to the changes in geometry of the connection during expansion due to the stresses applied at the threads, or joint area. For instance, conventional tubulars expanded at the joint may disengage allowing the lower tubing to fall into the wellbore.
[0008] It is well known and understood that during the expansion of solid wall tubulars, the material in the tubing wall is plastically deformed in more than just the circumferential sense. In order for a tubular to increase in diameter by plastic deformation, the material to make-up the additional circumferential section of wall in the larger diameter must come from the tubing wall itself either by reduction in wall thickness or by reduction in tubular length or a combination of both. In a plain wall section of the tubular this process will normally take place in a relatively controlled and uniform way. However, at the point of a threaded connection, or joint, the changes in wall section, which are required in order to form an expandable threaded connection, introduce very complex and non-uniform stresses during and after expansion. These during-expansion stresses significantly change the thread form and compromise the connection integrity both in terms of its mechanical strength as well as in terms of its sealing capability.
[0009] Additionally, the larger elastic deformation caused by the reduced sections of the tubing wall at the roots of the thread will introduce much higher stresses than in other areas of the expanded tubular. This in turn may lead to joint failure due to these stresses approaching or exceeding the ultimate strength of the tubing material or by introduction of short cycle fatigue caused by the cyclic nature of some expansion processes being applied at these high stress levels.
[0010] In non-petroleum applications, thread inserts, in particular helical thread inserts, are employed as a means for repairing stripped, worn, or damaged threads. Briefly, where the threads in a bore are stripped or worn, repair is effected by drilling out the bore to remove remnants of the damaged threads, thereafter tapping the drilled out bore and then inserting in the tapped bore an insert, the outer diameter of which is intimately engaged in the threads of the re-tapped bore, the inner diameter of the insert providing a threaded pin receiver portion of the same size and pitch as that presented by the original threading of the bore. In addition to this method, wherein an insert is seated into the recesses of a box thread, the present invention envisions threading the pin threads of a tubular with an insert prior to make-up with a second tubular.
[0011] The objective of the present invention is to resolve many of the problematic areas associated with the expansion of threaded connections in wellbore tubulars. Preferably, the present invention consists of placing a helical or spiral thread insert in engagement with the threads of a first tubular before make-up with a second tubular. The insert bridges any gaps that naturally exist between the threads of a pin and the mating threads of a box. During expansion of the tubular joint, the insert is plastically deformed along with the threads such that a constant wall thickness is maintained. This innovative concept of using plastic deformation of an insert between the mating threads of a jointed system being described herein provides the essential step to making this invention a practical and novel solution to expandable wellbore tubular connections.
SUMMARY OF THE INVENTION
[0012] The present invention may be summarized as an improvement on expandable wellbore tubular connectors. In accordance with the invention, a metal insert, preferably helical or spiral in nature, is placed in engagement with the threads of a first tubular before make-up with the threads of a second tubular.
[0013] In operation, an insert is engaged between the threads of the tubulars prior to make-up of the tubulars. This may be accomplished by engaging the metal insert around the external threads, commonly referred to as a pin, of a first tubular before make-up with the internal threads, commonly referred to as a box, of a second tubular. As such, it may be desirable to have deeper recesses or grooves, and/or shallower teeth, within the thread profile of one or both of the tubulars.
[0014] In the preferred embodiment, a helically wound wire insert is formed around a tapered lead, however a straight lead is an alternative. In the tapered lead embodiment, the insert itself may be formed to carry any number of similar, or dissimilar internal or external thread profiles. As expansion of the threaded joint occurs, the wire insert will plastically deform within the area between the pin-threads and the box-threads to seal any gaps occurring in the thread profile due to internal expansion. The expansion of the insert may occur due to stretching, or drawing of its circumferential length as the thread connection is expanded, or through slippage, relative to the encapsulating box and pin profiles.
[0015] In another embodiment, the insert would be made from a work-hardenable corrosive resistance alloy. Additionally, the wire insert could be coated with Teflon, or some other inert sealing medium known to those in the arts. Such a coating would provide increased sealing benefits.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] So that the manner in which the above recited features, advantages and objects of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
[0017] It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0018] [0018]FIG. 1 is an elevation view of the present invention schematically showing the tubulars within a borehole and a representative expander tool at the jointed area.
[0019] [0019]FIG. 2 is a side view of an insert of the present invention. As shown, the insert has ends with coils in between, wherein the inner diameter of the insert fits the thread profile of a tubular end having a pin or male connection, and wherein the outer diameter of the insert fits the thread profile of a tubular end having a box or female connection.
[0020] [0020]FIG. 3 is an isometric view of the insert showing the positioning of the insert in relationship to the two tubular members and their respective threads.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0021] Generally shown in FIG. 1 are some of the components of the system of the present invention. Visible are a representative rig 2 , a borehole 10 , a ground surface 6 , a formation 4 , a drill string or running string 8 , a first tubular 200 , a second tubular 300 , a representative expander tool 40 comprising a body 42 and an expansion member 45 , or roller, a bore 400 running through the tubulars, and an expandable make-up area, or joint area, of the first and second tubulars 60 .
[0022] In operation the first 200 and second 300 tubulars would be mated together on the surface with the only deviation from normal stab-in and threading procedures being that of adding a wire insert (not shown) between the threads of the connection. After run-in, the tubulars could be expanded from within by any method known to those in the arts, and the connection or joint 60 of the tubulars would be capable of being expanding without losing its mechanical or sealing integrity.
[0023] As shown, a running tool with an expander element 40 or tool attached thereto would be run down the bore 400 of the tubulars. At a desired location, an operator would begin expanding the tubulars. When the expander tool 40 reaches the joint 60 of the two tubulars, the external threads, or pin threads, of the first tubular 200 would be compressed into the internal threads, or box threads, of the second tubular 300 . The wire insert (not shown) that is located between the thread profiles of the two tubulars would be plastically deformed and would “fill-in” any gaps occurring during the expansion process, as well as, ensuring that a more-constant wall thickness is being expanded at the joint area.
[0024] In further description of the expander tool, the expander tool 40 has a body 42 that is hollow and generally tubular. The hollow body 42 allows the passage of fluids through the interior of the expander tool 40 . The body 42 further has a plurality of recesses (not shown) to hold a respective roller 45 , or expansion member. Each of the recesses has parallel sides and holds a roller 45 capable of extending radially from the radially perforated tubular core of the tool 40 . In one embodiment of the expander tool 40 , rollers 45 are near-cylindrical and slightly barreled. Each of the rollers 45 is supported by a shaft (not shown) at each end of the respective roller 45 for rotation about a respective rotational axis. The rollers 45 are generally parallel to the longitudinal axis of the tool 40 . The plurality of rollers 45 may be radially offset at mutual circumferential separations around the central body 40 . In the arrangement shown, only a single row of rollers 45 is employed. However, additional rows may be incorporated into the body 40 . In addition, the arrangement of FIG. 1 presents three rollers spaced apart at 120-degree mutual intervals. However, other configurations may be used.
[0025] In further description of the expandable members, or rollers 45 , the rollers 45 illustrated have generally cylindrical or barrel-shaped cross sections; however, it is to be appreciated that other roller shapes are possible. For example, a roller 45 may have a cross-sectional shape that is conical, truncated conical, semi-spherical, multifaceted, elliptical or any other cross sectional shape suited to the expansion operation to be conducted within the tubular's bore 400 .
[0026] Each shaft is formed integral to its corresponding roller 45 and is capable of rotating within a corresponding piston (not shown). The pistons are radially slidable, one piston being slidably sealed within each radially extended recess. The backside of each piston is exposed to the pressure of fluid within the hollow bore of the tool 40 . In this manner, pressurized fluid provided from the surface of the well can actuate the pistons and cause them to extend outwardly whereby the rollers 45 contact the inner surface, or bore 400 , of the tubular to be expanded.
[0027] The expander tool 40 is preferably designed for use at or near the end of a working string 80 . In order to actuate the expander tool 40 , fluid is injected into the working string 80 . Fluid under pressure then travels downhole through the working string 80 and into the perforated tubular bore of the tool 40 . From there, fluid contacts the backs of the pistons. As hydraulic pressure is increased, fluid forces the pistons from their respective recesses. This, in turn, causes the rollers 45 to make contact with the inner surface of the tubular to be expanded. Fluid finally exits the expander tool 40 through a connector at the base of the tool 40 . The circulation of fluids to and within the expander tool 40 is preferably regulated so that the contact between and the force applied to the inner wall of tubular 400 is controlled. The pressurized fluid causes the piston assembly to extend radially outward so as to place the rollers 45 into contact with the inner surface of the tubular 400 . With a predetermined amount of fluid pressure acting on the piston surface, the tubulars are expanded past their elastic limits.
[0028] [0028]FIG. 2 is a side view of an insert 100 of the present invention. As shown, the insert has ends 110 , 120 with coils 150 in between wherein an inner diameter 130 of the insert fits the thread profile of a first tubular end (not shown) having a pin or male connection, and wherein an outer diameter 140 of the insert fits the thread profile of a second tubular end (not shown) having a box or female connection.
[0029] In operation, the insert 100 is preferably mated and engaged around the external threads of a first tubular; however it is also envisioned that the process could happen with the insert 100 first being placed in engagement with the box thread profile of the second tubular prior to the pin threads of the first tubular being inserted therein. Preferably, the inner diameter 130 of the insert 100 engages the external threads, pin, of a first tubular in much the same way as a nut screws around the threads of a bolt. The outer diameter 140 of the insert 100 is designed such that a second tubular can be threaded around the insert 100 and pin thread combination. The outer diameter 140 thus mates with a corresponding thread profile of the second tubular (not shown). The outer diameter 140 may or may not make contact with the box threads during make-up.
[0030] Typically, the threaded insert is malleable in nature and is helically or spirally shaped. Malleability may come from the insert being metallic in composition. 4140 steel, 316 stainless, or an alloy such as Hastelloy G3 or Incoloy 825 are but a few examples of the possible materials that the insert may be comprised from. Depending upon wellbore and downhole fluid characteristics, the insert 100 could also be coated with Teflon or another inert sealing material known to those in the field in order to add another layer of sealing protection, especially for gas wells.
[0031] [0031]FIG. 3 is an isometric view of the insert showing the positioning of the insert in relationship to the tubular threads. Shown in FIG. 3 is the make-up orientation of the tubulars with the insert positioned between the pin 210 and box 310 threads of the two tubulars. Typically, the insert 100 would be wound or aligned around the pin threads 210 prior to connecting of the two tubulars.
[0032] After the tubulars 200 , 300 are made-up they are ready to be run downhole. Expansion of the tubulars 200 , 300 occurs within a wellbore, shown in FIG. 1, wherein an expanded tool plastically deforms the bore 400 of the tubulars 200 , 300 to a predetermined size. When expanding the joint of the tubulars, the threads of the pin 210 and box 310 will plastically deform and force the insert 100 to maintain a mechanical and sealing relationship between the tubulars 200 , 300 .
[0033] The connection arrangement shown in FIGS. 2 and 3 are but one example of a connector of the present invention. Other arrangements and embodiments may be utilized within the spirit and scope of the present invention.
[0034] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
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The present invention provides a connector arrangement for connecting a first tubular to a second tubular. In particular, the present invention relates to a method for connecting tubulars in such a way that the connection is prevented from becoming unmade in response to expansion of the tubulars in a wellbore. More particularly, the present invention provides a tubular connection using a helical or spiral thread insert to seal and maintain mechanical strength in a tubular connection after expansion.
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BACKGROUND OF THE INVENTION
The invention relates to a lifting and depositing device for portable containers, e.g., containers, shelters, superstructure replacement parts or the like, with a plurality of rack and pinion jacks to be fastened on the container, of which the jack housings can be connected with the container, and can be raised and lowered along a support leg with a rack, and the jacks have parts which can be pivoted away or removed.
A lifting and depositing device of this type is already disclosed in German Pat. No. 1,586,723. With this device, the jack housings can be opened to the outside by the parts which can be pivoted to the side or removed, so that the support legs can be inserted from the outside transversely to the lift direction into the open jack housing, which provides the advantage that the support legs can be connected at practically any height on the container with the rack and pinion jacks on the side of the container. Thus, time-consuming cranking which is otherwise necessary for the two idle strokes during a work cycle (depositing the container from the vehicle onto the ground and later the reverse) is unnecessary.
It is known that the separate rack and pinion jacks are moved together when not in use, saving space during storage. Because of the possibilof separation of the support legs from the rack and pinion jacks, detachably attached to the portable containers, this lifting and depositing device is divided into individual lightweight parts which are easy to handle. However, here the rack and pinion gear, forming one part with the bracket, is still relatively heavy and therefore correspondingly difficult to handle. Also, with the jack housing parts pivoted away, the support legs could not be manually moved axially into the jack housing, in order to optionally by-pass the required idle stroke. For this purpose, the support legs must always be moved to the side out of the opened jack housings.
A lifting and depositing device for portable containers is also disclosed in German Pat. No. 2,540,400, in which the bracket can be separated from the rack and pinion jacks and their housings. Here, however, the rack and pinion jack gearing with relatively high jack housings are again in one part and form a correspondingly heavy structural part. One further drawback of this known device resides in the fact that, because of the closed jack housing, the idle stroke must both upwards and downward be by-passed continuously by means of the rack and pinion gearing by means of time-consuming cranking.
SUMMARY OF THE INVENTION
The object of the invention is a lifting and depositing device for portable containers, in which the time-consuming idle stroke over the jack gearing can be avoided by manual movement of the support legs in the jack housings, and at the same time more weight is saved because of the separate parts of the lifting and depositing device, which facilitates handling. Furthermore, if needed, the gearing or at least the driving pinion of the rack and pinion jack and the racks in the jack area can be cleaned.
This is attained according to the invention in that the part of each jack housing which can be pivoted to the side or can be removed is configured as an accessory gearing.
When the accessory gearing is removed, the weight of the individual parts of each rack and pinion jack is further reduced, so that they are simpler to handle. If the accessory gearing is pivoted to the side or away, further required cleaning of the gearing could be carried out simply. This is not possible with the lifting and depositing device of German Pat. No. 1,586,723, since here the jack gears are arranged on the bracket between the container and the individual racks and support legs, and the racks on the support legs are turned toward the container. The same is also true for the lifting and depositing device of German Pat. No. 2,540,400, in which the jack gearing housings are connected with the guide parts of the jack housings for the support legs.
The invention furthermore makes it possible that with accessory gears pivoted to the side, the idle stroke as by-passed by operation of the jack gearing is unnecessary, and the support legs need only be moved up or down with their rack and pinions in their jack housings. Upon disassembly of the lifting and depositing device, the support legs with their racks can be drawn completely out of the jack housing.
The present invention provides the advantage that with the friction brake device, when the accessory gearing is pivoted out or removed, the support leg and rack can be secured in the guide part of the jack housing against undesired slippage. The additional security against withdrawal combined with the friction brake device prevents any subsequent undesired tearing of the support leg from the jack housing.
In accordance with another refinement of the invention, even when the accessory gearing is pivoted out or removed, with the outwardly opened jack housing, the racks (with the support leg) can be fixed on the guide part of the jack housing. This advantage then appears as very important when the lifting and depositing device is very dirty and carries a more or less heavy container, so that poor operation or total blocking of the rack and pinion jack for manipulation of the container is to be feared. In this case, one need only exchange or remove the accessory gearing, so that at least the driving pinion and the area of the racks of the gearing can be easily cleaned. This work can take place while the lifting and depositing device is loaded, because if the gearing is pivoted out or removed, the relevant rack is fixed on the jack housing by the stop device. The associated lifting device advantageously allows release or separation of the gearing from the relevant loaded rack. This embodiment of the invention also provides more advantageously than when the containers are mounted and braced on the lifting and depositing device, the accessory gearing can be removed and can be stored at a safe site, which secures it against misuse, so that it will last longer. However, it is also possible to use the removed accessory gearing with other containers to be lifted or deposited, which means that a series of gearings can be used for the operation of a plurality of lifting and depositing devices one after the other.
The invention provides the advantage that it is simpler to produce a satisfactory operative connection between any one accessory gearing and a rack. The guide part, which slips along on the support leg, also forms a guide for the housing of the attached accessory gearing.
When the guide part of the jack housing also forms a part which is connected detachably with a bracket to be mounted on the container, the weights of the individual parts of the lifting and depositing device are reduced and they are thus made still easier to handle.
When the accessory gearing is connected detachably by cotter bolts on its top and bottom ends with the guide part of the jack housing, only the part connected by one cotter pin can advantageously be pivoted out upwardly or downwardly around the other cotter pin for cleaning.
A further embodiment of the invention shows that the guide parts of the jack housing cannot buckle if the support legs are at an obtuse angle.
Also, when the accessory gearing with at least one gearwheel overlaps the side of the guide part of the jack housing, a relatively large reduction ratio can be produced advantageously with relatively smoothly constructed gearing.
In accordance with another simple embodiment of the lifting and stopping device, the wedge-shaped parts can be moved toward or away from each other by a spindle which is axially immovable in the stop element but which can be manually rotated, with right and left threading on the ends which engage in corresponding threads in the wedge-shaped parts.
In the use of the present invention, the stop element can be relatively small, which means a saving of weight, and the safety shaft prevents the support leg from breaking out from the guide part of the jack housing (around the stop element) when it has stopped.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be further clarified relative to the drawings of exemplary embodiments. They show:
FIG. 1 is a side elevational view of a rack and pinion jack on a container, the jack working on a support leg of the lifting and depositing device, wherein only one part of the support leg and the container is shown;
FIG. 2 is a front elevational view of the device of FIG. 1;
FIGS. 3, 4 and 5 are transverse cross-sectional views taken substantially along lines A--A, B--B and C--C, respectively, of FIG. 1;
FIG. 6 is a side elevational view of the accessory gearing of a rack and pinion jack corresponding to FIG. 1;
FIG. 7 is a side elevational view similar to FIG. 1, showing the accessory gearing pivoted outwardly;
FIG. 8 is a side elevational view of the guide part of the jack housing with a part of a support leg with a rack, the stop element and the safety shaft being in an operational state;
FIG. 9 is a front elevational view of the device of FIG. 8;
FIGS. 10 and 11 are partial cross-sectional views taken substantially along the lines D--D and E--E, respectively of FIG. 9;
FIG. 12 is an enlarged view, partly in cross section, of the bottom portion of the device of FIG. 9;
FIG. 13 is a side elevational view of the device of FIG. 12;
FIG. 14 is a side elevational view of a second embodiment of the invention with the jack housing having its side closed, and one attached accessory gearing;
FIG. 15 is a side elevational view of the guide part of the jack housing for the support leg with rack corresponding to the device of FIG. 14;
FIG. 16 is a side elevational view of the accessory gearing of the rack and pinion jack corresponding to that of FIG. 14;
FIG. 17 is a side elevational view similar to that of FIG. 15, with a friction brake device, combined with an extraction safety for the support leg; and
FIG. 18 is a partial plan view of a portion of the device of FIG. 17, taken in the direction of the arrow A.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The embodiments of the invention corresponding to FIGS. 1-13 and 14-18 represent lifting and depositing devices intended for containers of generally rectangular shape. Both exemplary embodiments have four support legs 11 with associated rack and pinion jacks 12 and 12', which can be detachably mounted on brackets 13 and 13' on the side of a container, e.g., 10, or on its corner. A container can be lifted by means of this lifting and depositing device, and can be deposited on the loading surface of a truck, or vice versa can be lifted from this loading surface and, with the device in lifted state, can be transported and can even be deposited on the ground or on a special carrying platform. A rack and pinion jack 12 with connected support leg 11 is described in the following. All rack and pinion jacks 12 and support legs 11 are identical.
The rack and pinion jack 12 has a guide part 14 supported on an essentially U-shaped support leg 11. Support leg 11 can be a quadrangular tube. A footplate 15 is at the bottom end of support leg 11. Guide part 14 in the embodiment is connected inflexibly with bracket 13, but these parts can also be detachably connected. Bracket 13, as aforementioned, can be mounted detachably on the side wall of container 10 near the corner. A rack 16 is preferably found in the middle of the outside of support leg 11.
Rack and pinion jack 12 also has an accessory gearing 17 which is arranged on guide part 14 so that it can be pivoted outward or removed. The housing of accessory gearing 17 is encased separately, and in the attached state it extends fitting partially into U-shaped guide part 14, as shown in FIGS. 3 to 5. In the embodiment, accessory gearing 17 is connected detachably with guide part 14 by identical cotter pins 18 which, fitting through corresponding bores 20, 21, extend into guide part 14 or 22 in the housing of gearing 17. On the bottom end, cotter pins 18 have a part 23 with an inward directed screw thread, which cooperates with an outward directed screw thread on parts 24, which are found on the outside of guide part 14. Cotter pins 18 extend through middle bores in parts 24. The opposite ends of cotter pins 18 are provided with grooves 25 to receive safety flanges 26 which have corresponding slots. When safety flanges 26 are inserted, with suitable rotation of cotter pins 18 by means of the lever 27 based on the cooperation of the screw threads on parts 23 and 24, the housing of accessory gearing 17 can be braced in guide part 14. In this state, cotter pins 18 also secure guide part 14 against "spreading" as a result of support leg 11, when pivot forces engage on it, which can occur when the ground is not level. An additional or alternative security can be formed as shown in the embodiment of two holding strips 28 mounted at the same level on the housing of accessory gearing 17 (FIGS. 1 and 4), which, when gearing 17 is attached, overlap guide part 14 at the side.
The crank handle of gearing 17 is 29 and some of the gearwheels of the accessory gearing in FIG. 1 are 30, 31, and 32. With the desired reduction ratio, in order to attain a relatively smooth accessory gearing 17, gearwheel 32 with the largest diameter is arranged in a housing part 34, which overlaps guide part 14 at the side. Gearwheel 32 sits nonrotatably on a shaft 33 (FIG. 5), on which the driving pinion 35 for rack 16 on support leg 11 is also mounted.
In dusty areas, when container 10 is carried for a long time raised up from support legs 11, driving pinion 35 and racks 16 can get dirty, which can slow the operation or even block the rack and pinion jacks 12. In case of this, so as to be able to clean driving pinion 35 as well as racks 16 for the operation of rack and pinion jacks 12, also relative to the accessory gearing 17, accessory gears 17 are either removed by guide parts 14 or can be pivoted out, as shown in FIG. 7. For this, safety flanges 26 are first removed, so that the cotter pins 18 of FIG. 2 can be drawn out to the right. Thereupon the accessory gearing 17 can only be cleaned when accessory gearing 17 is pivoted out of the way, for example only the bottom cotter pin 18 is removed, so that gearing 17 can be pivoted upward around top cotter pin 18 (FIG. 7). A lifting and depositing device is to be found between each guide part 14 and support leg 11 or its rack 16, in order to facilitate removal of accessory gearing 17 from guide parts 14 or their pivoting out under a load (i.e., with raised container 10), which is to be explained hereinafter with reference to FIGS. 8 to 13.
Guide part 14 of the jack housing is U-shaped and both arms are provided near the front with countersunk openings 36 and 37 on the sides. These are open downward. A stop element 38 fits in side openings 37 for the withdrawal of one or both cotter pins 18, and stop element 38 is provided with teeth 39 (FIG. 10), and brought into contact with rack 16. When stop element 38 is positioned in this manner in openings 37, wedge-shaped parts 41 are driven from the outside inward into the remaining intermediate spaces 40 between the top edge of stop element 38 and openings 37, and parts 41 cause an insignificant lift of guide part 14 in relation to support leg 11, and the friction between driving pinion 35 and the (loaded) rack 16 is reduced so that, after removal of one or both cotter pins 18 from guide part 14, accessory gear 17 can be removed or pivoted out. However, a safety shaft 42 is still inserted through openings 36, and when accessory gearing 17 is removed, it prevents support leg 11 from buckling forward out of guide part 14. For this purpose, safety shaft 42 stands in position with rack 16. It is to be noted that the rack and pinion jacks 12 are of a known embodiment under self-limiting load.
The oblique surfaces 46 of wedge-shaped parts 41 cooperate with corresponding oblique surfaces 45 on stop element 38. A spindle 43 is axially tightly mounted in a longitudinal bore 47 in stop element 38, but is rotatable, and the ends are each provided with a left or right threading 48, 49. An annular collar 50 is provided thereon for axial fixation of spindle 43, which is held by a bushing 51 pressed into the flared part of longitudinal bore 47, against a stop 52 in longitudinal bore 47. The left or right threading 48, 49 of spindle 43 engages with corresponding inner threading on sheathed operating parts 54, 55 for wedge-shaped parts 41. The sheathed operating parts 54, 55 for this purpose are axially movable in longitudinal bore 47 or in bushing 51, and are height adjustable in connection with wedge-shaped parts 41. With suitable manual rotation of spindle 43 by means of its knob 44, wedge-shaped parts 41 are forced against each other, by means of operating parts 54, 55 and they wander upward because of their cooperating oblique surfaces 45, 46, and by-pass intermediate spaces 40 and finally lift guide part 14 slightly in relation to rack 16 and support leg 11, so that the aforementioned friction closure between driving pinion 35 and rack 16 is lifted. Wedge-shaped parts 41 can again be held fast, as a result of opposite rotation of threaded spindle 43, so that, according to the structure of accessory gearing 17, stop element 38 can be removed again.
In FIG. 7 is to be noted that guide part 14 is shown in its bottom setting, in which it rests on a collar 56 on support leg 11, and stop element 38 is not required here when accessory gearing 17 is pivoted out.
In the embodiment of FIGS. 14-18, the rack and pinion jack 12' has a lifting and lowering, round, closed guide part 14' on support leg 11, which is relatively longer (approximately the height of the container), which is detachably mounted on bracket 13' on the side of the container (not shown) or on its corner. Support leg 11 with rack 16 corresponds essentially to that of the first embodiment. Tubular guide part 14' is closed off at the top by a cover 60, which can be removed for cleaning. Furthermore, guide part 14' has two top and two bottom strips 61 and 62 on the outside which are at some distance from the side, with bores 63 countersunk in the sides, as well as a cutout 64 which frees a section of rack 16.
Accessory gearing 17' in this embodiment has a housing 65 with top and bottom protrusions 66 and 67, with bores 68. The protrusions 66 and 67 fit exactly between the pairs of strips 61 and 62. When consequently accessory gearing 17' is to be connected with guide part 14', protrusions 66 and 67 need only be inserted between pairs of strips 61, 62 and bores 63, 68 countersunk side by side, so that cotter bolts 18' can fit through these bores. Housing 65 of accessory gearing 17' thus houses the U-shaped section 69 around guide part 14' and driving pinion 35' of gearing 17' comes into contact with rack 16. In FIGS. 14 and 16, 70 is the square drive shaft of accessory gearing 17', on which a handle (not shown) can be mounted for shifting gears. If only top cotter pin 18' connects accessory gearing 17' with guide part 14', gearing 17' can be pivoted away in clockwise direction as in FIG. 14, so that driving pinion 35' is separated from rack 16. To avoid an idle stroke during shifting of gears in this state or even with completely removed gearing 17', it is simply possible to move support leg 11' upward or downward in guide part 14' when the container is being deposited with the rack and pinion jack, e.g., on the loading surface of a truck. As in the first embodiment, it is advantageously possible to clean it when gearing 17' is pivoted out or removed.
Upon detachment of driving pinion 35' from rack 16, to avoid an undesired relative movement between support leg 11 and guide part 14' as a result of the force of gravity, a friction brake device 70 which cooperates with support leg 11 can be provided on guide part 14' (FIGS. 17, 18). This device 70 has a sheathing 71 mounted axially movably on guide part 14', but a bolt 72 is mounted nonrotatably, which engages on a friction body 73 at one end, which is pressed by a spring 74 against support leg 11 to prevent movement between parts 11 and 14'. Spring 74 is stretched for this purpose between an annular collar 75 on bolt 72 and a perforated disk 76 mounted inside on sheathing 71. A pin 77 extends through bolt 72, guided in sheathing 71 in slots 78 which are open to the outside. When brake device 70 is in operational state, which is shown in FIGS. 17 and 18, pin 77 is in contact with slot 78. If the friction brake device 70 should be inoperative, bolts 72 need to be drawn out by means of knob 79 against the pressure of spring 74, in order to bring pin 77 into position with the outside free edge of sheathing 71.
In the embodiment of FIG. 17, a cutout 80 is provided with a detent 81 on its top end, at the top of support leg 11, and friction brake device 70 also prevents extraction. Detent 81 remains suspended on friction body 73 on bolt 72, telescoped by spring pressure, when support leg 11 slips downward in guide part 14'. The friction brake device can also be in the hollow support leg and can cooperate with one or two friction bodies with the inside wall of guide part 14' (not shown).
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A lifting and depositing device for portable containers comprising a plurality of rack and pinion jacks, some of which are mounted on support legs of the container. Each rack and pinion jack has an accessory gearing which can be pivoted outwardly or removed, so that when accessory gearing is pivoted outwardly, a support leg can be manually moved axially relative to its guide part, if the container, e.g., is offset on the loading surface of a truck. Thus, the gearing operation and time-consuming crank work required until now for two idle strokes per work cycle is avoided.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a continuation application, under 35 U.S.C. §120, of copending International Application PCT/EP2015/053414, filed Feb. 18, 2015, which designated the United States; this application also claims the priority, under 35 U.S.C. §119, of German Patent Application DE 10 2014 202 970.8, filed Feb. 18, 2014; the prior applications are herewith incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The invention relates to a radial braiding machine including a bobbin gear through which stationary yarn and braiding yarn are fed, a braiding ring through which the stationary and braiding yarns are guided, a core to be over-braided and at least one transportation device for transporting the core. The invention also relates to a braiding ring for use in a radial braiding machine and to a flat braid obtained by over-braiding a core using a radial braiding machine with a braiding ring through which yarns are guided by a bobbin gear. The flat braid includes stationary yarns extending in the longitudinal direction of the braid, and braiding yarns interwoven with the stationary yarns and extending at an oblique angle to the stationary yarns, the course of the braiding yarns differing from an ideal, straight course of a nominal layer by an angle of twist and each stationary yarn being at a distance from an adjacent stationary yarn. The invention additionally relates to a method of producing the flat braid.
[0003] A generic radial braiding machine is disclosed, for example, in German Patent Application DE 2 112 499, corresponding to U.S. Pat. No. 3,599,529, and is equipped with a bobbin gear, through the use of which stationary yarns and braiding yarns are guided to a braiding ring and guided therethrough. Furthermore, a transportation device for transporting a core to be over-braided must be present. The device is likewise moved through the braiding ring. Conventionally, the braiding ring which is always perpendicular to a core having a round cross section, also has a round inside diameter.
[0004] In practice, by using a radial or round braiding machine of that type, solely round braided sleeves could be produced, which had high requirements in terms of uniformity and yarn course. However, when producing braids for diameters which are not circular, the yarns warp and irregularities occur. That applies in particular to flat braids which are produced on such machines, for which a tubular round braid which is created is merely flattened. Undesirable warping of the yarns occurs in particular at the edges of the resulting flat braid.
SUMMARY OF THE INVENTION
[0005] It is accordingly an object of the invention to provide a radial braiding machine, a braiding ring, a flat braid and a method of producing the flat braid, which overcome the hereinafore-mentioned disadvantages of the heretofore-known machines, rings, braids and methods of this general type, which allow the precise production of various braids and which provide an improved flat braid.
[0006] With the foregoing and other objects in view there is provided, in accordance with the invention, a radial braiding machine, comprising a bobbin gear through which stationary yarn and braiding yarn are fed, the bobbin gear spanning a yarn outlet plane, a braiding ring through which the stationary and braiding yarns are guided, the braiding ring having a non-round internal cross section when projected onto the yarn outlet plane, a core to be over-braided, and at least one transportation device for transporting the core.
[0007] In this case, the point of the deposition of the braiding yarns on the core to be over-braided and the tension of the yarns is influenced by the braiding ring having a non-round internal cross section, that is to say an internal cross section which differs from the circular shape, and more specifically when projected onto a yarn outlet plane which is spanned by the bobbin gear. This can, of course, preferably be brought about by a braiding ring, which itself has a non-round internal cross section, but also by a ring having a round cross section which is mounted in an oblique or twisted manner with respect to the bobbin gear in such a way that only the projection of the internal cross section thereof is not round. This likewise has the effect of a non-round internal cross section. Good results can be achieved by using a braiding ring having an internal cross section with an oval or elliptical shape when projected onto the yarn outlet plane. However, it is preferable for the braiding ring itself to have an oval or elliptical internal cross section.
[0008] Another influence on the yarn tension and deposition position of the yarns on the core to improve the braid properties can be achieved on a braiding machine in which the front side of the braiding ring, through which the yarns are substantially diverted, protrudes in regions from the yarn outlet plane which is spanned by the bobbin gear or from a plane which is parallel thereto. As a result of the fact that the front side protrudes only in regions, but not completely, and to different extents from the yarn outlet plane or the parallel plane in the opposite direction to the transportation direction of the braid core, specific regions of the braiding and stationary yarns are guided in a controlled manner in such a way that they come to rest on the core sooner or later than other yarns, or obtain another tension. Another adjustment and/or fine adjustment can take place by placing the braiding ring in the radial or round braiding machine in a pivoted manner, and more specifically about at least one of two pivot axes which are orthogonal to one another, so that the yarn diverter protrudes to different extents at the points of intersection with one or both of the pivot axes on each side of the braiding ring. The configuration can be selected in such a way that the yarn diverter protrudes to different extents or projects at different heights at all four points of intersection of the pivot axes with the braiding ring.
[0009] With the objects of the invention in view, there is also provided a braiding ring for use in radial or round braiding machines, the front side of which that diverts the stationary and braiding yarns, referred to as the yarn diverter, according to the invention spans an imaginary surface which is curved at least in regions. That is to say that a surface which would be in contact with all of the points of the yarn diversion of the braiding ring would not be a planar, straight surface. A braiding ring of this type can also have in particular an inner contour which differs from the circular shape, preferably an elliptical inner contour. The yarn diverter of a braiding ring of this type can also protrude to different extents at the points of intersection of two intersecting inside diameter axes.
[0010] With the objects of the invention in view, there is additionally provided a flat braid obtained by over-braiding a core using a radial braiding machine with a braiding ring through which yarns are guided by a bobbin gear. The flat braid comprises stationary yarns extending in a longitudinal direction of the braid, each of the stationary yarns being disposed at a distance from a respective adjacent stationary yarn, and braiding yarns being interwoven with the stationary yarns and extending at an oblique angle to the stationary yarns, the braiding yarns following a course differing from an ideal, straight course of a nominal layer by an angle of twist. The angle of twist is at most +/−3° and is obtained by influencing a position and a time of deposition of the stationary and braiding yarns on the core by modifying the braiding ring from a circular shape taking into consideration a shape of the core, providing the braiding ring with an internal cross section having a non-round shape when projected onto a yarn outlet plane being spanned by the bobbin gear and providing the braiding ring with an inner contour being at a different distance from an outer contour of the core to be over-braided.
[0011] In this case, braiding errors or deviations from the ideal braiding yarn course, which are referred to as an S twist or Z twist, are reduced to an angle of twist of at most +/−3°. This can be produced by a braiding method in which the position and time of deposition and the yarn tension are influenced by modifying the braiding ring of the braiding machine from a circular shape, while taking into consideration a core shape to be selected in such a way that the internal cross section of the braiding ring has a non-round shape when projected at least onto the yarn outlet plane which is spanned by the bobbin gear, and the inner contour of the braiding ring is at a different distance from the outer contour of the core to be over-braided. For this purpose, substantially rectangular braiding cores can also be selected, which can also be very flat and thus already come close to the later shape of the flat braid. The differences in tension in the braiding yarns at the outer edges of the flat braid, which are unavoidable in the prior art, are avoided or minimized in this case. Preferably, a flat braid is thus achieved having distances between the stationary yarns with an average standard deviation of only at most 5%, more preferably at most 2%. With the specification of the average standard deviation, the fact has also been taken into account that the distance between two stationary yarns is never 100% constant over the length of the flat braid. The distance between two stationary yarns is therefore accordingly specified as an average. The average standard deviation is thus the standard deviation of the average distances between the stationary yarns in the flat braid.
[0012] The deposition of the yarns on the core including the yarn tension can in this case be influenced by using a special construction and/or mounting of the braiding ring so that the front side thereof which diverts the braiding yarns (yarn diverter) protrudes at various positions to different extents over the yarn outlet plane or a plane which is parallel thereto.
[0013] When using a non-round core having different cross-sectional dimensions of a maximum height and a maximum width, the braid properties can be influenced in a positive manner when the internal cross section of the braiding ring (when projected at least onto the yarn outlet plane El) differs in an inverse manner from the circular shape, that is to say that the distance thereof from the core at the position of the maximum core cross-sectional dimension is selected so as to be smaller than at the position of the minimum core cross-sectional dimension. It also has a positive effect when the yarn diverter on the front side of the braiding ring protrudes further at the position of the maximum cross-sectional dimension of the core than at the position of the minimum core cross-sectional dimension.
[0014] A braiding ring having a front side which protrudes to different extents on each side of the maximum and/or minimum cross-sectional dimension of the core, or mounting a braiding ring in such a way that a spatial positioning of this type occurs can also influence the braid in a positive way, in particular when using braiding cores having a longitudinal axis which is not straight. One way of achieving this influence by using the mounting of the braiding ring is to mount the ring in a tilted and/or pivoted manner with respect to the yarn outlet plane.
[0015] All of the embodiments of the braiding ring which are disclosed in relation to the braiding machine can be combined with the method according to the invention and vice versa.
[0016] Other features which are considered as characteristic for the invention are set forth in the appended claims.
[0017] Although the invention is illustrated and described herein as embodied in a radial braiding machine, a braiding ring, a flat braid and a method of producing the flat braid, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
[0018] The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0019] FIG. 1 is a diagrammatic, side-elevational view of a radial braiding machine according to the invention;
[0020] FIG. 2 is a perspective view as seen in the direction II of FIG. 1 ;
[0021] FIG. 3 is a perspective view and two side-elevational views of the braiding ring of FIG. 1 ;
[0022] FIG. 4 is a perspective view as seen in the direction IV of FIG. 1 ;
[0023] FIG. 5 is a diagrammatic, plan view of a flat braid according to the invention; and
[0024] FIG. 6 is a diagrammatic, perspective view of an angle of twist in a braid.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Referring now to the figures of the drawings in detail and first, particularly, to FIG. 1 thereof, there is seen a simplified view of a radial braiding machine which has a bobbin gear 1 from which stationary yarns and braiding yarns 2 , 3 are guided through a yarn-diverting front side 4 , also referred to as a yarn diverter, of a braiding ring 5 and subsequently guided therethrough. In order to create the braid, a core 6 to be over-braided is pushed through the braiding ring 5 in a transport direction 7 by a transportation device 10 . In so doing, the then interweaving yarns 2 , 3 are located on the core 6 as a braid, which is only suggested in FIG. 1 . The bobbin gear 1 is annular and spans a yarn outlet plane E 1 . The yarns 2 , 3 emerge from the inside of the bobbin gear 1 , which is only diagrammatically indicated in FIG. 1 .
[0026] FIG. 2 is an oblique front view as seen from a position II in FIG. 1 , which shows only part of the bobbin gear 1 , but in a much more detailed and perspective view. It can be seen in this figure that the core 6 has a flat, rectangular cross section which is disposed so as to be opposed to an elliptical internal cross section of the braiding ring 5 in the embodiment shown.
[0027] FIG. 3 is a detailed view of the braiding ring 5 and four retaining elements 8 thereof, through the use of which the ring is attached to the non-illustrated bobbin gear. The braiding ring 5 has not only an oval inside diameter, but also outwardly curved sides 15 on the front side 4 thereof, which protrude from a plane (E 2 ) that is parallel to the yarn outlet plane E 1 (see also FIG. 1 ) which is spanned by the bobbin gear. By contrast, upper and lower ends 25 of the front side 4 of the braiding ring 5 are aligned with the plane (E 2 ) so that the front side 4 of the braiding ring 5 protrudes from the plane (E 2 ) only in regions, but not all over. Through the use of this construction, the deposition of the braiding and stationary yarns 2 , 3 on the core 6 to be over-braided can be influenced in a targeted manner. The yarn-diverting front side 4 of the braiding ring 5 thus spans an imaginary surface which is curved at least in regions and which clearly differs from a planar, straight surface of conventional braiding rings.
[0028] A particularity of the braiding machine according to the invention is the fact that the braiding ring 5 as shown in FIG. 4 can be disposed so as to be pivoted by an angle α with respect to the planes E 1 and (E 2 ). As a result, the deposition of the yarns 2 , 3 can be influenced to a greater extent, in particular when using braiding cores 6 which have no straight longitudinal extension or longitudinal axis L, but rather have, for example, a curved one. For the sake of clarity, neither the core nor the yarns are shown in FIG. 4 .
[0029] Preferably, the braiding ring 5 can be mounted so as to be pivoted about pivot axes S 1 and S 2 (see FIG. 3 ) which are orthogonal to one another. The pivoted mounting in FIG. 4 corresponds in this case to a mounting in which a distance A 4 between the plane E 1 and the point of intersection of the yarn-diverting front side 4 of the braiding ring 5 with the pivot axis S 2 protrudes the furthest. A distance A 3 on the opposite side is slightly smaller due to the pivoting, and distances A 1 and A 2 (points of intersection with the pivot axis S 1 ) are even smaller due to the special construction of the yarn-diverting front side 4 of the braiding ring 5 .
[0030] In the perspective view of FIG. 3 , the braiding core 6 is further shown diagrammatically in order to show how the geometry thereof is preferably to be constructed with respect to the braiding ring 5 . In order to achieve a flat braid, an already flat core 6 having a preferably rectangular diameter can be selected. Contrary to what may be assumed, in this case, the construction and configuration of the braiding ring 5 with respect to the braiding core 6 has an advantageous effect on the uniformity of the braid to be obtained, in which distances k 1 between a maximum width B of the core 6 are smaller than, preferably substantially smaller, than distances K 2 between the core 6 in the case of a maximum height H of the core 6 and the inside diameter of the braiding ring at each position. Likewise, the braiding ring 5 is disposed in such a way that the further protruding side regions 15 thereof are to be found at the maximum cross-sectional dimensions of the core 6 , in this case the width B, and the less protruding upper and lower faces 25 are to be found at the positions of the minimum cross-sectional dimension, in this case the height H, of the core 6 .
[0031] FIG. 5 is a diagrammatic view of a flat braid which is produced on the braiding machine according to the invention. This flat braid can be obtained by flattening the braided sleeve which is produced or by cutting open the sleeve on one or both sides.
[0032] The width, the distance and the angle of twist of the yarns 2 and 3 are not shown to scale in this figure. In this case, stationary yarns 2 extend in the longitudinal direction L of the braid, and braiding yarns 3 extend at an oblique angle to the stationary yarns 2 . Distances G (also referred to as gaps) are located between each of the stationary yarns. In the case of the braid which is produced, a uniformity can be achieved so that the average value of the distances G between the stationary yarns 2 is at most 5%.
[0033] FIG. 6 is a likewise purely diagrammatic illustration of a braid which can be obtained according to the prior art and includes a circular braiding ring, which is located in a plane that is parallel to the plane E 1 . In FIG. 6 , braiding yarns 3 are only shown in one direction, whereas the braiding yarns which are oblique in the opposite direction are not shown therein. The stationary yarns 2 extend in parallel and are aligned only in the perspective shown. On one hand, it can be seen that the braiding yarns 3 do not have an ideal straight course, which is referred to as a nominal position N, but rather differ from that nominal position N, which is the straight line that cuts through the braiding yarn 3 in the center of the flat braid in the manner of a cross section and extends at a tangent to the braiding yarn 3 , in that they have a curved course in the manner of a stretched letter S. This is referred to as an S twist. An inverse curvature, which is not shown therein, is referred to as a Z twist. The size of the twist is measured in an angle of twist β which is defined between the nominal position N and a straight line W that is lain through the points at which the braiding yarn 3 is in contact with the two outer stationary yarns 2 . The angle which is spanned between N and W is the angle of twist β. In the case of the braid according to the invention, the uniformity is so high that the angle of twist β is at most +/−3°. On the other hand, it can be seen in FIG. 6 that the distances between the stationary yarns 2 clearly decrease from the center of the flat braid towards the outside. In the case of the braid according to the invention, the uniformity is so high that the distances between the stationary yarns 2 have an average standard deviation of only at most 5%, preferably at most 2%.
[0034] Through the use of the configuration of the radial braiding machine and the braiding ring 5 thereof according to the invention, the flat braid according to the invention can be produced, which thus meets the high requirements in terms of uniformity. In this case, taking into consideration a shape of the core 6 which is selected in each case, it is possible to influence the position and time of deposition of the yarns 2 , 3 in order to optimize the braid.
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A radial braiding machine includes a bobbin gear through which stationary yarns and braiding yarns are fed, a braiding ring through which the stationary yarns and braiding yarns are guided, and at least one transport device for transporting a core to be over-braided. The braiding ring has a non-round internal cross-section when projected onto a yarn outlet plane spanned by the bobbin gear. A braiding ring, a flat braid and a method of producing the flat braid are also provided.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 62/090,869, filed on Dec. 11, 2014, and No. 62/166,883, filed on May 27, 2015, both of which are incorporated herein by reference in their entireties.
FIELD OF THE INVENTION
[0002] The present invention relates to substituted 2-anilinopyrimidine derivatives and pharmaceutically acceptable salts and compositions thereof useful for the treatment or prevention of diseases or medical conditions mediated through mutated forms of epidermal growth factor receptor (EGFR), such as various cancers.
BACKGROUND OF THE INVENTION
[0003] The epidermal growth factor receptor (EGFR, Her1, ErbB1) is a principal member of the ErbB family of four structurally-related cell surface receptors with the other members being Her2 (Neu, ErbB2), Her3 (ErbB3) and Her4 (ErbB4). EGFR exerts its primary cellular functions though its intrinsic catalytic tyrosine protein kinase activity. The receptor is activated by binding with growth factor ligands, such as epidermal growth factor (EGF) and transforming growth factor-alpha (TGF-α), which transform the catalytically inactive EGFR monomer into catalytically active homo- and hetero-dimers. These catalytically active dimers then initiate intracellular tyrosine kinase activity, which leads to the autophosphorylation of specific EGFR tyrosine residues and elicits the downstream activation of signaling proteins. Subsequently, the signaling proteins initiate multiple signal transduction cascades (MAPK, Akt and JNK), which ultimately mediate the essential biological processes of cell growth, proliferation, motility and survival.
[0004] EGFR is found at abnormally high levels on the surface of many types of cancer cells and increased levels of EGFR have been associated with advanced disease, cancer spread and poor clinical prognosis. Mutations in EGFR can lead to receptor overexpression, perpetual activation or sustained hyperactivity and result in uncontrolled cell growth, i.e. cancer. Consequently, EGFR mutations have been identified in several types of malignant tumors, including metastatic lung, head and neck, colorectal and pancreatic cancers. In lung cancer, mutations mainly occur in exons 18 to 21, which encode the adenosine triphosphate (ATP)-binding pocket of the kinase domain. The most clinically relevant drug-sensitive EGFR mutations are deletions in exon 19 that eliminate a common amino acid motif (LREA) and point mutations in exon 21, which lead to a substitution of arginine for leucine at position 858 (L858R). Together, these two mutations account for nearly 85% of the EGFR mutations observed in lung cancer. Both mutations have perpetual tyrosine kinase activity and as a result they are oncogenic. Biochemical studies have demonstrated that these mutated EGFRs bind preferentially to tyrosine kinase inhibitor drugs such as erlotinib and gefitinib over adenosine triphosphate (ATP).
[0005] Erlotinib and gefitinib are oral EGFR tyrosine kinase inhibitors that are first line monotherapies for non-small cell lung cancer (NSCLC) patients having activating mutations in EGFR. Around 70% of these patients respond initially, but unfortunately they develop resistance with a median time to progression of 10-16 months. In at least 50% of these initially responsive patients, disease progression is associated with the development of a secondary mutation, T790M in exon 20 of EGFR (referred to as the gatekeeper mutation). The additional T790M mutation increases the affinity of the EGFR kinase domain for ATP, thereby reducing the inhibitory activity of ATP-competitive inhibitors like gefitinib and erlotinib.
[0006] Recently, irreversible EGFR tyrosine kinase inhibitors have been developed that effectively inhibit the kinase domain of the T790M double mutant and therefore overcome the resistance observed with reversible inhibitors in the clinic. These inhibitors possess reactive electrophilic functional groups that react with the nucleophilic thiol of an active-site cysteine. Highly selective irreversible inhibitors can be achieved by exploiting the inherent non-covalent selectivity of a given scaffold along with the location of a particular cysteine residue within the ATP binding site. The acrylamide moieties of these inhibitors both undergo a Michael reaction with Cys797 in the ATP binding site of EGFR T790M to form a covalent bond. This covalent mechanism is thought to overcome the increase in ATP affinity of the T790M EGRF double mutant and give rise to effective inhibition. However, these inhibitors may cause various undesired toxicities. Therefore, development of new inhibitors for treatment of various EGFR-related cancers is still in high demand.
SUMMARY OF THE INVENTION
[0007] The present invention provides novel compounds as EGFR tyrosine kinase inhibitors that are therapeutically useful in the treatment or prevention of a number of EGFR-related diseases or disorders, such as various cancers.
[0008] In one aspect, the present invention provides compounds of formula I:
[0000]
[0000] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein:
[0009] G is selected from substituted or unsubstituted 1H-indol-3-yl, substituted or unsubstituted 1H-indazol-3-yl, substituted or unsubstituted 2H-indazol-3-yl, and substituted or unsubstituted pyrazolo[1,5-a]-pyridin-3-yl, and substituted or unsubstituted 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-3-yl;
[0010] X is selected from oxygen, sulfur, and methylene;
[0011] R 1 is selected from hydrogen, halogen, methyl, trifluoromethyl, and cyano;
[0012] R 2 , R 3 , and R 4 are the same or different and are independently selected from hydrogen, halogen and trifluoromethyl;
[0013] R 5 is selected from lower alkyl, optionally substituted 3- to 6-membered heterocyclyl, R 7 R 8 N-(lower alkyl), and R 7 R 8 N-(cycloalkylalkyl), wherein R 7 and R 8 are the same or different and are independently selected from hydrogen and lower alkyl; and
[0014] R 6 is selected from lower alkoxy and lower alkyl.
[0015] In some preferred embodiments, in formula I, G is a 1H-indol -3-yl or 1H-indazol-3-yl moiety having a formula
[0000]
[0000] and the present invention provides a compound of formula II:
[0000]
[0000] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein:
[0016] X is O, S, or CH 2 ;
[0017] Q is C—R 10 or N
[0018] R 9 is CH 3 or CH 2 CH 2 F; and
[0019] R 10 is H or CH 3 .
[0020] In some other preferred embodiments, in formula I, G is pyrazolo[1,5-a]-pyridin-3-yl, and the present invention provides a compound of formula V:
[0000]
[0021] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein X is O, S, or CH 2 .
[0022] In another aspect the present invention provides pharmaceutical compositions comprising any of the compounds, or a pharmaceutically acceptable salt, solvate, or prodrug thereof, and a pharmaceutically acceptable carrier.
[0023] The compounds and compositions of the present invention are useful for treating diseases, disorders, or conditions associated with one or more EGFR mutations. Such diseases, disorders, or conditions include those described herein, such as various cancers.
[0024] Thus, in another aspect, the present invention provides methods of treating diseases or disorders associated with EGFR activities, such as various cancers associated with one or more EGFR mutations, or use of the compounds or compositions in the manufacture of medicaments for treatment of these diseases or disorders.
[0025] In another aspect, the compounds of this invention are useful for the study of kinases in biological and pathological phenomena; the study of transduction pathways mediated by such kinases; and the comparative evaluation of new kinase inhibitors.
[0026] In another aspect, the present invention provides methods of synthesizing the compounds disclosed herein.
[0027] Other aspects or advantages of the present invention will be better appreciated in view of the detailed description and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 illustrates the H1975 tumor growth inhibition assay results for Example 1 in mice.
[0029] FIG. 2 illustrates the H1975 tumor growth inhibition assay results for Example 2 in mice.
[0030] FIG. 3 illustrates the HCC827 tumor growth inhibition assay results for Example 1 in mice.
[0031] FIG. 4 illustrates the average concentrations of Example 1 in plasma, brain and tumor tissues in mice following oral administration of a 25 mg/kg dose in the HCC827 mouse xenograft model.
DETAILED DESCRIPTION OF THE INVENTION
[0032] In one aspect, the present invention provides a compound of the formula I:
[0000]
[0000] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein:
[0033] G is selected from the group consisting of substituted or unsubstituted 1H-indol-3-yl, substituted or unsubstituted 1H-indazol-3-yl, substituted or unsubstituted 2H-indazol-3-yl, substituted or unsubstituted pyrazolo[1,5-a]-pyridin-3-yl, and substituted or unsubstituted 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-3-yl;
[0034] X is oxygen, sulfur, or methylene;
[0035] R 1 is hydrogen, halogen, methyl, trifluoromethyl, or cyano;
[0036] R 2 , R 3 , and R 4 are the same or different and are independently selected from the group consisting of hydrogen, halogen, and trifluoromethyl;
[0037] R 5 is selected from the group consisting of lower alkyl, optionally substituted 3- to 6-membered heterocyclyl, R 7 R 8 N-(lower alkyl), and R 7 R 8 N-(cycloalkylalkyl), wherein R 7 and R 8 are the same or different and are each independently selected from hydrogen and lower alkyl; and
[0038] R 6 is lower alkoxy or lower alkyl.
[0039] In one embodiment of this aspect, G is selected from the group consisting of 1H-indo1-3-yl, 1-methyl-1H-indol-3-yl, 1-(2-fluoroethyl)-1H-indol-3-yl, 1,2-dimethyl-1H-indol-3-yl, pyrazolo[1,5-a]-pyridin-3-yl, 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-3-yl, 1-methyl-1H-indazol-3-yl, and 2-methyl-2H-indazol-3-yl.
[0040] In a preferred embodiment, G is selected from the group consisting of 1-methyl-1H-indo1-3-yl, 1-(2-fluoroethyl)-1H-indol-3-yl, 1,2-dimethyl-1H-indol-3-yl, pyrazolo[1,5-a]-pyridin-3-yl, and 1-methyl-1H-indazol-3-yl.
[0041] In a more preferred embodiment, G is 1-methyl-1H-indol-3-yl, 1-(2-fluoroethyl)-1H-indol-3-yl, or 1,2-dimethyl-1H-indol-3-yl, and more preferably 1-methyl-1H-indol-3-yl.
[0042] In another more preferred embodiment, G is pyrazolo[1,5-a]-pyridin-3-yl.
[0043] In another more preferred embodiment, G is 1-methyl-1H-indazol-3-yl.
[0044] In another embodiment of this aspect, R 5 is selected from the group consisting of C 1 -C 6 alkyl, substituted or unsubstituted azetidinyl, substituted or unsubstituted pyrrolidinyl, substituted or unsubstituted piperidinyl, R 7 R 8 N—(CH 2 ) n — (n is an integer selected from 1 to 5), R 7 R 8 N—(C 3 -C 6 cycloalkyl)-(CH 2 ) m — (m=1, 2, 3), wherein R 7 and R 8 are the same or different and are independently selected from hydrogen and lower alkyl.
[0045] In a preferred embodiment of this aspect, R 5 is selected from the group consisting of methyl, 1-(dimethylamino)-cyclopropylmethyl, 3-(dimethylamino)cyclobutyl, 1-methylazetidin-3-yl, (R)-methylpyrrolidin-3-yl, (S)-1-methylpyrrolidin-3-yl, and 1-methylpiperidin-4-yl, and 2-dimethylamino-ethyl.
[0046] In a more preferred embodiment, R 5 is 2-dimethylamino-ethyl [i.e., (CH 3 ) 2 NCH 2 CH 2 —].
[0047] In another embodiment of this aspect, R 1 is hydrogen, halogen, or methyl.
[0048] In a preferred embodiment of this aspect, R 1 is hydrogen.
[0049] In another embodiment of this aspect, R 2 is hydrogen or halogen, wherein halogen is preferably F or Cl.
[0050] In another embodiment of this aspect, R 3 is hydrogen, F, Cl, or —CF 3 .
[0051] In another embodiment of this aspect, R 4 is hydrogen.
[0052] In another embodiment of this aspect, R 2 is hydrogen, F, or Cl; R 3 is hydrogen, F, Cl, or —CF 3 ; and R 4 is hydrogen.
[0053] In a preferred embodiment of this aspect, R 2 , R 3 , and R 4 are all hydrogen.
[0054] In a preferred embodiment of this aspect, R 6 is lower alkoxy, preferably methoxy or ethoxy.
[0055] In a more preferred embodiment, R 6 is methoxy.
[0056] In another embodiment of this aspect, sometimes preferred, X is oxygen.
[0057] In another embodiment of this aspect, sometime preferred, X is sulfur.
[0058] In another embodiment of this aspect, sometimes preferred, X is —CH 2 —.
[0059] As would be understood by a person skilled in the art, any plausible and structurally allowable combinations of all the embodiments or preferred embodiments disclosed herein are encompassed and hereby specifically included in the present invention.
[0060] For example, in some embodiments of this aspect, G is selected from the group consisting of 1H-indol-3-yl, 1-methyl-1H-indol-3-yl, 1-(2-fluoroethyl)-1H-indol-3-yl, 1,2-dimethyl-1H-indol-3-yl, pyrazolo[1,5-a]-pyridin-3-yl, 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-3-yl, 1-methyl-1H-indazol-3-yl, and 2-methyl-2H-indazol-3-yl;
[0061] X is selected from the group consisting of oxygen, sulfur, and methylene;
[0062] R 1 is selected from the group consisting of hydrogen, halogen, methyl, trifluoromethyl, and cyano;
[0063] R 2 , R 3 , and R 4 are the same or different and are independently selected from the group consisting of hydrogen, halogen, and trifluoromethyl;
[0064] R 5 is selected from the group consisting of 1-(dimethylamino)-cyclopropylmethyl, 3-(dimethylamino)cyclobutyl, 1-methylazetidin-3-yl, (R)-1-methylpyrrolidin-3-yl, (S)-1-methylpyrrolidin-3-yl, and 1-methylpiperidin-4-yl, and 2-dimethylamino-ethyl; and
[0065] R 6 is lower alkoxy.
[0066] In some preferred embodiments, G is a 1H-indol-3-yl or 1H-indazol-3-yl moiety having a formula
[0000]
[0000] and the present invention provides a compound of formula II:
[0000]
[0000] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein:
[0067] X is O, S, or CH 2 ;
[0068] Q is C—R 10 or N
[0069] R 9 is CH 3 or CH 2 CH 2 F; and
[0070] R 10 is H or CH 3 .
[0071] In one preferred embodiment, in formula II, Q is C—R 10 , and the present invention provides a compound of formula III:
[0000]
[0072] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein R 9 is CH 3
or CH 2 CH 2 F; and R 10 is H or CH 3 .
[0074] In another preferred embodiment, in the compound of formula III, R 9 is CH 3 and R 10 is H.
[0075] In another preferred embodiment, in the compound of formula III, R 9 is CH 3 and R 10 is CH 3 .
[0076] In another preferred embodiment, in the compound of formula III, R 9 is 2-fluoroethyl (FCH 2 CH 2 —), and R 10 is H.
[0077] In another preferred embodiment, in formula III, R 9 is CH 3 , R 10 is H, and X is O, the compound having the structure of formula 1:
[0000]
[0078] In another preferred embodiment, in formula III, R 9 is CH 3 , R 10 is CH 3 , and X is O, the compound having the structure of formula 8:
[0000]
[0079] In another preferred embodiment, in formula III, R 9 is CH 3 , R 10 is H, and X is S, the compound having the structure of formula 2:
[0000]
[0080] In another preferred embodiment, in formula III, R 9 is CH 3 , R 10 is H, and X is CH 2 , the compound having the structure of formula 4:
[0000]
[0081] In another preferred embodiment, in formula III, R 9 is —CH 2 CH 2 F, R 10 is H, and X is O, the compound having the structure of formula 11:
[0000]
[0082] In one preferred embodiment, in formula II, Q is N, and the present invention provides a compound of formula IV:
[0000]
[0083] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein: R 9 is H or CH 3 ; and X is O, S, or CH 2 .
[0084] In a more preferred embodiment, in formula IV, R 9 is H or CH 3 , and X is O, the compound having the structure of formula 10:
[0000]
[0085] In some other preferred embodiments, in formula I, G is pyrazolo[1,5-a]-pyridin-3-yl, and the present invention provides a compound of formula V:
[0000]
[0086] or a pharmaceutically acceptable salt, solvate, or prodrug thereof, wherein X is O, S, or CH 2 .
[0087] In a more preferred embodiment, in formula V, X is O, the compound having the structure of formula 9:
[0000]
[0088] In some other preferred embodiments, the present invention provides a compound selected from the group consisting of the Examples listed, or a pharmaceutically acceptable salt, solvate, or prodrug thereof.
[0089] The more preferred compounds are listed below:
[0000]
[0090] In another aspect, the present invention provides a pharmaceutical composition comprising any one of the compounds of formulas I, II, III, IV, and V, or a pharmaceutically acceptable salt, solvate, or prodrug thereof, and a pharmaceutically acceptable carrier, adjuvant, diluent, and/or vehicle.
[0091] In one embodiment of this aspect, the composition further comprises a second therapeutic agent.
[0092] In another embodiment of this aspect, the second therapeutic agent is a different EGFR modulator.
[0093] In another embodiment of this aspect, the second therapeutic agent is a chemotherapeutic agent.
[0094] In another aspect, the present invention provides a method of treating a disease or disorder associated with an EGFR activity, comprising administration of a therapeutically effective amount of a compound according to any one of formulas I, II, III, IV, and V, or a pharmaceutically acceptable salt, solvate, prodrug, or a pharmaceutical composition thereof, to a patient in need of treatment.
[0095] In one embodiment of this aspect, the disease or disorder is associated with one or more mutants of EGFR.
[0096] In another embodiment of this aspect, the mutant or mutants of EGFR are selected from L858R activating mutants L858R, delE746-A750, G719S; the Exon 19 deletion activating mutant; and the T790M resistance mutant.
[0097] In another embodiment of this aspect, the disease or disorder is a cancer.
[0098] In another embodiment of this aspect, the cancer is selected from brain cancer, lung cancer, kidney cancer, bone cancer, liver cancer, bladder cancer, head and neck cancer, esophageal cancer, stomach cancer, colon cancer, rectum cancer, breast cancer, ovarian cancer, melanoma, skin cancer, adrenal cancer, cervical cancer, lymphoma, and thyroid tumors and their complications.
[0099] In another embodiment of this aspect, the method is used in conjunction with administering to the patient a second therapeutic agent.
[0100] In another embodiment of this aspect, the second therapeutic agent is a chemotherapeutic agent.
[0101] In another embodiment of this aspect, the second therapeutic agent is a different EGFR modulator.
[0102] In another aspect, the present invention provides a method of inhibiting a mutant of EGFR in a subject, comprising contacting a biological sample of said subject with a compound of any one of formulas I, II, III, IV, and V according to any embodiment disclosed herein, or a pharmaceutically acceptable salt, solvate, or prodrug thereof. Such inhibition can be in vitro or in vivo. If in vivo, the method may comprise administering to said subject a compound of any one of formulas I, II, III, IV, and V according to any embodiment disclosed herein, or a pharmaceutically acceptable salt, solvate, or prodrug thereof. If in vitro, such inhibition may be conducted in a medium in any container known to those skilled in the art.
[0103] In another aspect, the present invention provides use of a compound of any one of formulas I, II, III, IV, and V according to any embodiment disclosed herein, or a pharmaceutically acceptable salt, solvate, or prodrug thereof, or a composition of any one of formulas I, II, III, IV, and V according to any embodiment disclosed herein, in the manufacture of a medicament for treatment of a disease or disorder associated with an EGFR activity.
[0104] In one embodiment of this aspect, disease or disorder is a cancer selected from the group consisting of brain cancer, lung cancer, kidney cancer, bone cancer, liver cancer, bladder cancer, head and neck cancer, esophageal cancer, stomach cancer, colon cancer, rectum cancer, breast cancer, ovarian cancer, melanoma, skin cancer, adrenal cancer, cervical cancer, lymphoma, and thyroid tumors and their complications. In a preferred embodiment, the cancer is brain cancer or lung cancer. The lung cancer includes, but is not limited to, non-small cell lung cancer and small cell lung cancer.
[0105] The terms in the present application, if not specifically defined, take their ordinary meanings as would be understood by those skilled in the art.
[0106] As used herein, the term “halo” or “halogen” refers to F, Cl, or Br.
[0107] The term “lower alkyl” refers to a branched or straight-chain alkyl group having from one to seven carbon atoms, preferably one to four, and more preferably one to two carbon atoms.
[0108] The term “lower alkoxy” refers to an alkoxy group (—OR) having from one to seven, preferably one to four, and more preferably one to two carbon atoms.
[0109] The term “cyano” refers to —CN.
[0110] The term “pharmaceutically acceptable,” as used herein, refers to those compounds, materials, compositions, and/or dosage forms which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of patients without excessive toxicity, irritation, allergic response, or other problem or complication commensurate with a reasonable benefit/risk ratio, and are effective for their intended use.
[0111] As used herein, the term “pharmaceutically acceptable salt” refers to those salts which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of humans and lower animals without undue toxicity, irritation, allergic response and the like, and are commensurate with a reasonable benefit/risk ratio. Pharmaceutically acceptable salts of the compounds of this invention include those derived from suitable inorganic and organic acids and bases. Examples of pharmaceutically acceptable, nontoxic acid addition salts are salts of an amino group formed with inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid and perchloric acid or with organic acids such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid or malonic acid or by using other methods used in the art such as ion exchange. Other pharmaceutically acceptable salts include adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2-hydroxy-ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, p-toluenesulfonate, undecanoate, valerate salts, and the like.
[0112] The term “solvate,” as used herein, means a physical association of a compound of this invention with a stoichiometric or non-stoichiometric amount of solvent molecules. For example, one molecule of the compound associates with one or more, preferably one to three, solvent molecules. It is also possible that multiple (e.g., two) molecules of the compound share one solvent molecule. This physical association may include hydrogen bonding. In certain instances the solvates will be capable of isolation as crystalline solid. The solvent molecules in the solvate may be present in a regular arrangement and/or a non-ordered arrangement. Exemplary solvates include, but are not limited to, hydrates, ethanolates, methanolates, and isopropanolates. Methods of solvation are generally known in the art.
[0113] The term “prodrug,” as used herein, refers to a derivative of a compound that can be transformed in vivo to yield the parent compound, for example, by hydrolysis in blood. Common examples include, but are not limited to, ester and amide forms of an active carboxylic acid compound; or vice versa, an ester from of an active alcohol compound or an amide form of an active amine compound. Such amide or ester prodrug compounds may be prepared according to conventional methods as known in the art. For example, a prodrug of a compound of formula II of the present invention could be in the form of the following formula VI:
[0000]
[0114] wherein R x and R y are independently H and —C(O)—R, wherein R is C 1 -C 4 alkyl, preferably methyl or ethyl, and more preferably methyl. Other prodrugs of the present invention can be prepared similarly from any of formulas I, II, III, IV, and V.
[0115] When it is possible that, for use in therapy, therapeutically effective amounts of a compound of the present invention, or pharmaceutically acceptable salts or solvates thereof, may be administered as the raw chemical, it is possible to present the active ingredient as a pharmaceutical composition. Accordingly, the disclosure further provides pharmaceutical compositions, which include any compounds of the present invention, or pharmaceutically acceptable salts or solvates thereof, and one or more, preferably one to three, pharmaceutically acceptable carriers, diluents, or other excipients. The carrier(s), diluent(s), or other excipient(s) must be acceptable in the sense of being compatible with the other ingredients of the formulation and not deleterious to the subject being treated.
[0116] Pharmaceutical formulations may be presented in unit dose forms containing a predetermined amount of active ingredient per unit dose. Typically, the pharmaceutical compositions of this disclosure will be administered from about 1 to about 5 times per day or alternatively, as a continuous infusion. Such administration can be used as a chronic or acute therapy. The amount of active ingredient that may be combined with the carrier materials to produce a single dosage form will vary depending on the condition being treated, the severity of the condition, the time of administration, the route of administration, the rate of excretion of the compound employed, the duration of treatment, and the age, gender, weight, and condition of the patient. Preferred unit dosage formulations are those containing a daily dose or sub-dose, as herein above recited, or an appropriate fraction thereof, of an active ingredient. Generally, treatment is initiated with small dosages substantially less than the optimum dose of the compound. Thereafter, the dosage is increased by small increments until the optimum effect under the circumstances is reached. In general, the compound is most desirably administered at a concentration level that will generally afford effective results without causing substantial harmful or deleterious side effects.
[0117] When the compositions of this disclosure comprise a combination of a compound of the present disclosure and one or more, preferably one or two, additional therapeutic or prophylactic agent, both the compound and the additional agent are usually present at dosage levels of between about 10 to 150%, and more preferably between about 10 and 80% of the dosage normally administered in a monotherapy regimen.
[0118] Pharmaceutical formulations may be adapted for administration by any appropriate route, for example, by the oral (including buccal or sublingual), rectal, nasal, topical (including buccal, sublingual, or transdermal), vaginal, or parenteral (including subcutaneous, intracutaneous, intramuscular, intra-articular, intrasynovial, intrasternal, intrathecal, intralesional, intravenous, or intradermal injections or infusions) route. Such formulations may be prepared by any method known in the art of pharmacy, for example by bringing into association the active ingredient with the carrier(s) or excipient(s). Oral administration or administration by injection is preferred.
[0119] Pharmaceutical formulations adapted for oral administration may be presented as discrete units such as capsules or tablets; powders or granules; solutions or suspensions in aqueous or non-aqueous liquids; edible foams or whips; or oil-in-water liquid emulsions or water-in-oil emulsions.
[0120] For instance, for oral administration in the form of a tablet or capsule, the active drug component can be combined with an oral, non-toxic pharmaceutically acceptable inert carrier such as ethanol, glycerol, water, and the like. Powders are prepared by comminuting the compound to a suitable fine size and mixing with a similarly comminuted pharmaceutical carrier such as an edible carbohydrate, as, for example, starch or mannitol. Flavoring, preservative, dispersing, and coloring agent can also be present.
[0121] Capsules are made by preparing a powder mixture, as described above, and filling formed gelatin sheaths. Glidants and lubricants such as colloidal silica, talc, magnesium stearate, calcium stearate, or solid polyethylene glycol can be added to the powder mixture before the filling operation. A disintegrating or solubilizing agent such as agar-agar, calcium carbonate, or sodium carbonate can also be added to improve the availability of the medicament when the capsule is ingested.
[0122] Moreover, when desired or necessary, suitable binders, lubricants, disintegrating agents, and coloring agents can also be incorporated into the mixture. Suitable binders include starch, gelatin, natural sugars such as glucose or beta-lactose, corn sweeteners, natural and synthetic gums such as acacia, tragacanth or sodium alginate, carboxymethylcellulose, polyethylene glycol, and the like. Lubricants used in these dosage forms include sodium oleate, sodium chloride, and the like. Disintegrators include, without limitation, starch, methyl cellulose, agar, betonite, xanthan gum, and the like. Tablets are formulated, for example, by preparing a powder mixture, granulating or slugging, adding a lubricant and disintegrant, and pressing into tablets. A powder mixture is prepared by mixing the compound, suitable comminuted, with a diluent or base as described above, and optionally, with a binder such as carboxymethylcellulose, an aliginate, gelating, or polyvinyl pyrrolidone, a solution retardant such as paraffin, a resorption accelerator such as a quaternary salt and/or and absorption agent such as betonite, kaolin, or dicalcium phosphate. The powder mixture can be granulated by wetting with a binder such as syrup, starch paste, acadia mucilage, or solutions of cellulosic or polymeric materials and forcing through a screen. As an alternative to granulating, the powder mixture can be run through the tablet machine and the result is imperfectly formed slugs broken into granules. The granules can be lubricated to prevent sticking to the tablet forming dies by means of the addition of stearic acid, a stearate salt, talc, or mineral oil. The lubricated mixture is then compressed into tablets. The compounds of the present disclosure can also be combined with a free flowing inert carrier and compressed into tablets directly without going through the granulating or slugging steps. A clear or opaque protective coating consisting of a sealing coat of shellac, a coating of sugar or polymeric material, and a polish coating of wax can be provided. Dyestuffs can be added to these coatings to distinguish different unit dosages.
[0123] Oral fluids such as solution, syrups, and elixirs can be prepared in dosage unit form so that a given quantity contains a predetermined amount of the compound. Syrups can be prepared by dissolving the compound in a suitably flavored aqueous solution, while elixirs are prepared through the use of a non-toxic vehicle. Solubilizers and emulsifiers such as ethoxylated isostearyl alcohols and polyoxyethylene sorbitol ethers, preservatives, flavor additive such as peppermint oil or natural sweeteners, or saccharin or other artificial sweeteners, and the like can also be added.
[0124] Where appropriate, dosage unit formulations for oral administration can be microencapsulated. The formulation can also be prepared to prolong or sustain the release as for example by coating or embedding particulate material in polymers, wax, or the like.
[0125] It should be understood that in addition to the ingredients particularly mentioned above, the formulations may include other agents conventional in the art having regard to the type of formulation in question, for example those suitable for oral administration may include flavoring agents.
[0126] The term “patient” or “subject” includes both human and other mammals.
[0127] The term “mammal” or “mammalian animal” includes, but is not limited to, humans, dogs, cats, horses, pigs, cows, monkeys, rabbits and mice. The preferred mammals are humans.
[0128] The term “therapeutically effective amount” refers to an amount of a compound or composition that, when administered to a subject for treating a disease, is sufficient to effect such treatment for the disease. A “therapeutically effective amount” can vary depending on, inter alia, the compound, the disease and its severity, and the age, weight, or other factors of the subject to be treated. When applied to an individual active ingredient, administered alone, the term refers to that ingredient alone. When applied to a combination, the term refers to combined amounts of the active ingredients that result in the therapeutic effect, whether administered in combination, serially, or simultaneously.
[0129] The term “treating” or “treatment” refers to: (i) inhibiting the disease, disorder, or condition, i.e., arresting its development; (ii) relieving the disease, disorder, or condition, i.e., causing regression of the disease, disorder, and/or condition; or (iii) preventing a disease, disorder or condition from occurring in a subject that may be predisposed to the disease, disorder, and/or condition but has not yet been diagnosed as having it. Thus, in one embodiment, “treating” or “treatment” refers to ameliorating a disease or disorder, which may include ameliorating one or more physical parameters, though maybe indiscernible by the subject being treated. In another embodiment, “treating” or “treatment” includes modulating the disease or disorder, either physically (e.g., stabilization of a discernible symptom) or physiologically (e.g., stabilization of a physical parameter) or both. In yet another embodiment, “treating” or “treatment” includes delaying the onset of the disease or disorder.
[0130] When the term “about” is applied to a parameter, such as amount, temperature, time, or the like, it indicates that the parameter can usually vary by ±10%, preferably within ±5%, and more preferably within ±2%. As would be understood by a person skilled in the art, when a parameter is not critical, a number provided in the Examples is often given only for illustration purpose, instead of being limiting.
[0131] The term “a,” “an,” or “the,” as used herein, represents both singular and plural forms. In general, when either a singular or a plural form of a noun is used, it denotes both singular and plural forms of the noun.
[0132] The following non-limiting Examples further illustrate certain aspects of the present invention.
EXAMPLES
Chemical Synthesis
[0133] The compounds of the present invention are prepared generally according to Synthetic Schemes 1 to 8 in the illustrative, non-limiting Examples described below.
Abbreviations
[0134] The following abbreviations may be used:
[0135] THF=Tetrahydrofuran;
[0136] conc.=concentrated
[0137] DIEA=DIPEA=Diisopropylethylamine;
[0138] sat.=saturated aqueous solution;
[0139] FCC=flash column chromatography using silica;
[0140] TFA=Trifluoroacetic acid;
[0141] r.t.=room temperature;
[0142] DI=deionized;
[0143] DME=1,2-Dimethoxyethane
[0144] DMF=N,N-Dimethylformamide;
[0145] DMSO=Dimethylsulfoxide;
[0146] DMA=N,N-Dimethylacetamide;
[0147] HATU=O-(7-Azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluoro-phosphate;
[0148] EtOAc=Ethyl acetate;
[0149] h=hour(s);
[0150] NMM=N-Methylmorpholine
[0151] Pd 2 (dba) 3 =Tris(dibenzylideneacetone)dipalladium(0);
[0152] P(o-tol) 3 =Tri(o-tolyl)phosphine.
Example 1
N-(2-(2-(Dimethylamino)ethoxy)-4-methoxy-5((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (1)
[0153]
[0154] N-(4-(2-(Dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Scheme 1, Intermediate B). To a slurry of NaH (30 mmol, 60% oil dispersion prewashed with hexanes) and 50 mL of 1,4-dioxane was added 2-dimethylaminoethanol (27 mmol, 2.7 mL) dropwise with stirring under N 2 . After stirring for 1 h, a slurry of A (5.4 mmol) in 50 mL of 1,4-dioxane was added portion-wise over 15 min under a stream of N 2 . The resulting mixture was stirred overnight, then poured into water and the solid was collected, rinsed with water, and dried under vacuum to yield 2.6 g of product as a yellow solid. A purified sample was obtained from chromatography (silica gel; CH 2 Cl 2 —CH 3 OH gradient). 1 H NMR (300 MHz, DMSO) δ 2.26 (s, 6H), 2.70 (t, 2H, J=6 Hz), 3.87 (s, 3H), 4.01 (s, 3H), 4.32 (t, 2H, J=6 Hz), 7.00-7.53 (m, 5H), 8.18-8.78 (m, 5H); C 24 H 26 N 6 O 4 m/z MH + 463.
[0155] 4-(2-(Dimethylamino)ethoxy)-6-methoxy-N1-(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Scheme 1, Intermediate C). A suspension of 2.6 g of Intermediate B, 1.6 g of Fe 0 , 30 mL of ethanol, 15 mL of water, and 20 mL of conc. HCl was heated to 78° C. for 3 h. The solution was cooled to room temperature, adjusted to pH 10 with 10% NaOH (aq) and diluted with CH 2 Cl 2 . The mixture was filtered through Dicalite, and the filtrate layers were separated. The aqueous phase was extracted with CH 2 Cl 2 twice, and the combined organic extracts were dried over Na 2 SO 4 and concentrated. Column chromatography (silica gel, CH 2 Cl 2 —MeOH gradient) afforded 1.2 g of Intermediate C as a solid. C 24 H 28 N 6 O 2 m/z MH + 433.
[0156] N-(2-(2-(Dimethylamino)ethoxy)-4-methoxy-5((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (1). To a solution of Intermediate C (2.8 mmol) in 50 mL of THF and 10 mL of water was added 3-chloropropionychloride (2.8 mmol) dropwise with stirring. After 5 h of stirring, NaOH (28 mmol) was added and the mixture was heated at 65° C. for 18 h. After cooling to room temperature, THF was partially removed under reduced pressure, and the mixture was extracted with CH 2 Cl 2 , dried over Na 2 SO 4 , and concentrated. Chromatography of the crude product (silica gel, CH 2 Cl 2 —MeOH) afforded 0.583 g of Example 1 as a beige solid. 1 H NMR (300 MHz, DMSO) δ 2.28 (s, 6H), 2.50-2.60 (m, 2H), 3.86 (s, 3H), 3.90 (s, 3H), 4.19 (t, 2H, J=5.5 Hz), 5.73-5.77 (m, 1H), 6.21-6.27 (m, 1H), 6.44-6.50 (m, 1H), 6.95 (s, 1H), 7.11-7.53 (overlapping m, 3H), 7.90 (s, 1H), 8.27-8.30 (overlapping m, 3H), 8.55 (s, 1H), 8.84 (s, 1H), 9.84 (s, 1H) ppm; C 27 H 30 N 6 O 3 m/z MH + 487.
Example 2
N-(2-((2-(Dimethylamino)ethypthio)-4-methoxy-5((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (2)
[0157]
[0158] N-(4-((2-(Dimethylamino)ethypthio)-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Scheme 2, Intermediate D). To a slurry of NaH (54 mmol, 60% oil dispersion prewashed with hexanes) and 25 mL of DMF was added a slurry of 2-dimethylaminoethanethiol hydrochloride (27 mmol) in 25 mL of DMF under a stream of N 2 . After stirring for 45 min, a slurry of A (5.4 mmol) in 25 mL of DMF was added portionwise over 15 min to the mixture under a stream N 2 . The resulting mixture was stirred overnight, then poured into water and the solid was collected, rinsed repeatedly with water, and dried under vacuum to yield 2.5 g of product as a yellow solid. C 24 H 26 N 6 O 3 S m/z MH + 479.
[0159] 4-((2-(Dimethylamino)ethypthio)-6-methoxy-N 1 -(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Scheme 2, Intermediate E). A suspension of 2.5 g of Intermediate D, 3.0 g of Fe 0 , 50 mL of ethanol, 20 mL of water, and 7 mL of conc. HCl was heated to 78° C. for 3 h. The solution was cooled to room temperature, adjusted to pH 10 with 10% NaOH (aq), and diluted with CH 2 Cl 2 . The mixture was filtered through Dicalite, and the filtrate layers were separated. The aqueous phase was extracted with CH 2 Cl 2 twice, and the combined organic extracts were dried over Na 2 SO 4 and concentrated. Column chromatography (silica gel, CH 2 Cl 2 —MeOH gradient) afforded 1.2 g of Intermediate E as a solid. C 24 H 28 N 6 OS m/z MH + 449.
[0160] N-(2-((2-(Dimethylamino)ethyp)thio)-4-methoxy-5((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (2). To a solution of Intermediate E (2.7 mmol) in 50 mL of THF and 10 mL of water was added 3-chloropropionychloride (4.0 mmol) dropwise with stirring. After 2 h of stirring, NaOH (27 mmol) was added and the mixture was heated at 65° C. for 18 h. After cooling to room temperature, THF was partially removed under reduced pressure, and the mixture was extracted with CH 2 Cl 2 , dried over Na 2 SO 4 , and concentrated. Chromatography of the crude product (silica gel, CH 2 Cl 2 —MeOH—NH 4 OH gradient) afforded 0.622 g of Example 2 as an off-white solid: 1 H NMR (300 MHz, DMSO) δ 2.19 (s, 6H), 2.34 (t, 2H, J=6.5 Hz), 2.98 (t, 2H, J=6.5 Hz), 3.91 (s, 3H), 3.93 (s, 3H), 5.50-6.57 (overlapping m, 3H), 7.12-9.88 (overlapping m, 10H), 10.17 (s, 1H) ppm. C 27 H 30 N 6 O 2 S m/z MH + 503.
Example 3
N-(2,4-Dimethoxy-5-((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)-phenyl)acrylamide (3)
[0161]
[0162] N-(2,4-Dimethoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Scheme 3, Intermediate F). Sodium methoxide, 25 wt. % solution in methanol (40 mL, 175 mmol), was slowly poured into a stirred, ambient temperature, suspension of N-(4-fluoro-2-metho xy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Scheme 1, Intermediate A; 5.8 g, 14.7 mmol) in methanol (125 mL) and heated at reflux for 4 days under nitrogen blanket, during which time the solid did not dissolve. The reaction was cooled, product precipitate isolated by filtration, washed with cold methanol, and dried to yield 5.45 g of N-(2,4-dimethoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Intermediate F) as a yellow powder. C 21 H 19 N 5 O 4 m/z MH + 406.
[0163] 4,6-Dimethoxy-N 1 -(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Scheme 3, Intermediate G). Stannous chloride dihydrate (8.9 g, 39.4 mmol) was added to a stirred, ambient temperature suspension of N-(2,4-dimethoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Intermediate F; 3.2 g, 7.9 mmol) in ethyl acetate (200 mL) and heated at reflux under nitrogen blanket for 3 h. The reaction was allowed to cool, then poured into a 5% (w/v) solution of sodium bicarbonate in DI water (400 mL) and stirred for 1 h. The multiphase mixture was then filtered through tightly packed Celite, with ethyl acetate rinsing of the filter cake. The filtrate was transferred to a separatory funnel and the liquid phases separated. The retained ethyl acetate solution of product was washed with brine and dried over anhydrous calcium sulfate. Filtration and evaporation yielded 1.6 g of crude product. Purification by gradient flash chromatography (SiO 2 , 0 to 70% hexanes/ethyl acetate over 20 min.) provided 0.9 g of 4,6-dimethoxy-N 1 -(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Intermediate G) as a yellow foam. C 21 H 21 N 5 O 2 m/z MH + 376.
[0164] N-(2,4-Dimethoxy-5-((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (3). 3-Chloropropanoyl chloride (90 μL, 0.92 mmol) was rapidly added by syringe to a rapidly stirred, ambient temperature, nitrogen blanketed solution of 4,6-dimetho xy-N 1 -(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Intermediate G; 351 mg, 0.94 mmol) and N-methylmorpholine (0.11 mL, 1.0 mmol) in ethyl acetate (9.4 mL), precipitate immediately formed, and reaction was allowed to proceed for 40 min., evaporated to dryness, and dissolved in 10% (v/v) DI water/tetrahydrofuran. Solid sodium hydroxide (3 g, 75 mmol) was added and the stirred mixture heated to 50° C. for 17 h. The reaction solution was cooled, partitioned between brine and ethyl acetate. The ethyl acetate phase was dried over anhydrous calcium sulfate, filtered, and then chilled in an ice bath with stirring while slowly being diluted with hexanes to precipitate the product. This material was isolated by filtration and dried to provide 189 mg of Example 3 as fine light-yellow powder. 1 H NMR (300 MHz, DMSO) δ 3.88 (s, 6H), 3.90 (s, 3H), 5.70 (dd, 1H, J=10.15, 1.92 Hz), 6.22 (dd, 1H, J=16.95, 2.03 Hz), 6.70 (q, 1H, J=9.06 Hz), 6.85 (s, 1H), 7.11-7.17 (m, 2H), 7.23 (t, 1H, J=6.96 Hz), 7.50 (d, 1H, J=8.23 Hz), 7.93 (s, 1H), 8.28 (m, 2H), 8.47 (s, 1H), 8.67 (s, 1H), 9.38 (s, 1H) ppm. 13 C NMR (75 MHz, DMSO) δ 33.4, 56.5, 56.7, 97.3, 107.1, 110.8, 113.0, 118.5, 119.5, 121.3, 121.5, 122.3, 122.5, 125.9, 126.4, 132.8, 133.8, 138.1, 147.3, 148.3, 157.8, 160.8, 162.3, 163.5 ppm. C 24 H 23 N 5 O 3 m/z MH + 430.
Example 4
N-(2-(3-(Dimethylamino)propyl)-4-methoxy-5-((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (4)
[0165]
[0166] N-(4-(3-(Dimethylamino)prop-1-yn-1-yl)-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Scheme 4, Intermediate H). A solution of 3-dimethylamino-1-propyne (1.37 mL,12.7 mmol) in 1,4-dioxane (60 mL) was treated with 1 M lithium bis(trimethylsilyl)amide (12.7 mL, 12.7 mmol) and stirred for 30 min at RT under a nitrogen atmosphere. The resulting reaction mixture, which appeared as a white slurry, was treated with N-(4-fluoro-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Intermediate A; 1.00 g, 2.54 mmol) in one portion and heated at 80° C. while vigorously stirring under nitrogen for 5 h. The reaction mixture was cooled to RT, quenched by the addition of 10 mL of water and subsequently concentrated in vacuo. The residue was partitioned between water (100 mL) and CH 2 Cl 2 (50 mL). The basic aqueous layer was extracted with CH 2 Cl 2 (2×50 mL) and the combined organic extracts were washed with brine (2×50 mL), dried (Na 2 SO 4 ), filtered and concentrated in vacuo to furnish 1.0 g of the crude product as a dark reddish-brown solid. This material was purified by gradient flash chromatography on SiO 2 eluting with 0 to 10% methanol (containing 2% NH 4 OH) in CH 2 Cl 2 over 60 min to afford 98 mg of N-(4-(3-(dimethylamino)prop-1-yn-1-yl)-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Intermediate H) as an orange solid. C 25 H 24 N 6 O 3 m/z MH + 457.
[0167] 4-(3-(Dimethylamino)propyl)-6-methoxy-N 1 -(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Scheme 4, Intermediate I). 10% Pd/C (10 mg) was added under a nitrogen atmosphere to a solution of N-(4-(3-(dimethylamino)prop-1-yn-1-yl)-2-metho xy-5-nitrophenyl)-4-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine (Intermediate H; 50 mg, 0.109 mmol) in 10 mL of THF/methanol (1:1). A hydrogen-filled balloon was connected to the reaction vessel and the reaction was stirred at RT under a hydrogen atmosphere for 6 h. The reaction mixture was filtered through Celite 545 and concentrated in vacuo to give 50 mg of crude product. This material was purified by gradient flash chromatography on SiO 2 eluting with 0 to 10% methanol (containing 2% NH 4 OH) in CH 2 Cl 2 over 50 min to afford 34 mg of 4-(3-(dimethylamino)propyl)-6-methoxy-N 1 -(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Intermediate I) as a foam. C 25 H 30 N 6 O m/z MH + 431.
[0168] N-(2-(3-(Dimethylamino)propyl)-4-methoxy-5((4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (4). 3-Chloropropanoyl chloride (18.2 μL, 0.190 mmol) was rapidly added to a solution of 4-(3-(dimethylamino)propyl)-6-methoxy-N 1 -(4-(1-methyl-1H-indol-3-yl)pyrimidin-2-yl)benzene-1,3-diamine (Intermediate I; 34 mg, 0.079 mmol) in 3.2 mL of THF/water (9:1) while stirring under nitrogen at RT. After 3 h, 1M aq NaOH (0.79 mL, 0.79 mmol) and the reaction mixture was heated at 65° C. for 17 h. The reaction mixture was cooled to RT, diluted with water (15 mL) and the resulting light gray precipitate was isolated by filtration to give 31 mg of crude product. This material was purified by gradient flash chromatography on SiO 2 eluting with 0 to 10% methanol (containing 2% NH 4 OH) in CH 2 Cl 2 over 35 min to afford 22 mg of Example 4 as an off-white solid. 1 H NMR (300 MHz, CDCl 3 ) δ 1.81-1.92 (m, 2H), 2.16 (t, 2H, J=5.9 Hz), 2.27 (s, 6H), 2.69 (t, 2H, J=6.3 Hz), 3.89 (s, 3H), 3.98 (s, 3H), 5.71 (dd, 1H, J=10.1, 1.9 Hz), 6.25 (dd, 1H, J=16.9, 10.1 Hz), 6.48 (dd, 1H, J=16.9, 1.9 Hz), 6.66 (s, 1H), 7.17 (d, 1H, J=5.3 Hz), 7.22-7.43 (m, 3H), 7.72 (s, 1H), 8.05-8.12 (m, 1H), 8.37 (d, 1H, J=5.3 Hz), 8.85 (s, 1H), 9.33 (s, 1H), 10.95, (br s, 1H); C 28 H 32 N 6 O 2 m/z MH + 485.
Examples 5, 6, and 7
[0169]
N-(2-(2-(Dimethylamino)ethoxy)-4-methoxy-5((4-(2-methyl-2H-indazol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (5)
[0170]
[0171] N-(2-((2-(Dimethylamino)ethypthio)-4-methoxy-5-((4-(2-methyl-2H-indazol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (6)
[0000]
[0172] N-(2,4-Dimethoxy-5-((4-(2-methyl-2H-indazol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (7)
[0000]
[0173] The synthesis of N-(4-fluoro-2-methoxy-5-nitrophenyl)-4-(2-methyl-2H-indazol-3-yl)pyrimidin-2-amine (Intermediate J) is shown above in Scheme 5. Examples 5, 6, and 7 are prepared as in Schemes 1, 2, and 3, respectively, by substituting Intermediate J for Intermediate A in each of those schemes.
Example 8
N-(5-((4-(1,2-Dimethyl-1H-indol-3-yl)pyrimidin-2-yl)amino)-2-(2-(dimethylamino)ethoxy)-4-methoxyphenyl)acrylamide (8)
[0174]
[0175] 3-(2-Chloropyrimidin-4-yl)-1,2-dimethyl-1H-indole (Scheme 6, Intermediate K). Ferric chloride (5.8 g, 34.7 mmol) was rapidly added to a degassed, clear yellow solution of 1,2-dimethyl-1H-indole (4.9 g, 33.8 mmol) and 2,4-dichloropyrimidine (5.2 g, 33.9 mmol) dissolved in anhydrous 1,2-dimethoxyethane (100 mL) while stirring at the ambient temperature. The resultant black, opaque solution was stirred at ambient temperature for 3 h under dry nitrogen atmosphere, then slowly poured into rapidly stirred 5% (w/v) aqueous NaHCO 3 (400mL). Crude product was isolated by filtration, and washed with DI water on the filter. The precipitate was suspended in methanol (200 mL) and evaporated to dryness to remove excess water, then triturated in hot acetonitrile, allowed to cool, and filtered to isolate 6.2 g of 3-(2-chloropyrimidin-4-yl)-1,2-dimethyl-1H-indole (Intermediate K) as a brown powder. 1 H NMR (300 MHz, DMSO) δ 2.77 (s, 3H), 3.79 (s, 3H), 7.23 (quin, 2H, J=7.53 Hz), 7.57 (d, 1H, J=7.25 Hz), 7.72 (d, 1H, J=5.61 Hz), 8.10 (d, 1H, J=7.46 Hz), 8.61 (d, 1H, J=5.43 Hz) ppm. 13 C NMR (75 MHz, DMSO) δ 12.8, 30.3, 108.8, 110.8, 117.5, 120.0, 121.8, 122.5, 125.8, 137.4, 142.6, 159.8, 160.4, 165.2 ppm. C i4 H 12 ClN 3 m/z MH + 258.
[0176] 4-(1,2-Dimethyl-1H-indol-3-yl)-N-(4-fluoro-2-methoxy-5-nitrophenyl)-pyrimidin-2-amine (Scheme 6, Intermediate L). Reagent grade 1,4-dioxane (57 mL) was added to a mixture of 3-(2-chloropyrimidin-4-yl)-1,2-dimethyl-1H-indole (1.47 g, 5.70 mmol), 4-fluoro-2-methoxy-5-nitroaniline (1.06 g, 5.69 mmol), and p-toluenesulfonic acid monohydrate (1.31 g, 6.89 mmol) contained in a 100 mL round bottom flask fitted with a reflux condenser and blanketing nitrogen inlet. The magnetically stirred suspension was heated to reflux under nitrogen blanket. While approaching reflux temperature the suspended solid dissolved. Reflux was continued overnight, then the reaction was cooled and poured into rapidly stirring DI water (250 mL) to precipitate the product. Crude product was isolated by filtration, washed with water and recrystallized from boiling 2-propanol to yield 2.06 g of 4-(1,2-dimethyl-1H-indol-3-yl)-N-(4-fluoro-2-methoxy-5-nitrophenyl)-pyrimidin-2-amine (Intermediate L) as a fine yellow powder. 1 H NMR (300 MHz, DMSO) δ 2.71 (s, 3H), 3.78 (s, 3H), 4.01 (s, 3H), 7.10-7.20 (m, 3H), 7.41 (d, 1H, J=13.4 Hz), 7.55 (d, 1H, J=7.99 Hz), 7.98 (d, 1H, J=7.90 Hz), 8.44 (d, 1H, J=5.70 Hz), 8.83 (br s, 1H), 8.93 (d, 1H, J=8.38 Hz). C 21 H 18 FN 5 O 3 m/z MH + 408.
[0177] 4-(1,2-Dimethyl-1H-indol-3-yl)-N-(4-(2-(dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl) pyrimidin-2-amine (Scheme 6, Intermediate M). 2-Dimethylaminoethanol (0.43 mL, 4.27 mmol) was added, by syringe over 5 min., to a stirred suspension of 60 wt. % sodium (173 mg, 4.33 mmol) in anhydrous 1,4-dioxane at the ambient temperature. Gas evolution was readily observed. After ten min., with no further observable gas evolution, 4-(1,2-dimethyl-1H-indol-3-yl)-N-(4-fluoro-2-methoxy-5-nitrophenyl)-pyrimidin-2-amine (Intermediate J) (351 mg, 0.86 mmol) was added, neat, to the rapidly stirred pot as one bolus. The reaction suspension immediately changed to a turbid red-brown color. After 5 min. an aliquot of the reaction was withdrawn, quenched into DI water, and extracted into ethyl acetate. Analysis of this extract by UHPLC-MS revealed the reaction to be complete. The pot contents were then poured into a stirred solution of ammonium chloride (0.23 g, 4.30 mmol) in DI water (150 mL) to precipitate the product. The yellow precipitate was isolated by filtration, washed with DI water, and allowed to dry to afford 386 mg of 4-(1,2-dimethyl-1H-indol-3-yl)-N-(4-(2-(dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl) pyrimidin-2-amine (Intermediate M). C 25 H 28 N 6 O 4 m/z MH + =477.
[0178] N 1 -(4-(1,2-Dimethyl-1H-indol-3-yl)pyrimidin-2-yl)-4-(2-(dimethylamino)-ethoxy)-6-methoxybenzene-1,3-diamine (Scheme 6, Intermediate N). Stannous chloride dihydrate (1.73 g, 7.67 mmol) was added to a stirred suspension of 4-(1,2-dimethyl-1H-indol-3-yl)-N-(4-(2-(dimethyl-amino)ethoxy)-2-methoxy-5-nitrophenyl) pyrimidin-2-amine (Intermediate M; 386 mg, 0.81mmol) in ethyl acetate (40 mL) at the ambient temperature, and the mixture was heated at reflux under nitrogen blanket for 17 h. The reaction was allowed to cool, then poured into a 1% (w/v) solution of sodium hydroxide in DI water (200 mL) and stirred for 1 h. The multiphase mixture was filtered through tightly-packed Celite, with ethyl acetate rinsing of the filter cake. The filtrate was transferred to a separatory funnel and the liquid phases were separated. The retained ethyl acetate solution of product was washed with brine, dried over anhydrous calcium sulfate, filtered and evaporated to provide a brown solid foam which was purified by gradient flash chromatography (SiO 2 , 2% NH 4 OH in MeOH/ethyl acetate, 0 to 20% over 40 min.) to provide 186 mg of N 1 -(4-(1,2-dimethyl-1H-indol-3-yl)pyrimidin-2-yl)-4-(2-(dimethylamino)-ethoxy)-6-methoxybenzene-1,3-diamine (Intermediate N) as yellow solid. 1 H NMR (300 MHz, DMSO) δ 2.34 (s, 6H), 2.70 (t, 2H, J=6.90 Hz), 2.75 (s, 3H), 3.58 (br s, 2H), 3.74 (s, 3H), 3.83 (s, 3H), 4.07 (t, 2H, J=5.34 Hz), 6.57 (s, 1H), 6.95 (d, 1H, J=5.19 Hz), 7.17-7.27 (m, 2H), 7.32-7.35 (m, 1H), 7.55 (s, 1H), 8.09 (dd, 1H, J=6.96, 1.77 Hz), 8.18 (s, 1H), 8.38 (d, 1H, J=5.22 Hz) ppm. C 25 H 30 N 6 O 2 m/z MH + =447.
[0179] N-(5-((4-(1,2-Dimethyl-1H-indol-3-yl)pyrimidin-2-yl)amino)-2-(2-(dimethyl-amino)ethoxy)-4-methoxyphenypacrylamide (8). N 1 -(4-(1,2-Dimethyl-1H-indol-3-yl)pyrimidin-2-yl)-4-(2-(dimethylamino)etho xy)-6-methoxy-benzene-1,3-diamine (Scheme 6, Intermediate N) is converted into Example 8 by reaction with 3-chloropropionychloride followed by treatment with NaOH by using the procedures described in the preparation of Example 1.
Example 9
N-(2-(2-(Dimethylamino)ethoxy)-4-methoxy-5-((4-(pyrazolo[1,5-a]pyridin-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (9)
[0180]
[0181] N-(4-(2-(Dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(pyrazolo[1,5-a]pyridin-3-yl) pyrimidin-2-amine (Scheme 7, Intermediate P). To a slurry of NaH (21 mmol, 60% oil dispersion prewashed with hexanes) and 20 mL of 1,4-dioxane was added 2-dimethylaminoethanol (20 mmol, 2.4 mL) dropwise with stirring under N 2 . After stirring for 45 min, a slurry of compound O (7.9 mmol) was added portion-wise, with stirring and under a stream of N 2 . The resulting mixture was stirred overnight, then poured into water and the solid was collected, rinsed with water, and dried under vacuum to yield 1.7 g of Intermediate P as a yellow solid, which was used in the next step without further purification: C 22 H 23 N 7 O 4 m/z MH + 450.
[0182] 4-(2-(Dimethylamino)ethoxy)-6-methoxy-N1-(4-(pyrazolo[1,5-a]pyridin-3-yl)benzene)-1,3-diamine (Scheme 9, Intermediate Q). A suspension of 0.7 g of Intermediate P, 0.9 g of Fe 0 , 7 mL of ethanol, 3 mL of water, and 2 mL of glacial acetic acid was heated to 78° C. for 1 h. The solution was cooled to room temperature, filtered through Dicalite, adjusted to pH 10 with 1 N NaOH (aq) and diluted with CH 2 Cl 2 . The filtrate layers were separated, and the aqueous phase was extracted with CH 2 Cl 2 twice, and the combined organic extracts were dried over Na 2 SO 4 and concentrated. Column chromatography (silica gel, CH 2 Cl 2 —MeOH gradient) afforded 0.28 g of Intermediate Q as tan solid. C 22 H 25 N 7 O 2 m/z MH + 420.
[0183] N-(2-(2-(Dimethylamino)ethoxy)-4-methoxy-5-(4-(pyrazolo[1,5-a]pyridin-3-yl)benzene)-acrylamide (9). To a solution of Intermediate Q (0.6 g, 1.4 mmol) in 10 mL of THF and 4 mL of water was added 3-chloropropionychloride (0.15 mL, 1.6 mmol) dropwise with stirring. After 22 h of stirring, NaOH (0.7 g, 17 mmol) was added and the mixture was heated at 65° C. for 5 h. After cooling to room temperature, THF was removed under reduced pressure, and the mixture was extracted with CH 2 Cl 2 , dried over Na 2 SO 4 , and concentrated. Chromatography of the crude product (silica gel, CH 2 Cl 2 —MeOH) afforded 0.294 g of Example 9 as a beige solid. C 25 H 27 N 7 O 3 m/z MH + 474. 1 H NMR (300 MHz, DMSO) δ 2.28 (s, 6H), 2.61-2.62 (m, 2H), 3.82 (s, 3H), 4.20-4.22 (m, 2H), 5.69-5.73 (m, 1H), 6.20-6.22 (m, 1H), 6.42-6.48 (m, 1H), 6.90-7.11 (m, 2H), 7.15-7.40 (m, 2H), 8.10-8.59 (overlapping m, 4H), 8.72-8.96 (m, 2H), 10.13 (s, 1H) ppm.
Example 10
N-(2-(2-(Dimethylamino)ethoxy)-4-methoxy-5-(4-(1-methyl-1H-indazol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (10)
[0184] N-(4-Fluoro-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indazol-3-yl)pyrimidin-2-amine (Scheme 8, Intermediate R). Into a 1000-mL 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 1H-indazole (10 g, 84.65 mmol, 1.00 equiv) in N,N-dimethylformamide (500 mL), I 2 (21.5 g, 84.65 mmol, 1.00 equiv). This was followed by the addition of KOH (19 g, 338.62 mmol, 4.00 equiv) in several batches at 0° C. The resulting solution was stirred overnight at room temperature. The reaction was then quenched by the addition of 200 mL of aqueous Na 2 S 2 O 3 . The resulting solution was extracted with 3×500 mL of ethyl acetate and the organic layers combined. The resulting mixture was washed with 3×500 mL of brine. The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. The resulting mixture was washed with 1×100 mL of hexane. This resulted in 14 g (68%) of 3-iodo-1H-indazole as a white solid.
[0000]
[0185] Into a 500-mL 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 3-iodo-1H-indazole (14 g, 57.37 mmol, 1.00 equiv) in tetrahydrofuran (200 mL). This was followed by the addition of NaH (65%) (2.5 g, 1.20 equiv) in several batches at 0° C. The mixture was stirred for 30 min at 0° C. To this was added iodomethane (9.7 g, 68.34 mmol, 1.20 equiv) dropwise with stirring at 0° C. The resulting solution was stirred for 1 h at room temperature. The reaction was then quenched by the addition of 300 mL of water/ice. The resulting solution was extracted with 2×300 mL of ethyl acetate and the organic layers combined. The resulting mixture was washed with 1×300 mL of brine. The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (1:5). This resulted in 8 g (54%) of 3-iodo-1-methyl-1H-indazole as a yellow solid
[0186] Into a 500-mL 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 3-iodo-1-methyl-1H-indazole (5 g, 19.38 mmol, 1.00 equiv) in 1,4-dioxane (200 mL), hexamethyldistannane (12 g, 36.63 mmol, 2.00 equiv), tetrakis(triphenylphosphane) palladium (2.2 g, 1.90 mmol, 0.10 equiv). The resulting solution was stirred for 6 h at 100° C. The reaction mixture was cooled to room temperature with a water/ice bath. The reaction was then quenched by the addition of 30 mL of aqueous KF (1 N) dropwise with stirring. The resulting solution was stirred for 0.5 h at room temperature. The resulting solution was diluted with 200 mL of H 2 O. The resulting solution was extracted with 2×200 mL of ethyl acetate and the organic layers combined. The resulting mixture was washed with 3×200 mL of brine. The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (1:5). This resulted in 3.9 g (68%) of 1-methyl-3-(trimethylstannyl)-1H-indazole as yellow liquid.
[0187] Into a 250-mL 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed 1-methyl-3-(trimethylstannyl)-1H-indazole (3.9 g, 13.22 mmol, 1.00 equiv), 1,4-dioxane (100 mL), 2,4-dichloropyrimidine (2.0 g, 13.42 mmol, 1.00 equiv), tetrakis(triphenylphosphane) palladium (1.5 g, 1.30 mmol, 0.10 equiv). The resulting solution was stirred overnight at 105° C. The reaction mixture was cooled to room temperature with a water/ice bath. The reaction was then quenched by the addition of 200 mL of water/ice. The solids were collected by filtration. The filter cake was washed with 1×100 mL of Et 2 O. This resulted in 2.1 g (65%) of 3-(2-chloropyrimidin-4-yl)-1-methyl-1H-indazole as a light yellow solid.
[0188] Into a 250-mL 3-necked round-bottom flask, was placed 3-(2-chloropyrimidin-4-yl)-1-methyl-1H-indazole (2.9 g, 11.85 mmol, 1.00 equiv), 4-fluoro-2-methoxy-5-nitroaniline (2.2 g, 11.82 mmol, 1.00 equiv), 2-propanol (80 mL), TsOH (2.4 g, 13.94 mmol, 1.20 equiv). The resulting solution was stirred overnight at 80° C. The reaction mixture was cooled to room temperature with a water/ice bath. The solids were collected by filtration. The filter cake was washed with 100 mL of CH 3 CN. The solid was dried in an oven. This resulted in 1.06 g (23%) of N-(4-fluoro-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indazol-3-yl)pyrimidin-2-amine (Intermediate R) as a yellow solid. (ES, m/z): [M+H] + =395; 1 H-NMR (300 MHz, DMSO-d 6 ,) δ 8.96 (br, 1H), 8.87-8.85 (d, J=8.4Hz, 2H), 8.56-8.54 (d, J=5.4Hz, 1H), 8.49-8.46 (d, J=8.1Hz, 1H), 7.77-.775 (d, J=8.4Hz, 1H),7.58-7.57 (d, J=5.1Hz, 1H), 7.52-7.47 (t, J=7.2Hz, 1H), 7.44-7.40 (d, J=13.5Hz, 1H), 7.26-7.21 (t, J=7.5Hz, 1H), .4.19 (s, 1H), 4.01 (s, 1H) ppm.
[0189] N-(4-(2-(Dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indazol-3-yl)pyrimidine-2-amine (Scheme 8, Intermediate S). To a suspension of NaH (31 mg, 1.3 mmol) in 10 mL of 1,4-dioxane was added 2-dimethylaminoethanol (0.16 mL, 1.3 mmol) dropwise with stirring under N 2 . After stirring for 1.5 h, Intermediate R (0.2 g, 0.51 mmol) was added portionwise. After 0.5 h, the reaction mixture was quenched with water and extracted with CH 2 Cl 2 . The organic phase was dried over Na 2 SO 4 , filtered and concentrated to yield 0.23 g of N-(4-(2-(dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indazol-3-yl)pyrimidine-2-amine (Intermediate S): m/z MH + =464.
[0190] 4-(2-(Dimethylamino)ethoxy)-6-methoxy-N 1 -(4-(1-methyl-1H-indazol-3yl )pyrimidin-2-yl)benzene-1,3-diamine (Scheme 8, Intermediate T). A suspension of N-(4-(2-(dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(1-methyl-1H-indazol-3-yl)pyrimidine-2-amine (0.23 g), 0.28 g of Fe 0 , 10 mL of 70% ethanol/H 2 O, and 0.5 mL of acetic acid was heated at reflux with stirring for 2 h. The mixture was cooled to room temperature, then filtered. The filtrate was adjusted to pH 10, then extracted with CH 2 Cl 2 . The organic phases were combined, dried over Na 2 SO 4 , filtered and concentrated. The crude product was purified by chromatography (silica gel, CH 2 Cl 2 -1% NH 4 OH/MeOH gradient) to afford 4-(2-(dimethylamino)ethoxy)-6-methoxy-N 1 -(4-(1-methyl-1H-indazol-3yl )pyrimidin-2-yl)benzene-1,3-diamine (Intermediate T) as an off-white solid: m/z MH + 434.
[0191] N-(2-(2-(Dimethylamino)ethoxy)-4-methoxy-5-((4-(1-methyl-1H-indazol-3-yl)pyrimidin-2-yl)amino)phenyl)acrylamide (Example 10). To a solution of 4-(2-(dimethylamino)ethoxy)-6-metho xy-N1-(4-(1-methyl-1H-indazol-3 yl)pyrimidin-2-yl)benzene-1,3-diamine (60 mg, 0.14 mmol) dissolved in 10 mL of 4:1 THF:H 2 O was added 3-chloropropionyl chloride (17 mg, 0.14 mmol). After 4h, NaOH (1.4 mmol, 56 mg) was added and the mixture was heated at reflux for 5 h. THF was removed under reduced pressure, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, washed with H 2 O, dried (Na 2 SO 4 ) and concentrated. The crude product was purified by chromatography (silica gel, CH 2 Cl 2 —MeOH gradient) to afford Example 10 as a solid: C 26 H 29 N 7 O 3 m/z MH + 488; 1 H NMR (300 MHz, DMSO) δ 2.28 (s, 6H), 2.51-2.63 (m, 2H), 3.80 (s, 3H), 4.14-4.44 (overlapping m, 5H), 5.68-5.76 (m 1H), 6.11-6.19 (m, 1H), 6.43-6.48 (m, 1H), 6.95 (s, 1H), 7.11-7.17 (m, 1H), 7.37-7.45 (overlapping m, 2H), 7.68-7.07 (d, 1H, J=8.4 Hz), 8.39-8.43 (overlapping m, 4H), 9.75 (s, 1H) ppm.
Example 11
N-(2-(2-(Dimethylamino)ethoxy)-5-((4-(1-(2-fluoroethyl)-1H-indolyl-3-yl)pyrimidin-2-yl)amino)-4-methoxyphenyl)acrylamide (11)
[0192] 1-(2-Fluoroethyl)-1H-indole (Scheme 9). Sodium hydride, 60 wt. % in oil (2.3g, 57.5 mmol) was added to stirred, 0° C., clear, colorless solution of indole (10.1g, 86.2 mmol) in anhydrous tetrahydrofuran at as rapid a rate consistent with maintaining control of the concomitant hydrogen evolution. Solution was stirred at 0° C. under N 2 blanket until gas evolution ceased, and reaction had become a fine white suspension. A solution of 1-fluoro-2-iodoethane (5g, 29 mmol) in anhydrous tetrahydrofuran (6mL) was then slowly added via syringe, the ice bath was removed and the pot heated to reflux overnight. The reaction mixture was cooled, diluted with a solution of ammonium chloride (4.6g, 86 mmol) in DI water (300mL), transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried (CaSO 4 ) and evaporated to provide a yellow oil, which was flash chromatographed (silica gel, 100% hexanes) to provide 4.2g of yellow oil, characterized by LC-MS as a 60/40 mixture of indole to desired product. This impure product was treated with benzene sulfonyl chloride to modify the elution characteristics of the mixture to allow for isolation of the desired product as follows: To a 0° C. solution of the above isolated 60/40 mixture of indole to desired product and tetrabutyl ammonium bisulfate 1.2 g, 3.4 mmol) in anhydrous toluene (100mL) was added a solution of sodium hydroxide (24.7g, 617.5 mmol) in DI water (25 mL). To the rapidly stirred, 0° C., mixture was then added benzene sulfonyl chloride (5.5 mL, 43.1 mmol) and the reaction allowed to stir and warm to ambient temperature under N 2 blanket overnight.
[0000]
[0193] The reaction mixture was then partitioned between ethyl acetate and DI water, the organic phase dried (CaSO 4 ) and flash chromatographed (silica gel, 10% acetone/ hexanes) to cleanly resolve the 1-phenylsulfonyl indole from the desired product affording 1.3g of 1-(2-fluoroethyl)-1H-indole as a clear, colorless liquid. 1 H NMR (300 MHz, DMSO) δ 4.45 (t, 1H, J=4.9Hz), 4.54 (t, 1H, J=4.9Hz), 4.64 (t, 1H, J=4.6Hz), 4.80 (t, 1H, J=4.4Hz), 6.46 (dd, 1H, J=3.1, 0.8Hz), 7.03 (m, 1H), 7.13 (m, 1H), 7.37 (d, 1H, J=3.2Hz), 7.49 (d, 1H, J=8.3Hz), 7.55 (m, 1H) ppm. 13 C NMR (75 MHz, DMSO) δ 46.4 (d, J CF =19.5Hz), 83.3 (d, J CF =166.5Hz), 101.4, 110.3, 119.6, 120.9, 121.6, 128.6, 129.3, 136.4 ppm. C 10 H 10 NF m/z MH + 164.
[0194] 3-(2-Chloropyrimidin-4-yl)-1-(2-fluoroethyl)-1H-indole (Scheme 9, Intermediate U). Ferric chloride (1.3 g, 7.9 mmol) was rapidly added to a stirring, ambient temperature, degassed, clear, colorless solution of 1-(2-fluoroethyl)-1H-indole and 2,4-dichloropyrimidine (1.2 g, 8.3 mmol) dissolved in anhydrous 1,2-dimethoxyethane (80mL). The resultant black, opaque, solution was stirred at 60° C. for 17 h under dry nitrogen atmosphere, cooled, and partitioned between ethyl acetate and saturated aqueous sodium chloride. The organic phase was dried (CaSO 4 ) and evaporated to provide 2.3 g of purple oil which was purified by flash chromatography (silica gel, 0 to 90% ethyl acetate in hexanes) to yield 557.5 mg of 3-(2-chloropyrimidin-4-yl)-1-(2-fluoroethyl)-1H-indole (U) as a light yellow powder. 1 H NMR (300 MHz, DMSO) δ 4.60 (t, 1H, J=4.7Hz), 4.69 (t, 1H, J=4.8Hz), 4.75 (t, 1H, J=4.4Hz), 4.90 (t, 1H, J=4.4 Hz), 7.31 (m, 2H), 7.67 (m, 1H), 7.88 (d, 1H, J=5.5Hz), 8.44 (m, 1H), 8.57 (m, 2H) ppm. 13 C NMR (75 MHz, DMSO) δ 47.2 (d, J CF =19.8Hz), 82.8 (d, J CF =167.7Hz), 111.6, 111.9, 115.0, 122.1, 122.3, 123.4, 125.8, 134.6, 137.8, 159.4, 160.8, 164.9 ppm. C 14 H 11 ClFN 3 m/z MH + 276.
[0195] N-(4-Fluoro-2-methoxy-5-nitrophenyl)-4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-amine (Scheme 9, Intermediate V). p-Toluene sulfonic acid monohydrate (442.8 mg, 2.3 mmol) was added to a stirred suspension of 3-(2-chloropyrimidin-4-yl)-1-(2-fluoroethyl)-1H-indole (U) (535.3 mg, 1.9 mmol) and 4-fluoro-2-methoxy-5-nitroaniline (361.4 mg, 1.9 mmol) in 1,4-dioxane (20 mL) and heated to reflux under nitrogen blanket. While approaching reflux temperature the suspended solid dissolved. Reflux was continued overnight, then the reaction was cooled and poured into a rapidly stirred 5% (w/v) solution sodium hydrogen carbonate in DI water (200 mL) to precipitate product. Product was isolated by filtration, washed with water and allowed to dry to yield 921.4 mg of N-(4-fluoro-2-methoxy-5-nitrophenyl)-4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-amine (V) as a fine yellow powder. C 21 H 17 F 2 N 5 O 3 m/z MH + =426.
[0196] N-(4-(2-(Dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-amine (Scheme 9, Intermediate W). 2-(Dimethylamino)ethanol (0.8 mL, 7.7 mmol) was slowly added to a stirred, N 2 blanketed, ambient temperature, suspension of sodium hydride, 60 wt. % in oil (306.4 mg, 7.7 mmol) in anhydrous 1,4-dioxane (24 mL). Anion formation was allowed to proceed for 0.5 h, then N-(4-fluoro-2-methoxy-5-nitrophenyl)-4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-amine (intermediate V) (652.0 mg, 1.53 mmol) was added all at once. The reaction immediately turned to a red color, and was allowed to stir. After 10 min., LC-MS reported the reaction to be complete. DI water (5 mL) was added to quench, then the mixture was partitioned between ethyl acetate and saturated aqueous sodium chloride. The organic extract was dried (CaSO 4 ) and evaporated to afford a yellow solid. This solid was recrystallized from boiling ethyl acetate/heptane, which upon cooling, precipitated a bright yellow crystalline powder. The powder was isolated by filtration, washed with heptane, and allowed to dry providing 572.0 mg of N-(4-(2-(dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-amine (W). 1 H NMR (300 MHz, DMSO) δ 2.27 (s, 6H), 2.71 (t, 2H, J=5.7Hz), 4.01 (s, 3H), 4.33 (t, 2H, J=5.6Hz), 4.56 (t, 1H, J=4.6Hz), 4.65 (t, 1H, J=4.6Hz), 4.73 (t, 1H, J=4.2Hz), 4.89 (t, 1H, J=4.6Hz), 7.01 (s, 1H), 7.10 (m, 1H), 7.25 (m, 2H), 7.61 (d, 1H, J=8.4Hz), 8.22 (s, 1H), 8.36 (m, 3H), 8.76 (s, 1H) ppm. 13 C NMR (75 MHz, DMSO) δ 46.2, 47.0 (d, J CF =19.5Hz), 57.3, 58.0, 69.0, 82.8 (d, J CF =166.6Hz), 99.2, 108.2, 111.1, 113.4, 119.2, 121.4, 122.4, 122.6, 122.8, 126.0, 131.3, 132.8, 137.6, 150.6, 156.2, 157.7, 160.5, 162.5 ppm. C 25 H 27 F N 6 O 4 m/z MH + 495.
[0197] 4-(2-(Dimethylamino)ethoxy)-N1-(4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-yl)-6-methoxybenzene-1,3-diamine (Scheme 9, Intermediate X). Stannous chloride dihydrate (708.3 mg, 3.1 mmol) was added to a stirred, ambient temperature yellow suspension of N-(4-(2-(dimethylamino)ethoxy)-2-methoxy-5-nitrophenyl)-4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-amine (W) (303.8 mg, 0.6 mmol) in ethyl acetate (30 mL) and heated at reflux under nitrogen blanket for 4h. The reaction was allowed to cool, then poured into a 5% (w/v) solution of sodium hydrogen carbonate in DI water (200 mL) and stirred for 0.5 h. The multiphase mixture was then filtered through tightly packed celite, with ethyl acetate rinsing of the filter cake. The filtrate was transferred to a separatory funnel and the liquid phases separated. The retained ethyl acetate solution of product was washed with saturated aqueous sodium chloride, dried (CaSO 4 ), and evaporated to provide a red oil which was purified by flash chromatography (silica gel, 2% NH 4 OH(aq.) in methanol/ethyl acetate; 0 to 10%,) to isolate X as 165.4 mg of red oil. C 25 H 29 FN 6 O 2 m/z MH + 465.
[0198] N-(2-(2-(Dimethylamino)ethoxy)-5((4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-yl)amino)-4-methoxyphenyl)acrylamide (11, Scheme 9). 3-Chloropropanoyl chloride (38 mL, 0.4 mmol) was slowly added, by syringe, to a rapidly stirred, 0° C., nitrogen blanketed solution of 4-(2-(dimethylamino)ethoxy)-N1-(4-(1-(2-fluoroethyl)-1H-indol-3-yl)pyrimidin-2-yl)-6-methoxybenzene-1,3-diamine (Intermediate X) in anhydrous tetrahydrofuran (20 mL). Upon this addition, precipitate immediately formed. The suspension was stirred at 0° C. for an additional 5 min. then the ice bath was removed. Upon confirmation of complete conversion to the 3-chloropropanamide intermediate, a solution of sodium hydroxide (726.0 mg, 18.2 mmol) in DI water (5.0 mL) was added to the reaction suspension which was heated to reflux for 1 h then cooled and partitioned with brine and additional tetrahydrofuran. The organic extract was dried (CaSO 4 ) and evaporated to yield 445.1mg of solid orange foam which was purified by gradient flash chromatography (silica gel, 2% NH 4 OH(aq.) in methanol/ethyl acetate; 0 to 10%), and crystalized from ethyl acetate/heptane to isolate 130 mg of Example 11 as a fine light yellow powder. 1 H NMR (300 MHz, DMSO) δ 2.28 (s, 6H), 2.58 (t, 2H, J=5.3Hz), 3.86 (s, 3H), 4.19 (t, 2H, J=5.3Hz), 4.58 (t, 1H, J=4.6Hz), 4.67 (t, 1H, J=4.5Hz), 4.72 (t, 1H, J=4.6Hz), 4.88 (t, 1H, J=4.6Hz), 5.75 (dd, 1H, J=10.4, 1.7Hz), 6.22 (dd, 1H, J=17.0, 1.9Hz), 6.48 (m, 1H), 6.95 (s, 1H), 7.14 (t, 1H, J=7.4Hz), 7.22 (m, 2H), 7.60 (d, 1H, J=8.2Hz), 7.94 (s, 1H), 8.30 (m, 2H), 8.56 (s, 1H), 8.80 (s, 1H), 9.83 (s, 1H) ppm. 13 C NMR (75 MHz, DMSO) δ 45.6, 46.9 (d, J CF =19.9Hz), 56.6, 57.9, 60.2, 69.4, 82.9 (d, J CF =168.2Hz), 101.6, 107.5, 111.1, 113.6, 116.9, 121.4, 122.3, 122.6, 123.2, 126.0, 126.6, 132.6, 133.2, 137.6, 145.3, 147.8, 158.0, 160.7, 162.1, 163.2 ppm. C 28 H 31 FN 6 O 3 m/z MH + 519.
[0199] The following non-limiting Examples further illustrate certain aspects of the present invention, which are prepared according to the general Synthetic Schemes 1 to 9 above:
[0000]
Biological Assays
[0200] Compounds of the formula I as novel EGFR tyrosine kinase inhibitors were evaluated for their activity against EGFR according to the procedures described below.
[0201] Cell Culture. A431 (passage 3) and NCI-H1975 (passage 5) cells (ATCC) were started from frozen stocks and cultured in RPMI 1640 medium supplemented with 10% heat-inactivated fetal bovine serum, 1× penicillin/streptomycin/glutamine, 1 mM sodium pyruvate, 10 mM 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), and 0.25% D-glucose (growth medium) in T175 flasks in a humidified 30° C., 5% CO 2 incubator. The cell monolayer was dispersed by 5 minute exposure to 0.25% Trypsin/EDTA solution (Life Technologies) and the solution was neutralized with a fresh growth medium. Pooled cells were pelleted by centrifugation (200×g, 8 min.), resuspended in the growth medium, and an aliquot was removed for cell counting using an automated cell counter (Logos Biosystems). The cells maintained normal morphology and growth characteristics during the period of the study.
[0202] Cell Proliferation Assay. Dispersed cells were pooled by centrifugation (200×g, 8 min.) and resuspended in a fresh medium to a concentration of 1.00E+04 cells/ml. 200 μL of the cell suspension was added to each well (2,000 cells/well) of a black-walled 96 well plate and the cells were allowed to attach overnight under normal culture conditions. After overnight culturing, 1 μL of a test compound (n=3 per concentration) was added per well to achieve final concentrations of 10, 3.33, 1.11, 0.370, 0.124, 0.0412, 0.0137, 0.0046, and 0.0015 μM. The final DMSO concentration in the well was 0.5% v/v. Vehicle, non-treated, and cell-free wells were also included in the assay. The cells were cultured under normal conditions for 72 hours with daily visual inspection.
[0203] Cell proliferation was measured using the dye Alamar Blue (resazurin). Resazurin is reduced by cellular enzymes to resorufin, which is fluorescent (544 nM excitation, 612 nm emission). Fluorescence intensity was proportional to cell number. A resazurin stock solution was prepared in a phosphate-buffered saline (PBS) to a stock concentration of 440 μM. The resazurin stock solution (40 μL each) was added to each well at hour 67 of the 72 hour incubation period. The plate was returned to normal culture conditions and fluorescence measurements were collected using a Cytation 3 multimode plate reader (Biotek) at 72 hours.
[0204] Data Analysis. Fluorescence measurements were normalized against cell-free (background) readings and the total growth over 72 hour time period was determined versus the average of the vehicle control wells. Average and standard deviation values were determined for each condition (n=3).
[0205] Table 1 contains illustrative data from study of representative compounds of the present invention, which demonstrate their excellent selectivity for inhibition of the growth of H1975 (double mutant) cells over A431 (wild type) cells.
[0000]
TABLE 1
Biological activity of selected compounds in the A431 (wild type) and
H1975 (double mutant) cell proliferation assays.
Example
A431 IC 50 (μM) a
H1975 IC 50 (μM) a
1
+
+++
2
+
+++
3
+
++
4
+
+++
5
++
++
8
++
+++
9
+
+++
10
++
+++
11
++
+++
a An IC 50 value greater than 1.0 μM is represented by “+”; an IC 50 in the range of 0.1-1.0 μM is represented by “++”, and an IC 50 value below 0.1 μM is represented by “+++”.
[0206] The in vivo anticancer activity of Examples 1 and 2 is also illustrated in FIGS. 1-4 .
[0207] Antitumor Activity of Example 1 in the H1975 Mouse Xenograft Model. The in vivo anticancer activity of Example 1 against tumors with the L858R/T790M double mutation is illustrated in FIG. 1 . Example 1 was evaluated in subcutaneously-implanted H1975 human non-small cell lung carcinoma xenographs in female nude mice at 6.25, 12.5 and 25 mg/kg. Example 1 was dosed orally once a day for 14 days (days 6-19). At all doses, Example 1 was well tolerated, resulting in no treatment-related mortality. Treatment with 1 at 6.25, 12.5 and 25 mg/kg produced a median time to evaluation size of 28.9, 31.6 and 34.3 days, respectively, resulting in a statistically significant (P<0.05) tumor growth delay of 14, 16.7 and 19.3 days, respectively. At 25 mg/kg, treatment produced a 100% incidence of complete regressions and 10% of the mice were tumor free survivors.
[0208] Antitumor Activity of Example 2 in the H1975 Mouse Xenograft Model. The in vivo anticancer activity of Example 2 against tumors with the L858R/T790M double mutation is illustrated in FIG. 2 . Example 2 was evaluated in subcutaneously-implanted H1975 human non-small cell lung carcinoma xenographs in female nude mice at 50 and 100 mg/kg. Example 2 was dosed orally once a day for 14 days (days 7-20). At 100 mg/kg oral dosing, Example 2 was well tolerated and produced significant (P<0.05) anticancer activity based upon the % tumor growth inhibition values (% TGI) of 110.5%, 116.6% and 116.6%, which were calculated from the median tumor burdens on days 10, 14 and 17, respectively. Time to evaluation size (750 mm 3 ) was 39.6 days, resulting in a tumor growth delay (T-C) of 22.2 days, which is also statistically significant. Treatment produced a 100% incidence of complete tumor regression and 12.5% of the mice remained tumor free (TFS) at the completion of the study.
[0209] Antitumor Activity of Example 1 in the HCC827 Mouse Xenograft Model. The in vivo anticancer activity of Example 1 against tumors with the delE746-A750 activating mutation is illustrated in FIG. 3 . Example 1 was evaluated in a subcutaneously-implanted HCC827 human non-small cell lung carcinoma xenographs in female nude mice at 6.25 mg/kg. Example 1 was dosed orally once a day for 14 days (days 13-26). At 6.25 mg/kg oral dosing, 1 was well tolerated, resulting in no treatment-related mortality. Treatment with 1 produced a median time to evaluation size of 61.5 days, resulting in a statistically significant (P<0.05) tumor growth delay of 33.2 days. Treatment produced a 100% incidence of complete tumor regression at the completion of dosing. FIG. 4 shows the average concentration of Example 1 in plasma, brain and tumor tissues following a 25 mg/kg oral dose in this model.
[0210] The foregoing examples and description of the preferred embodiments should be taken as illustrating, rather than as limiting the present invention as defined by the claims. As will be readily appreciated, numerous variations and combinations of the features set forth above can be utilized without departing from the present invention as set forth in the claims.
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This application discloses novel substituted 2-anilinopyrimidine derivatives, and pharmaceutically acceptable salts, solvates, prodrugs, and compositions thereof, which are useful for the treatment or prevention of diseases or medical conditions mediated by epidermal growth factor receptors (EGFRs), including but not limited to a variety of cancers.
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This application claims the benefit under 35 U.S.C. §119(e) of the U.S. provisional patent application No. 60/010924 filed Jan. 31, 1996.
1. Technical Field
The present invention relates to blood separation apparatus and more particularly to centrifuge bowl housings and cover latches thereof.
2. Background Art
Surgical operations, including more complex operations where a substantial amount of bleeding may occur, may require transfusions during the course of the surgery to maintain a sufficient blood volume and blood pressure. Whole human blood is composed of several components, including red blood cells, plasma, platelets, leukocytes or white blood cells, and cellular debris. Human blood can be separated into the constituent components so that only the desirable components are injected into a patient. Centrifuges have been developed for rapidly and efficiently separating blood or other biological fluids into constituent components.
Since many blood-borne diseases may exist including hepatitis, cancer and HIV, it is desirable to contain any fluids that could be spattered by a rapidly rotating centrifuge bowl if the bowl should break. It is also desirable to prevent injury to nearby personnel from flying pieces of a centrifuge bowl if a rapidly rotating centrifuge bowl breaks.
Centrifuges for blood separation disclosed in the prior art include a housing and a cover. Typically these centrifuges have a sensor between the housing and cover that sends a signal to the centrifuge controller when the cover is opened so that the controller will shut off power to the centrifuge drive motor. On centrifuges without a latch to hold the cover closed, spattered blood and flying bowl fragments from a broken centrifuge bowl can partially open the centrifuge cover and escape.
Some of the prior art centrifuges include a latch system that holds the cover closed. The cover on each of these centrifuges can be opened before the centrifuge stops spinning, presenting a risk of injury to an operator as well as the hazards of spattered blood and flying bowl fragments as discussed above.
Prior art centrifuges do not provide automatic collection of fluids spilled within the housing, prevention of contamination of the drive means bearings by corrosive spilled blood components, or positive sealing of the housing/cover interface to prevent leakage of fluids.
Centrifuges spin at high speeds. Any imbalance in the centrifuge mechanism or centrifuge bowl creates vibrations. Existing centrifuges use balanced seamless bowls or use elastomeric material for grip the bowl.
DISCLOSURE OF THE INVENTION
The centrifuge bowl housing and latch disclosed are suitable for use in a blood separation apparatus. The centrifuge bowl housing contains a centrifuge bowl which is rotated at high speeds for blood separation purposes. The cover seals the housing when closed, preventing leakage of blood or other fluids, and, in the situation where a centrifuge bowl breaks, preventing possible injury to an operator. The convex shape of the bottom drains fluids away from the centrifuge drive shaft and collects spilled fluids in a peripheral channel. A drain port which may be connected to a waste bag is connected to the peripheral channel for automatic collection of spilled fluid.
The latch prevents the centrifuge running if the cover is open. A latch lock prevents opening the cover if the centrifuge is running.
The centrifuge bowl housing is supported on shock absorbers which minimize transmission of vibration and eliminate the need for expensive balancing of the bowl or complex means for retaining the bowl.
BRIEF DESCRIPTION OF THE DRAWINGS
Details of this invention are described in connection with the accompanying drawings that bear similar reference numerals in which:
FIG. 1 is a perspective view of a centrifuge bowl housing embodying the present invention.
FIG. 2 is an exploded perspective view of a centrifuge bowl housing and latch embodying the present invention.
FIG. 3 is a cross sectional view of a centrifuge bowl housing and latch embodying the present invention.
FIG. 4 is an exploded perspective view of a first latch assembly for a centrifuge bowl housing.
FIG. 5 is an exploded perspective view of a second latch assembly for a centrifuge bowl housing.
FIG. 6 is a cross sectional view of a latch assembly for a centrifuge bowl housing.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1, the centrifuge housing and latch for blood separation apparatus, generally stated, includes a horizontal base 31, a housing 10 supported by base 31, a cover 20 pivotally attached at one end to housing 10, and a latch 35 latching the opposite end of the cover 20 to the housing 10.
Base 31 is in the form of a flat square plate and has a base leg 32 rigidly attached at each corner. A shock absorber 30 rigidly attaches to each base leg 32. A housing leg 29 supporting housing 10 rigidly attaches to each shock absorber 30. Each shock absorber 30 is a short cylinder of elastomeric or rubber material with a threaded metal projection a, each end for attachment to the base leg 32 and the housing leg 29. Shock absorbers 30 minimize the transmission of vibration between housing 10 and base 31.
Referring to FIG. 2, centrifuge bowl housing 10 has a circular bottom wall 14, a cylindrical lower wall portion 9 extending up from bottom wall 14, and a flat back wall 11 and a curved side and front wall 12 extending up from lower wall portion 9. The lower portion of centrifuge bowl housing 10 has a circular cross section while the upper portion flares out. The opening formed by the upper edge 16 of rear wall 11 and the upper edge 15 of side and front wall 12 is a truncated oval with a straight side. Bottom wall 14 has a convex upper side to drain liquid away from the center. A channel is formed between the periphery of bottom wall 14 and lower wall portion 9 to collect spilled liquid. Drain port 13 attached at the bottom of lower wall portion 9 drains liquids from the housing.
Referring to FIG. 3, a drive motor 28 is rigidly attached to the underside of bottom wall 14. Drive motor 28 has an output shaft 27 which protrudes through bottom wall 14 into the interior of housing 10. A drive flange 26 in the interior of housing 10 is rigidly attached to output shaft 27. A rotary plate 25 is rigidly attached to the upper surface of drive flange 26. A seal 33 attached to bottom wall 14 and closely encircling drive shaft 26 prevents leakage of liquid from housing 10.
Returning now to FIG. 2, the upper edge 15 of side and front wall 12 slopes downwardly and forwardly from upper edge 16 of rear wall 11. The exterior portions of upper edge 15 of side and front wall 12 and upper edge 16 of rear wall are relieved to define shoulder 18. Shoulder 18 supports sealing gasket 19 which is shaped to conform to edges 15, 16 of the housing walls.
The cover 20 is made of a high impact resistant transparent material such as polycarbonate. Cover 20 is convex forming a dome. The lower edge 23 of cover 20 has a V shape, the point of V shaped lower edge 23 is formed to compress the center of the top face of sealing gasket 19 when cover 20 is closed. Cover 20 is pivotally attached to housing 10 at upper edge 16 of rear wall 11 by hinge 21. Hinge 21 has a hinge section 22 rigidly attached to rear wall 11 and hinge section 24 rigidly attached to cover 20, the hinge sections being appropriately pivoted together. When closed and latched, cover 20 seals centrifuge bowl housing 10.
Latch 35 is formed by lower first latch portion 36 and upper second latch portion 37. First latch portion 36 is rigidly attached to the upper portion of side and front wall 12 at the front of housing 10, opposite rear wall 11. Second latch portion 37 is rigidly attached to cover 20 at the front of cover 20 so that when cover 20 is closed second and first latch portions 36, 37 interact to hold cover 20 closed.
Referring to FIG. 4, first latch portion 36 includes first latch block 40, a latch pin 38, a flag pin 47, a lock pin 55 and a first latch cover 57. First latch cover 57 is a flat plate which is fastened to the upper surface of first latch block 40 and is provided to facilitate assembly and retention of flag pin 47 and lock pin 55.
Latch pin 38 is cylindrical with a conical or tapered head 70 on one end, and a threaded section on the other end. An annular groove 71 is relieved in latch pin 38 adjacent to the head. The shoulder formed on the back of the head by the groove is the first latch face 72. A threaded aperture is formed in the upper surface of first latch block 40 to receive the threaded first portion of latch pin 38. A hole is formed in first latch cover 57 allowing latch pin 38 to project through first latch cover 57.
Lock pin 55, when in a first or lock position prevents unlatching of latch 35. Lock pin has an cylindrical first portion and cylindrical second portion of larger diameter than the first portion, forming a shoulder between the portions. A vertical cylindrical lock pin aperture with a closed first end and an open second end, and with a diameter greater than the second portion of the lock pin 55 is relieved in the top surface of the first latch block 40 to receive a coil spring 56 and lock pin 55. A lock pin hole is formed in first latch cover 57 that allows the smaller first portion of lock pin 55 to extend through first latch cover 57 but retains the second portion of lock pin 55. Coil spring 56 is assembled between the closed end of the lock pin aperture in first latch block 40 and the second portion of the lock pin 55, biasing the shoulder of the lock pin 55 against the lower surface of first latch cover 57 and thereby biasing lock pin 55 to the first or lock position. When lock pin 55 is in the lock position, the first portion of lock pin 55 extends beyond first latch cover 57 so that the end of lock pin 55 is planar with the first latch face.
Lock pin arm 52 has a forked first end with two prongs and a band shaped second end. The prongs of the forked first end of lock pin arm 52 fit through an aperture in the rear surface of the first latch block 40 that connects to the lock pin aperture in first latch block 40 and into horizontal slots formed in the second portion of lock pin 57. The band shaped second end of lock pin arm 52 is formed to receive the end a solenoid shaft 51 which is rigidly attached to the second end by a suitable fastener such as a screw. Solenoid shaft 51 is actuated by solenoid 50 which is rigidly attached to the first latch block 40. Actuation of the solenoid 50 pulls shaft 51 down, moving lock pin arm 52 down, pulling lock pin 55 down to a second or unlock position.
Emergency release 53 is cylindrical with an enlarged first end and a threaded second end. The threaded second end of emergency release 53 passes through a vertical slot in the front face of the first latch block 40 that communicates with the lock pin aperture in the first latch block 40 and is screwed into a threaded aperture in the second portion of lock pin 55 perpendicular to the cylindrical axis of lock pin 55. Downward force on the emergency release 53 moves lock pin 55 to the second or unlock position.
Optical sensor 42, flag 46, flag pin 47 and flag pin actuator 64 detect whether the cover 20 is closed. Flag pin 47 has a cylindrical first portion and cylindrical second portion of larger diameter than the first portion, forming a shoulder between the portions. A vertical cylindrical flag pin aperture with a closed first end and an open second end, and with a diameter greater than the second portion of the flag pin 47 is relieved in the top surface of the first latch block 40 to receive a coil spring 48 and flag pin 47. A flag pin hole is formed in first latch cover 57 that allows the smaller first portion of flag pin 47 to extend through first latch cover 57 but retains the second portion of flag pin 47. Coil spring 48 is assembled between the closed end of the flag pin aperture in first latch block 40 and the second portion of the flag pin 47, biasing the shoulder of the flag pin 47 against the first surface of first latch cover 57 and thereby biasing flag pin 47 to an first or nonflag position. The length of the first portion of flag pin 47 is the same as the thickness of first latch cover 57 so that the top surface of flag pin 47 is flush with the top surface of first latch cover 57 when flag pin 47 is in the first or nonflag position.
Flag 46 is generally cylindrical with a first end portion having a rectangular flag cross section and an opposite threaded end portion which passes through a vertical flag slot formed between the flag pin aperture and the rear face of the first latch block 40 and threads into a threaded aperture in flag pin 47 perpendicular to the cylindrical axis of flag pin 47. Depressing flag pin 47 through the flag pin aperture in first latch cover 57 moves flag 46 vertically to a second or flag position.
Optical sensor 42 has a transmitter first pole 44 and a receiver second pole 45, and is mounted with sensor cover 49 in a channel block 43 on the rear face of first latch block 40. Optical sensor 42 is positioned such that the optical path between first pole 44 and second pole 45 is not blocked by flag 46 when flag 46 is in the first or nonflag position and the optical path between first pole 44 and second pole 45 is blocked by flag 46 when flag 46 is in the second or flag position.
Second latch portion 37 includes a second latch block 41 having a longer top, bottom, front and back surface, and shorter right and left surface, a latch plate 39, a release button 59, a tube 60, a spring limit pin 61, a coil spring 62, and a second latch cover 63. FIG. 5 shows an exploded, perspective view of second latch 37 with the top, back and left surfaces of second latch block 41 toward the viewer. Latch plate 39 is U shaped with a center portion and a first and second upright portion, each upright portion having a threaded hole formed therein. A circular latch pin hole 75 of diameter slightly larger than the head of latch pin 38 is formed through the center portion of latch plate 39. A larger diameter circular depression 76 is formed through the upper half of the center portion of latch plate 39, concentric to the latch pin hole 75. The shoulder 78 formed by latch pin hole 75 provides a second latch face 77.
A horizontal cylindrical cavity is formed in the left surface of second latch block 41 to receive the spring limit pin 61, coil spring 62, tube 60, and release button 59. A latch plate channel which communicates with the horizontal cylindrical cavity is formed in the bottom surface of second latch block 41 to receive the latch plate 39, the latch plate channel being wider than the distance between the upright portions of latch plate 39 allowing latch plate 39 side to side movement in the latch plate channel.
Spring limit pin 61 has a larger cylindrical portion sized to fit within the inside diameter of coil spring 62, and a threaded portion which threads into the threaded hole in the first upright portion of latch plate 39 toward the second upright portion of latch plate 39, the threaded portion being longer than the thickness of the first upright portion of latch plate 39 and extending into the space between the first and second upright portions of latch plate 39. Release button 59 has a larger cylindrical portion sized to fit within the horizontal cylindrical cavity formed in second latch block 41, and a threaded portion which threads into the threaded hole in the second upright portion of latch plate 39 toward the first upright portion of latch plate 39, the threaded portion being longer than the thickness of the second upright portion of latch plate 39 and extending into the space between the first and second upright portions of latch plate 39. Tube 60 is the length of the distance between the first and second upright portions of latch 39 and has an inner diameter larger than the threaded portions of spring limit pin 61 and release button 59, so that tube 60 is assembled between the first and second upright portions of latch 39 and held in place by the parts of the threaded portions of spring limit pin 61 and release button 59 that extend into the space between the first and second upright portions of latch plate 39. Coil spring 62 fits around spring limit pin 61 and is assembled into the closed right end of the horizontal cylindrical cavity in second latch block 41, biasing latch plate 39 against the left side of the latch plate channel in second latch block 41. The cylindrical portion of spring limit pin 61 is shorter than the distance from the first upright portion of latch plate 39 to the closed right end of the horizontal cylindrical cavity in second latch block 41, allowing latch plate 39 to move to the right a predetermined distance when the end of the cylindrical portion of release button 59, which projects at least the predetermined distance beyond the left surface of second latch block 41, is pressed.
Second latch cover 63 is rigidly attached to the bottom surface of second latch block 41 and has a latch pin hole of diameter slightly larger than the head of latch pin 38 which aligns with the latch pin hole in latch plate 39 when latch plate 39 is moved to right as far as spring limit pin 61 allows, a lock pin hole of diameter slightly larger than the second portion of lock pin 55, the left edge of the lock pin hole aligning with the right side of the first upright of latch plate 39 when latch plate 39 is biased against the left side of the latch plate channel in the bottom surface of second latch block 41, and a flag pin actuator 64 which is a cylindrical projection of diameter slightly smaller than the flag pin aperture in first latch block 40 that aligns with the flag pin aperture in first latch block 40 when latch 35 is closed.
FIG. 6 shows the operation of latch 35. As cover 20 is closed the conical head 70 of latch pin 38 contacts the right edge of the latch pin hole 75 in latch plate 39. Downward pressure on second latch 37 forces the right edge of the latch pin hole 77 in latch plate 39 along the surface of the head 70 of latch pin 38, compressing coil spring 62 and moving latch plate 39 to the right until the right edge of the latch pin hole 75 in latch plate 39 is even with the periphery of latch pin 38. The right edge of latch plate 39 has moved to the right over the edge of lock pin 55 so that lock pin 55 is pushed down during latching. Second latch 37 moves down until the shoulder 78 on latch plate 39 in aligned with the annular groove 71 in latch pin 38 and the shoulder 78 on latch plate 39 is forced into the annular groove on latch pin 38 by pressure from coil spring 62, the second latch face 77 thereby overlapping first latch face 72 to retain latch 35 in a latched position. When the shoulder 78 in latch plate 39 moves into the annular groove 71 in latch pin 38, the right edge of latch plate 39 clears the top of lock pin 55, allowing lock pin 55 to extend to the lock position with the left side of lock pin 55 against the right side of latch plate 39, preventing movement of latch plate 39. During closure flag pin actuator 64 depresses flag pin 47, moving flag 46 to the flag position.
Solenoid 50 is coupled to the drive motor 28 so that solenoid 50 actuates when drive motor 28 is stopped. Retraction of lock pin 55 to the unlock position by actuation of solenoid 50 allows latch plate 39 to move to the unlatch position. Optical sensor 42 is coupled to drive motor 28 so that drive motor will only run when flag 46 is in the flag position.
Although the present invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made by way of example and that changes in details of structure may be made without departing from the spirit thereof.
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The present invention is a centrifuge bowl housing and cover latch suitable for use in a blood separation system. The housing is mounted on shock absorbers to minimize transmission of vibrations from the centrifuge. The housing is configured to retain spilled liquids, efficiently collect the spilled liquids, drain liquids away from the drive means, and drain liquids out of a drain port to a collection container. The housing has a transparent cover that opens to allow loading of centrifuge bowls into the housing. The cover is a shatter resistant material and when closed, seals the top of the housing, retaining blood components and flying pieces of a centrifuge bowl if the bowl breaks. The cover has a latch that prevents the centrifuge from spinning when the cover is open and prevents opening of the cover when the centrifuge is spinning.
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This application is a continuation of application Ser. No. 821,852, filed Jan. 23, 1986, now abandoned.
FIELD OF THE INVENTION
This invention relates to a shroud for concealing the trap under a lavatory.
BACKGROUND OF THE INVENTION
Shrouds have been used in the past to cover lavatory traps and to give a decorative appearance to lavatories. One familiar type of shroud is a pedestal, which fits underneath the lavatory and extends to the floor. The pedestal usually has a hollow interior into which the trap is inserted, and its weight is supported by the floor on which it stands.
Another type of enclosure which is known is a shroud which fastens to the wall. It is this latter type of wall-supported shroud to which the present invention relates. Prior art shrouds of this type are mounted by means of outwardly projecting flanges having holes for receiving bolts which bolt into the wall. The mechanism for mounting these shrouds is clearly visible, becuase the bolt heads are visible. This disrupts the highly decorative appearance (which is the main reason for having the shroud in the first place). Therefore, there has been a need in the art for a means for hiding the connection to the wall so as to fulfill the decorative purpose of the shroud. However, some solutions for hiding the connection, such as placing it much higher on the shroud so as to be completely hidden by the lavatory, result in designs which are very difficult to install.
SUMMARY OF THE INVENTION
The present invention provides a shroud for a lavatory trap which mounts on the wall of a building such that the mounting means are not readily visible and such that the shroud can be easily installed.
In one embodiment, the shroud has two side walls and a front wall that define a hollow interior which is upwardly open. The shroud also includes upper and lower rearward attachment regions which are substantially hidden by the shroud walls when the shroud is viewed from the front. There is a shroud fastening element (e.g. a flange) in the upper rearward attachment region which cooperates with a securing element (e.g. a clip) which is positionable above the fastening element, usually on the building wall. One of the elements (e.g. the flange) includes an insert portion and the other a receiving portion (e.g. the clip), so that, when the shroud fastening element is slid toward the securing element, the insert portion is slid into the receiving portion so as to restrict the forward movement of the shroud. Another connector (e.g. a bracket) is attachable to the wall of the building and also to the lower rearward attachment region of the shroud so as to support the shroud.
It is an object of this invention to provide a wall-mounted shroud for a lavatory trap in which the mounting means are not readily visible.
It is a further object of the invention to provide a shroud which can be installed easily.
It is a further object of the invention to provide a shroud which requires only a few simple tools for installation and does not require the use of specialized tools.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a shroud made in accordance with the present invention that has been mounted under a lavatory;
FIG. 2 is an exploded perspective view, partially in section, of the shroud of FIG. 1, including the wall and means for mounting the shroud on the wall;
FIG. 3 is a side sectional view, partially broken away, of the lavatory and shroud of FIG. 1;
FIG. 4 is an enlarged, broken away side sectional view of the shroud of FIG. 3, with the bracket positioned in an alternative position;
FIG. 5 is a perspective view, partially broken away, of a second embodiment of a shroud assembly made in accordance with the present invention;
FIG. 6 is an enlarged, broken away side sectional view of the upper portion of the shroud shown in FIG. 5 in an assembled position;
FIG. 7 is a perspective view, partially broken away, of a third embodiment of a shroud assembly made in accordance with the present invention;
FIG. 8 is a side view of the back portion of the shroud of FIG. 7; and
FIG. 9 is a broken away view partially in section of a fourth embodiment of a lavatory and shroud made in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1-3, the shroud 10 fits below the lavatory 12 in order to conceal the water outlet connection 11A and trap 10A. The shroud or shell has a front wall 14, first and second sides (or side walls) 16 and 18, a nose portion 20 at the bottom of the shroud, a top opening 22, and a back opening 24. The interior of the shroud 10 defines an upwardly open hollow interior portion 25.
Adjacent the top opening 22 is a top lip 26 which fits into a groove 28 in the lavatory so that it appears that the shroud 10 is a part of the lavatory 12 when the parts are installed. On the back of the shroud 10 are first and second flanges 30 and 32 (also called shroud fastening elements), which project inward from the first and second sides 16, 18, toward the second and first sides 18, 16, respectively.
The flanges 30, 32 are adjacent the top opening 22 and are flat so as to lie flat against the bathroom wall 11, which acts as a vertical support for the shroud. The region of the flange(s) may also be referred to as the upper rearward attachment region. The nose 20 is spaced forward from the flanges 30, 32 so as to leave a space or gap between the nose 20 and the wall 11 when the shroud 10 is installed. Between the nose 20 and the flanges 30, 32 is a bridge portion 34 which preferably is higher than the lowest part of the nose 20 and is therefore hidden by the nose 20. In the bridge portion 34 is a recessed area 36 which surrounds an aperture 38 for connecting the shroud 10 to the wall 11. This bridge portion 34 may also be referred to as the lower rearward attachment region.
The mounting apparatus of the shroud 10 includes securing elements in the form of first and second resilient clips (spring clips) 40, 42, each of which has an aperture 44 at one end for mounting the clip on the outside of the building wall 11 by means of bolts or screws 45. Below the aperture 44, each clip (40, 42) defines an S-shaped bend, so that the free ends (or the receiving portions) 46 of the clips 40, 42 are directed downwardly, while being spaced from the wall. This provides a tapered lead-in for the respective flange inserts 30, 32. The spring clips 40, 42 are mounted on the wall horizontally spaced from each other.
An L-shaped bracket (or connector) 48 is mounted on the outside of the wall 11 below the spring clips and approximately midway between them. The L-shaped bracket 48 has a first leg 50 and a second leg 52. The first leg 50 has holes for receiving screws or bolts for fastening the connector 48 to the wall 11. The second leg 52, which is approximately perpendicular to the first leg 50, has a single threaded opening 54 which receives a bolt 55 or other type of fastener for securing the shroud 10 to the wall. The L-shaped bracket 48 is designed to support the weight of the shroud.
In order to install the shroud, the lavatory is first installed and fastened to the wall by a method known in the art, with the usual water outlet hook-up llA and connection to the trap 10A. Next, the spring clips 40, 42 and bracket 48 are mounted on the wall. Then, the shroud 10 is slid upward along the wall, with the trap and water outlet connection entering into the shroud through the top and back openings, 22, 24.
As the shroud 10 is moved upward, the first and second flanges 30, 32 reach the free ends 46 of their respective spring clips 40, 42, and the shroud 10 continues to be moved upward until the first and second flanges 30, 32 are pressed against the wall by the bends 47 of the first and second spring clips 40, 42, respectively. Then, the aperture 38 in the shroud is aligned with the opening 54 in the L-shaped bracket 48, and a bolt 55 is extended through the aperture 38 and is fastened into the bracket 48 in order to support the shroud 10. In the present embodiment, the opening 54 is threaded and a bolt is used. However, other types of retainers are known in the art and could alternatively be used.
It will be noted that the only part of the mounting apparatus which extends outside of the shroud 10 below the lavatory is the head of the bolt 55. Since the bolt head is recessed in the recess 36 and is behind the nose portion 20, the bolt 55 is also hidden from view. Therefore, the means for mounting the shroud 10 are not readily visible after installation. Further, the installation of the clips can be made prior to that of the lavatory to make installation even easier.
Other embodiments of the invention are described herein. The parts of the alternative embodiments are numbered in analogous fashion to correspond to similar parts of the first embodiment.
FIG. 4 shows that the bracket 48 can be mounted so that the second leg 52 is outside the shroud 10, but is still hidden from view by the nose 20. The upper portion of the shroud 10 of FIG. 4 is retained in the same manner as in FIGS. 2 and 3. To reach the position shown, the shroud would have to be tipped as it is slid up into the clips so the bracket can be passed by bridge wall 99.
FIGS. 5 and 6 show a third alternative embodiment, in which there is a single flange 130, which extends from the first side 116 toward the second side 118, and is, in fact, connected to the second side 118. This flange 130 is retained by a single central ledge 140, which is not resilient. Instead, the ledge 140 has its free end 146 rigidly directed downward and spaced from the wall 111. The free end 146 has a wedge shape to provide a tapered lead-in 147, to help the installer insert the flange under the free end (or receiving portion) 146. The lower portion of this embodiment is retained in the same manner as in FIGS. 2 and 3, by means of the bracket 148 and bolt 155. Again, some tipping of the shroud is required during installation so the wall 130 can get past the bracket 148.
FIGS. 7 and 8 show another alternative embodiment, in which the shroud 210 includes a channel 213 adjacent the flanges 230, 232. The channel 213 provides a recess or bridge portion 34 in its lower rearward region for hiding the bolt 255 which extends laterally into the L-shaped bracket 248 for supporting the shroud 210. The clips 240 and 242 receive the flanges 230, 232 as in FIGS. 2 and 3, with the only difference being that the flanges 240, 242 are U-shaped, causing their back surfaces to be spaced further from the sides 216, 218.
FIG. 9 shows another alternative embodiment, in which, instead of retaining the upper portion of the shroud 310 by a clip which is attached directly to the wall, the upper portion is retained by a pair of pins or securing elements 330 (only one is shown), which project downward from the lavatory 312 (the lavatory, of course, being attached to the wall 311 by suitable means). The shroud 310 has a pair of receptacles or receiving portions 390 which receive their respective inserts or projections 330, when the shroud is slid upward along the wall 311. The lower portion of the shroud 310 is retained as shown in FIGS. 2 and 3.
It will be obvious to those skilled in the art that modifications could be made to the embodiments described above without departing from the scope of the present invention.
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A shroud apparatus which mounts under a wall-mounted lavatory to enclose the trap of a lavatory is disclosed. The shroud has upper and lower rearward attachment regions which are hidden by the walls of the shroud when the shroud is viewed from the front. The shroud defines a hollow interior portion which is upwardly open to receive the trap. It also includes a shroud fastening element in its upper rearward attachment region and a securing element that cooperates with said shroud fastening element so as to restrict the forward movement of the shroud. A connector is attachable to the bathroom wall and to the lower rearward attachment region of the shroud.
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STATEMENT OF GOVERNMENT INTEREST
The invention described was made in the performance of official duties by one or more employees of the Department of the Navy, and thus, the invention herein may be manufactured, used or licensed by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.
BACKGROUND
The invention relates generally to maritime cable cutting under emergency conditions. In particular, the invention relates to a mechanism to expeditiously and reliably sever a heavy-duty cable used between ships for supply operations.
Naval ship replenishment at sea, also known as an undersea replenishment (UNREP) operation, involves rendezvous of approach and control ships on parallel courses, followed by connection of ships by a span cable. For liquid supplies, e.g., fuel, the delivering ship extends a hose along the cable to the receiving ship for connection to the appropriate receptacle. Other supplies, such as weapon stores can also be exchanged via cable suspension.
FIG. 1 shows an elevation view 100 of a conventional rigging configuration for UNREP between a delivering ship 110 and a receiving ship 120 for refueling operation. Structures and supports on the delivering ship include a wire topping pendant 125 , a wire saddle whip 130 , and an anti-toppling device 135 . A span wire or cable 140 supports an inboard saddle 145 , operating in conjunction with mezzanine and outboard saddles 150 and 155 . The span wire 140 is typically 1⅜ inches (″) thick and comprises braided steel cable resistant to spontaneous breakage. The saddles 145 , 150 and 155 elevate a supply hose 160 accompanied by a stress wire 165 . After refueling completion a retrieving line returns the outboard saddle 155 to the delivering ship 110 . A supply outlet 180 delivers fuel through the hose 160 supported by a receiving structure 190 on the delivery ship 120 and connected to its receiver inlet 195 .
FIG. 2 shows an elevation view 200 of a conventional rigging configuration for weapons transfer between the delivering and receiving ships 110 and 120 to transfer a load 220 along a travel direction 225 . The delivering ship 110 includes a ram tensioner 230 , a high line winch 235 , and out-haul winch 240 , an in-haul winch 245 and a transfer head 250 , which holds a tensioned highline 255 , a tensioned in-haul line 260 , and a tensioned out-haul line 265 . The highline 255 and in-haul line 260 enable a trolley 270 to transfer the load 220 . The delivering ship 110 also includes a kingpost 275 to elevate the transfer head 250 . The receiving ship 120 includes a padeye 280 with an out-haul fairlead 285 to support the lines 255 , 260 and 265 .
In the event of an emergency replenishment termination, the cable is severed manually. This process is described in section 2.2.11 of “Underway Replenishment” especially pp. 2-11 through 2-15, issued as NWP 4-01.4 under the Chief of Naval Operations and available at http://www.hnsa.org/doc/pdf/unrepnwp04-01.pdf. FIG. 3 shows a perspective view 300 of the inboard ship 110 with its span wire 140 . A manual cable cutter 310 is positioned on the span wire 140 by an assigned operator 320 to sever the cable when authorized during an emergency and abort the inter-ship delivery operations.
SUMMARY
Conventional emergency severance devices for marine cables yield disadvantages addressed by various exemplary embodiments of the present invention. In particular, various exemplary embodiments provide a marine cable cutter for wirelessly severing wire responsive to an electromagnetic command signal. The cutter includes an explosive package for wrapping around the wire, and a clamshell case for containing the package around the wire.
In exemplary embodiments, the package includes a wireless receiver to receive the command signal, an electric pulse generator triggered by the receiver, an explosive initiated by the generator, and a platform for containing the receiver, generator and explosive. In further exemplary embodiments, the clamshell case includes a pair of envelopes connected along mutual first edges by a hinge and mutual second edges by respective clamps. The envelopes pivot on the hinge to open and receive the package with disposal of the wire therein, and subsequently to close and secure by the clamps. The envelopes can be composed of sheet metal with the clamps being flanges with aligned holes for receiving bolt fasteners.
BRIEF DESCRIPTION OF THE DRAWINGS
These and various other features and aspects of various exemplary embodiments will be readily understood with reference to the following detailed description taken in conjunction with the accompanying drawings, in which like or similar numbers are used throughout, and in which:
FIG. 1 is an elevation view of a first conventional UNREP configuration;
FIG. 2 is an elevation view of a second conventional UNREP configuration;
FIG. 3 is a perspective view of a conventional cable severing process;
FIG. 4A is a plan view of an exemplary wireless explosive package;
FIG. 4B is a perspective view of the wireless explosive package;
FIG. 5 is a diagramic view of an electronics control for the package;
FIG. 6 is an isometric view of a cable case for the package;
FIG. 7 is a plan view of a metal sheet for constructing the case;
FIGS. 8A and 8B are elevation views of the metal sheet after shaping;
FIG. 9 is an elevation view of a sheet metal edge flange; and
FIG. 10 is an elevation view of an exemplary installation operation.
DETAILED DESCRIPTION
In the following detailed description of exemplary embodiments of the invention, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific exemplary embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized, and logical, mechanical, and other changes may be made without departing from the spirit or scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims.
In accordance with a presently preferred embodiment of the present invention, the components, process steps, and/or data structures may be implemented using various types of operating systems, computing platforms, computer programs, and/or general purpose machines. In addition, those of ordinary skill in the art will readily recognize that devices of a less general purpose nature, such as hardwired devices, or the like, may also be used without departing from the scope and spirit of the inventive concepts disclosed herewith. General purpose machines include devices that execute instruction code. A hardwired device may constitute an application specific integrated circuit (ASIC) or a field programmable gate array (FPGA) or other related component.
FIG. 4A shows a plan view 400 of a wireless explosive package for an exemplary emergency cable cutter. A foam rubber block 410 provides a substrate structure for the package, into which cavities can be excised to disposal therein. Within the block 410 can be included a wireless trigger switch 420 connected by first electric wires 425 to a power oscillator 430 and second electric wires 435 to a battery 440 . The power oscillator 430 boosts voltage from the battery 440 and connects a third electric wires 445 to provides a high voltage pulse to a pair of blasting caps 450 on opposite sides of the block 410 . The block 410 is preferably flexible, such as comprising foam rubber.
Upon initiation, the caps 450 explode with the resulting shock transmitted via corresponding blast igniters 455 to respective linear shaped charges 460 that direct their explosive forces to the span wire 140 for severance on command from a wirelessly transmitted signal. Example charges 460 can be commercially available Semtex® RAZOR flexible explosives. FIG. 4B shows a perspective view 470 of the exemplary package 480 showing the configuration of the shaped charges 460 as a right angle to direct their blasts upward relative to the block 410 orientation.
FIG. 5 shows a circuit diagram view 500 of an exemplary power oscillator 430 . The electronics form resembles a stun gun for purposes of producing a high voltage pulse. A “555” timer integrated circuit 510 provides a switchable control with pins 1 (ground), 2 (trigger), 3 (output), 4 (reset), 5 (control voltage), 6 (threshold comparator), 7 (discharge) and 8 (voltage supply). Pins 2 and 7 connect to the switch 420 , and pins 1 and 8 connect respectively to the negative and positive terminals of the battery 440 , with a switch diode 520 interposing between pin 8 and the battery 440 .
The timer circuit 510 also connects to capacitors 530 and 535 , and to resistors 540 , 545 and 550 . Output pin 3 connects via the resistor 545 to an NPN transistor 560 in parallel with a rectifier diode 570 , which together with the battery 440 connect to input terminals of a voltage transformer 580 . The output terminals of the transformer 580 provide the high voltage pulse to the caps 445 .
Preferably, the switch diode 520 can, for example, be either 1N914 or 1N4148. The capacitor 530 is 0.1 μF or 0.47 μF, while the capacitor 535 is 0.01 μF. The resistors 540 and 545 are 1 kΩ each; the resistor 550 is 47Ω. The transistor is a TIP31 bipolar junction transistor with current flowing from collector (C) to emitter (E) when base (B) has higher voltage than emitter (E). The transformer 580 constitutes a miniature audio transformer receives input voltage from the battery 440 on the 1 kct (one-thousand loop) center-tap left side and supplies output voltage to the caps 445 from the 200 k (0.2 million loop) right side.
FIG. 6 shows an isometric view 600 of a clamshell housing case 610 for containing the package 480 around the span wire 140 . The case 610 can be substantially composed from sheet metal and includes radial semicircular frames to form an annular shell. The frames include lower and upper portions 620 and 625 , conformably capped at the proximal end by respective fore plates 630 and 635 , and at the distal end by respective aft plates 640 and 645 .
The portions 620 and 625 pivot along a laterally disposed axis along a common hinge 650 secured by a rod 655 . The portions 620 and 625 also join together laterally opposite the hinge 650 by respective flanges 660 and 665 that face each other. Each flange 660 and 665 has aligning through-holes 670 that to receive appropriate fasteners when they face each other along a common flat joint interface 680 . The housing 610 encloses an interior 690 in which the package 480 can wrap around the span wire 140 .
FIG. 7 shows a plan view 700 of a flat metal rectangular sheet 710 preferably having an overall length of 20½″ and width of 7″ for constructing the upper and lower portions 620 and 625 . The sheet 710 is cut along lines 725 to divide into left and right sections 730 and 740 , each having lengths of on the 10¼″ and 8.85″ on opposite sides with a transitional middle section edge of 1.40″. These sections 730 and 740 are designed to be identical and interchangeable for composing the portions 620 and 625 . At the longitudinal edges, through-holes 750 are drilled and the ends are folded along line 760 for an edge length of 1″.
FIGS. 8A and 8B show elevation views of one of the metal sheet sections 730 and 740 further modified to form the portions 620 and 625 . FIG. 8A illustrates an elevation view 800 of the modified section with a ledge 810 that forms one of the flanges 660 and 665 . A semi-circular arc 820 joins the ledge 810 at a corner 830 formed along line 760 . The arc 820 has a radius of 2½″ and extends tangent as an extension 840 opposite the ledge 810 . FIG. 8B illustrates another elevation view 850 of the modified section with the extension 840 curled to form a tight arc 860 that forms part of the hinge 650 . Two such modified sections can be joined together and joined by the rod 655 .
FIG. 9 shows a plan view 900 of a sheet metal plate 910 that forms any of the end plates 630 , 635 , 640 and 645 . The plate 910 has an outer diameter of 5″ and an inner diameter of 1⅜″ for the span wire 140 to be contained along the length of the case 610 . The outer diameter conforms to the arc 820 to provide closure between the portion 620 or 625 and the span wire 140 .
FIG. 10 shows elevation views 1000 of the wireless cable cutter components and their assembly together with the span wire 140 (shown in cross-section). In first elevation view 1010 , the upper portion 625 pivots 1020 along the hinge 650 relative to the lower portion 620 to open the case 610 . While maintaining the shaped charge 460 straight, the package 480 can be curled for insertion 1030 into the interior of the case 610 . In second elevation view 1040 , the span wire 140 is disposed for insertion 1050 between the longitudinal sides of the package 480 .
In third elevation view 1060 , the upper portion pivots 1070 on the hinge 650 to close the case 610 and bolt fasteners 1080 insert into the aligned through-holes 660 of the flanges 660 and 665 facing each other. The flanges 660 and 665 with the fasteners 1080 constitute clamps for securing the case 610 upon closure, and alternative configurations can be contemplated without departing from the inventive scope. The completed and installed assembly can operate to sever the span wire 140 on command. Upon receiving an electromagnetic commanding signal from a ship-board transmitter, the trigger switch 420 can initiate a pulse from the oscillator 430 for discharging the caps 450 to detonate their charges 460 .
The afore-described embodiments provide a mechanism to safely and reliably cut heavy braided steel span wires 140 , in the event of an emergency during heavy underway replenishment operations. The objective is to fabricate an emergency-use explosive cable cutter (as in view 1060 ), which is safe, reliable, and can meet safety certifications necessary for shipboard use. Flexible linear shaped charges 460 represent an exemplary reliable method for cutting the braided steel span wire 140 (typically 1⅜″ in diameter). Shipboard applications would enable minimization of fragmentation and blast effects from any explosive cable cutting system—while still ensuring effective use.
The exemplary embodiments provide a two-part modular assembly: first a heavy blast-resistant clamshell case 610 , designed to easily clamp around and fasten onto the braided steel cable; and second, a flexible conformal cutting charge package 480 , which readily inserts into the case 610 . This package 480 contains the secure wireless remote detonation switch 420 , a voltage multiplier-charge capacitor pulse generator 430 , a long-life battery 440 , two strips of flexible linear shaped charge 460 with industry-standard igniters 455 and blasting caps 450 . In the event of an emergency, such as the fouling of cables interconnecting two ships 110 and 120 during UNREP in heavy seas, the UNREP supervisor could press a button to remotely trigger the explosive cable cutting device, and sever the fouled span wire 140 or other similar cable.
Within the United States joint and international military community, such a device would have general applicability to combat engineering brigades, and potentially for purpose applications faced by special operations forces. Building demolition companies could employ such a device for dismantling bridges, and other structures with steel reinforcement bar of significant dimensions.
Conventional explosive cable cutters are not approved for shipboard operation due to blast and fragmentation considerations. Mechanical cutting systems, e.g., electric drive or hydraulic drive, are relatively slow and require unacceptably many seconds (or minutes) to sever a heavy braided steel cable. Further, these systems require support systems such as electricity, wiring, hydraulics, and hydraulic lines. Reliability and maintenance of these electrical and hydraulic systems over the long-haul are perceived to be cost prohibitive, as well as creating additional ship modifications. The described exemplary designs provide an effective alternative for such emergency cable severing operations.
While certain features of the embodiments of the invention have been illustrated as described herein, many modifications, substitutions, changes and equivalents will now occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the embodiments.
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A marine cable cutter is provided for wirelessly severing wire responsive to an electromagnetic command signal. The cutter includes an explosive package for wrapping around the wire, and a clamshell case for containing the package around the wire. The package includes a wireless receiver to receive the command signal, an electric pulse generator triggered by the receiver, an explosive initiated by the generator, and a platform for containing the receiver, generator and explosive. The clamshell case includes a pair of envelopes connected along mutual first edges by a hinge and mutual second edges by respective clamps. The envelopes pivot on the hinge to open and receive the package with disposal of the wire therein, and subsequently to close and secure by the clamps. The envelopes can be composed of sheet metal with the clamps being flanges with aligned holes for receiving bolt fasteners.
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REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional application of a pending prior application Ser. No., 09/939,336 filed on Aug. 24, 2001, which in term was based on a provisional application filed on Aug. 25, 2000, Ser., No., 60/228,318.
TECHNICAL FIELD OF THE INVENTION
[0002] This invention concerns a specialty bag construction and method of manufacturing the same. In particular, the bag wall has a number of venting bands for the proper venting of certain stored perishable items.
BACKGROUND OF THE INVENTION
[0003] Bulk bags are commonly used to store and transport many agricultural products. Many such products, especially those easily perishable ones, require the bag to be properly vented to prevent the build up of excessive moisture with ensuing growth of mold and deterioration of the content. Furthermore, these bags are usually non-reusable due to sanitation concern. Thus, these ventable bags need to be produced in high volume, having a specifiable degree of venting yet with very low cost. One common way to achieve this is to weave in a set of venting bands of specified width and density with a flat loom. However, the associated post operation involves, after cutting the panel to size, folding and sewing of two lines to form the bag. Additionally, the flat loom machine is quite an expensive investment. Thus, the overall production cost of the bag can be undesirably high.
SUMMARY OF THE INVENTION
[0004] The present invention consists of a method which inexpensively and efficiently manufactures such ventable bags in high volume with a specifiable range of design of venting bands. Thus, the bag itself is also encompassed by the present invention.
[0005] The bag is a traditional one having a cylindrical body panel with one end of the panel sown closed to form the storage cavity. The other end of the cylindrical body panel is left open for communication with the interior of the bag. However, the cylindrical body panel of the bag comprises a specified number and location of venting bands along the direction of the cylindrical axis. Furthermore, the width of the said venting bands is also specifiable by design.
[0006] The method of manufacturing the bag starts with the tubular weaving of yams of proper materials with a circular loom whereby an elongated tubular structure is formed with woven warp and weft strands. The direction of the warp strands is parallel to the tubular axis whereas the direction of the weft strands is perpendicular to the tubular axis.
[0007] However, around the periphery of a concentration ring of said circular loom a number of mechanical expansion blocks are disposed at the proper location replacing the otherwise warp strands to be fed thus woven into said cylindrical body panel of the bag. For convenience, these locations are to be called band locations. As there is an absence of warp strands at each such band location, the resulting woven wall structure of the said band consists of only weft strands. Without the interlocking power from the missing warp strands, the flexing weft strands within said band create substantially larger air gaps in between than otherwise possible with the presence of interlocking warp strands. These air gaps within said bands thus form the desired venting structure for the bag. Therefore, emerging from said circular loom with the adaptation of the invention embodiment is a woven tubular structure wherein a number of venting bands parallel to the tubular axis are built in wherever said invention embodiment is disposed along the circumferential periphery of the tube. It is also important to remark that, as part of the function of the circular loom, said emerging woven tubular structure is actually flattened into a continuous belt form and wound into a roll for easiness of subsequent handling.
[0008] The tubular structure is sectioned off along a set of lines with predetermined spacing to form a set of tubular segments, each tubular segment having the desired set of venting bands extending axially from a first open end to a second open end. For convenience, the first open end of the said tubular structure is to be called the top opening and the second open end of the said tubular structure is to be called the bottom opening.
[0009] The bottom opening of the said tubular structure is now sewn closed along the direction perpendicular to the tubular axis. The top opening of the said tubular structure is left open forming the desired bag opening.
[0010] Thus, a storage bag having a cylindrical body panel is described wherein a desired set of venting bands extending axially is built in on the body panel. Additionally, an inexpensive and efficient method is described herein for the manufacturing of such ventable bags in high volume. Furthermore, said method of manufacturing embodies the adaptation of a set of simple mechanical elements onto an existing circular loom.
[0011] Other features, objects and advantages of the present invention will become apparent with reference to the following drawings and associated descriptions.
BRIEF DESCRIPTION OF DRAWINGS
[0012] [0012]FIG. 1 is a perspective view of a portion of the weaving mechanism inside a circular loom wherein one mechanical expansion block of the present invention is disposed to replace an otherwise corresponding group of warp yams feeding the weaving mechanism;
[0013] [0013]FIG. 2 illustrates a section of a woven tubular structure coming out of an unmodified circular loom wherein the woven warp and weft strands are partially shown to illustrate their orientation;
[0014] [0014]FIG. 3 illustrates a section of a woven tubular structure coming out of a circular loom modified with the present invention wherein a set of six venting bands made with the present invention is also illustrated;
[0015] [0015]FIG. 4 is a perspective illustration of a small section of the detailed woven structure including the corresponding section of a venting band made with the present invention;
[0016] [0016]FIG. 5 illustrates a prior art finished bag made from a section of a woven tubular structure coming out of an unmodified circular loom, after the bottom opening of the sectioned tubular structure is sewn closed; and
[0017] [0017]FIG. 6 illustrates a finished bag made from a section of a woven tubular structure coming out of a circular loom modified with the present invention, after the bottom opening of the sectioned tubular structure is sewn closed.
DETAILED DESCRIPTION OF THE INVENTION
[0018] [0018]FIG. 5 illustrates a typical prior art bulk bag made with a circular loom. The cylindrical body panel 10 comprises many tightly interlocking strands of woven warp 2 A and woven weft 3 A woven by a well-known circular loom machine. The material for the warp and weft strands can be any of the many materials compatible with the circular loom. Some examples are polyethylene, polypropylene and nylon. It is important to remark that, as part of the function of the circular loom, the said emerging woven cylindrical body panel 10 is actually flattened into a continuous belt form and wound into a roll for easiness of subsequent handling. The bottom opening of the cylindrical body panel 10 is sewn closed to form a sewn bottom edge 12 . The top opening 11 comes naturally out of the sectioning operation of the tubular body structure into bag segments.
[0019] Although many such bulk bags are commonly used to store and transport a wide variety of products and materials, many such products, especially those easily perishable ones, require the bag to be adequately vented to the ambient to prevent the build up of excessive moisture with ensuing growth of mold and deterioration of the content. Some examples are potatoes and vegetables. For such products, the tightly interlocking strands of woven warp 2 A and woven weft 3 A of the prior art bulk bag does not allow adequate degree of venting to the ambient and means of controllably increasing the degree of venting must be devised to solve the problem.
[0020] [0020]FIG. 6 illustrates a bulk bag from the present invention whereby the desired degree of increase of venting is accomplished. As stated above, the cylindrical body panel 10 comprises many tightly interlocking strands of woven warp 2 A and woven weft 3 A. The bottom opening of the cylindrical body panel 10 is sewn closed to form a sewn bottom edge 12 . The top opening 11 comes out of the sectioning operation of the tubular body structure into bag segments. However, around the periphery of the cylindrical body panel 10 a set of venting bands 9 is disposed. Within each venting band 9 , instead of having both warp and weft strands, only woven weft in venting band 3 B exists. Without the interlocking power from the missing woven warp 2 A, the flexing woven wefts in venting band 3 B within the said venting band 9 now create substantially larger air gaps in between than otherwise possible with the presence of interlocking woven warp 2 A. These air gaps within said venting band 9 thus form the desired venting structure for the bag of the present invention. The method by which these venting bands 9 on the cylindrical body panel 10 are manufactured is described below.
[0021] The method of manufacturing the bag starts with the tubular weaving of yams of warp and weft materials with a well-known circular loom whereby an elongated tubular structure is formed with woven warp and weft strands. FIG. 1 is a perspective view of a portion of the weaving mechanism inside a circular loom wherein a full circle of radially converging warp strands 2 are interlockingly woven with another set of circumferentially directed weft strands 3 . For easiness of viewing, neither the full set of warp and weft strands nor the circular-weaving heads are shown. After passing through the underside of a concentration ring 1 , the just woven cylindrical web turns vertical in direction, forming a cylindrical body panel 10 and continues to be pulled upwards toward an ultimate take up roller which is not shown here. The direction of the woven warp 2 A is parallel to the tubular axis whereas the direction of the woven weft 3 A is perpendicular to the tubular axis.
[0022] Around the periphery of the concentration ring 1 of said circular loom a number of expansion blocks 7 are disposed at the proper location replacing the otherwise converging warp strands 2 to be fed thus woven into said cylindrical body panel 10 of the bag. For convenience, these locations are to be called band locations. For simplicity, only one expansion block 7 is shown. The expansion block 7 , through a cylindrical link 6 , is attached to a flexible belt 4 whose outer end is fixed at a convenient tie point 5 on the frame of the circular loom.
[0023] The absence of woven warp 2 A at each such band location results in the presence of only woven weft 3 B in said venting band 9 . Without the adaptation of the present invention, as illustrated in FIG. 2, a totally symmetric cylindrical structure would be formed wherein the whole cylindrical wall comprises tightly interwoven warp 2 A and woven weft 3 A. Whereas with the present invention, as shown in FIG. 3, a woven tubular structure wherein a number of venting bands 9 parallel to the tubular axis are produced wherever the invention embodiment is disposed along the circumferential periphery of the tube.
[0024] Additionally, with reference to FIG. 1, the width of the expansion block 7 is intentionally oversized with respect to the replaced width of the missing warp strands 2 . Thus, during the weaving operation, a controlled amount of lateral squeezing force is produced which causes a closer packing of the woven warp 2 A along the edge of the venting band 9 . This is illustrated in FIG. 4 which shows a perspective view of a small section of the detailed woven structure including the corresponding section of a venting band 9 made with the present invention. Along the two edges of the venting band 9 are formed two squeeze zones 8 wherein both the woven warps in left squeeze zone 2 A 1 and the woven warps in right squeeze zone 2 A 2 are packed with a pitch tighter than elsewhere on the woven web.
[0025] It should be understood that, with the present invention, the amount of venting for the bulk bag can be flexibly controlled with the proper combination of the selection of number, location and size of the expansion block 7 . The invention is applicable, in particularly, to the storage and transportation of potatoes where a proper degree of venting is needed to prevent the growth of mold thus causing deterioration of the potato while avoiding excessive sun exposure which also causes another type of deterioration.
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A specialty bag is formed from a circular loom adapted with a unique mechanism of the current invention such that the resulting woven tubular sheet contains at least one venting band extending along the length of the tubular sheet. The tubular sheet is then cut into individual bag segments. The individual bag segments are sewn together along their bottom edge to form the final bag having at least one venting band for the proper venting of the enclosed items.
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FIELD OF THE INVENTION
This invention relates to the use of special one-component polyurethanes for coating textile sheets by the reversal process. In the process according to the invention, segmented, substantially linear polyurethanes obtained from dihydroxy polyesters and/or dihydroxy polyethers, aromatic and/or aliphatic diisocyanates and a mixture of at least one glycol and at least one monoalkanolamine as chain lengthening agent are applied from solution to form a bonding coat and/or top coat. These polyurethanes not only have exceptionally advantageous properties as solutions but also give rise to coatings which have a high resistance to distortion under heat and pressure and can therefore be ironed at high temperatures.
BACKGROUND OF THE INVENTION
It is already known in the art to coat textiles such as woven or knitted fabrics and non-woven bonded webs with solutions of polyurethanes by the direct or the reversal process. The articles obtained are used for the manufacture of outer-wear garments, upholstery goods, luggage, shoe uppers, tents and tarpaulins, blinds and many other products.
In contrast to the two-component polyurethanes, which have been known for some time, the so-called one-component polyurethanes have been more recently introduced into the art. These products are obtained by the reaction of polyhydroxyl compounds, in practice mainly dihydroxy polyesters or dihydroxy polyethers, in combination with glycols, preferably butane diol-(1,4), and aromatic diisocyanates, preferably 4,4'-diphenylmethane diisocyanate as described in German Patent Specification No. 1,106,959 and German Auslegeschrift No. 1,112,291. Solutions of one component polyurethanes have a practically unlimited pot life. Formation of films from these polyurethanes is a purely physical process which, in contrast to the formation of films from two-component polyurethanes, is not accompanied by any chemical cross-linking reaction.
In contrast to chemical cross-linking, physical cross-linking is reversible, which means that one-component polyurethanes are thermoplastically deformable. This inevitably renders textile coats containing one-component polyurethanes to some extent sensitive to deformation by pressure at elevated temperatures. One consequence of this is that, in certain fields of application, for example in the manufacture of shoe uppers, these materials are insufficiently able to withstand ironing because the coating undergoes thermal deformation by pressure even below its melting range and irreversibly penetrates the fabric ("penetration by ironing" of the fabric structure).
An improvement in the resistance to ironing can generally be obtained by elevating the temperature range at which the polyurethane melts. The usual methods employed for elevating the polyurethane melting range are based, for example, on increasing the proportion of hard segments by using a higher molar proportion of chain-lengthening agents, by incorporating short, compact hard segments by using short chain glycols, preferably ethylene glcyol, as chain-lengthening agent, or by incorporating high melting aromatic hard segments, for example by using 1,4-phenylene-bis-(β-hydroxyethyl ether) as chain-lengthening agent. Unfortunately, this known method of elevating the polyurethane melting range invariably reduces the solubility of the polyurethanes in the usual commercial solvent combinations so that the resulting solutions are more or less viscous and in many cases even tend to be pasty and are difficult or even impossible to process in the usual coating installations.
It is known from German Auslegeschrift No. 2,161,340 and German Offenlegungsschrift No. 2,402,799 which corresponds to U.S. Ser. No. 542,734, filed Jan. 20, 1975 to Thoma et al. that the solubility of one-component polyurethanes can be improved by using an equimolar mixture of at least two different glycols instead of a single glycol as chain-lengthening agent. Unfortunately, however, the use of such mixtures of chain-lengthening agents significantly lowers the polyurethane melting range so that the dimensional stability at elevated temperatures and hence the resistance to ironing of the polyurethane coatings are again reduced.
SUMMARY OF THE INVENTION
It has now surprisingly been found that one-component polyurethanes which are readily soluble in the usual solvents to form solutions which are stable in storage and which have excellent resistance to distortion under pressure at elevated temperatures can be obtained by using a mixture of at least one glycol or a low molecular weight diol and at least one monoalkanolamine as chain-lengthening agent.
The present invention relates to a method of coating textile sheets by the reversal process with polyurethanes which have improved resistance to thermal pressure distortion and form solutions which are stable in storage, according to which the solution of a polyurethane which is substantially free from reactive end groups is applied as top coat to a separating substrate in a first stage of the process, the top coat is dried, an adhesive solution is applied to the top coat in a second stage of the process, the textile sheet is laminated thereto, the solvent in the adhesive coat is evaporated off in a second drying operation and the coated textile is then stripped from the separating substrate, characterized in that the substances used as top coat and/or adhesive coat are polyurethanes which have been obtained by the reaction of
(a) at least one dihydroxyl compound having a molecular weight of between about 500 and 5000,
(b) at least one diisocyanate, and
(c) a mixture of about 95-35 mol % of at least one diol having a molecular weight of about 62 to 450 and about 5-65 mol % of at least one monoalkanolamine having a molecular weight of from about 61 to approximately 200, the molar ratio of compounds (a) and (c) being between about 1:1 and 1:6.
The polyurethanes may be prepared solvent-free or in solution by known methods, either by the one shot process or by way of a prepolymer.
DETAILED DESCRIPTION OF THE INVENTION
Particularly suitable dihydroxyl compounds with a molecular weight of from about 500 to 5000, preferably about 800 to 2500 are dihydroxy polyesters and/or dihydroxy polyethers.
The dihydroxy polyesters are obtained in known manner from one or more dicarboxylic acids preferably having at least six carbon atoms and one more dihydric alcohols.
Instead of free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof may be used for preparing the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and they may be substituted, e.g. by halogen atoms, and/or unsaturated. The following are examples: succinic acid; pimelic acid; adipic acid; suberic acid; azeleic acid; sebacic acid; phthalic acid; isophthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrophthalic acid anhydride; hexahydrophthalic acid anhydride; tetrachlorophthalic acid anhydride; endomethylene tetrahydrophthalic acid anhydride; glutaric acid anhydride; maleic acid; maleic acid anhydride, fumaric acid; dimeric and trimeric fatty acids such as maleic acid which may be mixed with monomeric fatty acids; dimethyl terephthalate and terephthalic acid-bis-glycol esters. Aliphatic dicarboxylic acids are preferred and adipic acid is particularly preferred. Suitable dihydric alcohols include e.g. ethylene glycol; propylene glycol-(1,2) and -(1,3); butylene glycol-(1,4) and -(2,3); hexane diol-(1,6); octane diol-(1,8); neopentylglycol; 1,4-bis-hydroxymethylcyclohexane; 2-methyl-1,3-propane diol; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycols; dipropylene glycol; polypropylene glycols; dibutylene glycol and polybutylene glycols. Polyesters of lactones such as ε-caprolactone or of hydroxy carboxylic acids such as ε-hydroxycaproic acid may also be used.
Apart from these polyesters, hydroxy polycarbonates are also suitable for preparing the polyurethanes used according to the invention, particularly the hydroxy polycarbonates obtained from hexane diol-(1,6) and diarylcarbonates and the esterification products of straight chain hydroxy alkane monocarboxylic acids having at least 5 carbon atoms or the corresponding lactone polymers or polymer diols such as polybutadiene diol.
Polyethers with two hydroxyl groups which may be used according to the invention are also known per se and may be prepared, for example by the polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, either each on its own, for example in the presence of boron trifluoride or by chemical addition of these epoxides, either as mixtures or successively, to starting components which contain reactive hydrogen atoms, such as alcohols or amines, e.g. water, ethylene glycol, propylene glycol-(1,2) or -(1,3), 4,4'-dihydroxydiphenyl propane, aniline, ethanolamine or ethylene diamine.
Dihydroxybutylene glycol polyethers and dihydroxy propylene glycol polyethers are particularly preferred.
Starting components to be used according to the invention also include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75-136, for example ethylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers; 1-methyl-2,6-diisocyanato cyclohexane; 1-methyl-2,4-diisocyanato cyclohexane; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane per hydro-2,4'- and/or -4,4'-diphenylmethane-diisocyanate; phenylene-1,3- and -1,4- diisocyanate and any mixtures of these isomers; tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and/or 4,4'-diisocyanate; naphthylene-1,5-diisocyanate; 4,4'-diphenyl-dimethyl methane diisocyanate and any mixtures of these compounds. 4,4'-diphenylmethane diisocyanate is particularly suitable.
The low molecular weight diol components with a molecular weight of from about 62 to 450 are used as chain-lengthening agent components for the preparation of the polyurethanes used according to the invention. Various types of diol components may be used according to the invention, for example
(a) alkane diols such as ethylene glycol; propylene glycol-(1,3) and -(1,2); butane diol-(1,4); pentane diol-(1,5); dimethylpropane diol-(1,3) and hexanediol-(1,6);
(b) ether diols such as diethyleneglycol; triethylene glycol or 1,4-phenylene-bis-(β-hydroxyethyl ether);
(c) amino diols such as N-methyl-diethanolamine or N-methyl-dipropanolamine;
(d) ester diols of the general formulae
HO--(CH.sub.2).sub.y --CO--O--(CH.sub.2).sub.x --OH
and
HO--(CH.sub.2).sub.x --O--CO--R--CO--O--(CH.sub.2).sub.x --OH
in which
R represents an alkylene or arylene group having from 1 to 10, preferably 2 to 6 carbon atoms,
x=2-6 and
y=3-5
e.g. δ-hydroxybutyl-ε-hydroxy-caproic acid ester, ω-hydroxyhexyl-γ-hydroxybutyric acid ester; adipic acid-bis-(β-hydroxyethyl) ester and terephthalic acid-bis(β-hydroxyethyl) ester;
(e) diol urethanes of the general formula
HO--(CH.sub.2).sub.x --O--CO--NH--R'--NH--CO--O(CH.sub.2).sub.x --OH
in which
R' represents an alkylene, cycloalkylene or arylene group having from 2 to 15, preferably 2 to 6 carbon atoms and
x represent an integer between 2 and 6,
e.g. 1,6-hexamethylene-bis-(β-hydroxyethyl urethane) or 4,4'-diphenylmethane-bis-(δ-hydroxybutyl urethane).
The monoalkanolamines used as chain lengthening agent components for the preparation of the polyurethanes used according to the invention have molecular weights of from about 61 to about 200 and they contain both a primary amino group and an aliphatic hydroxyl group. Typical examples of this class of compounds include 2-amino ethanol; N-methyl-N-(2-hydroxyethyl)-ethylene diamine; N-methyl-N-(2-hydroxyethyl)-trimethylene diamine; 1-amino-3-propanol; 1-amino-2-propanol; 4-amino-2-butanol; 4-amino-1-butanol; 2-amino-2-methylpropanol; 2-(p-aminophenyl)-ethanol; p-aminophenyl-methylcarbinol and 2-(p-aminocyclohexyl)ethanol.
The chain-lengthening agents used according to the invention consist of a mixture of from about 95 to 35 mol %, preferably 90 to 50 mol %, of at least one diol of the kind mentioned above and about 5 to 65 mol %, preferably 10 to 50 mol %, of at least one monoalkanolamine of the kind mentioned above.
Chain-lengthening agent mixtures of ethylene glycol and/or butane diol with monoethanolamine and/or 1-amino-3-propanol are preferred. Chain-lengthening agent mixtures containing, for example, about 5 to 35 mol % of monoethanol-amine and about 95 to 65 mol % of ethylene glycol are particularly preferred.
The molar ratio of higher molecular weight polyesters or polyethers on the one hand to the mixture of low molecular weight chain-lengthening agents on the other should be between about 1:1 and 1:6, preferably between about 1:1.5 and 1:5. The polyurethanes are substantially free from reactive end groups. They are generally prepared at an NCO/OH ratio of between about 0.95 and 1.05, preferably between about 0.96 and 1.01.
The solvents used for the polyurethanes according to the invention may be either highly polar or less polar solvents known per se, or mixtures of such solvents. Examples include dimethylformamide; dimethylacetamide; dimethylsulphoxide, ethylacetate; methylglycol acetate; methylethyl ketone; acetone; cyclohexanone, tetrahydrofuran; dioxane; halogenated hydrocarbons such as chlorobenzene or dichloroethylene and aromatic hydrocarbons such as toluene or xylene.
When the polyurethanes are used as adhesive coats according to the invention, highly polar solvents such as dimethylformamide are preferably present in quantities of not more than about 65% by weight and most preferably not more than about 50% by weight, based on the total quantity of solvent mixtures.
If desired, the top coats according to the invention may be applied to the textile substrates together with two-component polyurethane systems known per se. These generally consist of solutions of a mixture of polyurethane prepolymers which contain hydroxyl end groups and have a molecular weight of about 10,000 to 80,000, preferably 20,000 to 50,000, polyisocyanates and catalysts. Apart from the polyisocyanates already mentioned above, compounds containing more than two isocyanate groups or reaction products of polyhydroxyl compounds with excess polyisocyanates may also be used, for example a 75% solution in ethyl acetate of a polyisocyanate from trimethylol propane and 2,4-tolylene diisocyanate having an isocyanate content in the form of free tolylene diisocyanate of less than 0.3%.
The solutions used for the adhesive coats often contain catalysts known per se, e.g. tertiary amines such as triethylamine; tributylamine; N-methyl-morpholine; N-ethylmorpholine; N,N,N',N'-tetramethyl-ethylene diamine; 1,4-diaza-bicyclo-(2,2,2)-octane; N-methyl-N'-dimethyl-aminoethyl-piperazine; N,N-dimethylbenzylamine; bis-(N,N-diethylaminoethyl)-adipate; N,N-diethylbenzylamine; pentamethyldiethylene triamine; N,N-dimethylcyclohexylamine; N,N,N' ,N'-tetramethyl-1,3-butane diamine; N,N-dimethyl-β-phenylethylamine; 1,2-dimethylimidazole or 2-methylimidazole.
The following are examples of tertiary amines containing hydrogen atoms which are reactive with isocyanate groups; triethanolamine; triisopropanolamine; N-methyldiethanolamine; N-ethyl-diethanolamine and N,N-dimethyl-ethanolamine and their reaction products with alkylene oxides such as propylene oxide and/or ethylene oxide.
Silaamines with carbon-silicon bonds such as the compounds described in German Patent Specification No. 1,229,290 may also be used as catalysts, e.g. 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl-tetramethyldisiloxane. Organic metal compounds may also be used as catalysts according to the invention, in particular organic titanium compounds.
Other examples of catalysts which may be used according to the invention and details concerning their activity may be found in Kunststoff-Handbuch, Vol. VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 96- 102 and Polyurethanes: Chemistry and Technology, Vol. I Chemistry, Saunders and Frisch, Interscience, 1964.
The adhesive coat and top coat solutions which contain the polyurethanes used according to the invention may also contain the usual pigments, fillers, polymer resins and other auxiliary agents such as stabilizers against hydrolysis, UV stabilizers, anti-oxidants, polysiloxanes, cross-linking agents and accelerators.
EXAMPLES OF APPLICATION
The thermal pressure resistance (resistance to ironing) of the polyurethanes was tested by means of a Hoekstra-Plastometer manufactured by Nederlandsche Optieken Instrumentenfabriek Dr. C. E. Bleeker N. V., Zeist Holland. A test foil about 1 mm in thickness was preheated for 30 seconds between two presses heated to the test temperature and the foils were then subjected to a pressure of 10 kp/cm 2 for 2 minutes. The percentage residual thickness of foils could be read off an instrument scale. After removal of the pressure from the samples, the remaining percentage residual thickness of the foils was taken as a measure of the thermal pressure distortion.
EXAMPLE 1a
Adhesive coat solution H 1 is a 35% solution of a polyester urethane in dimethylformamide (DMF)/methylethyl ketone (MEK) (1:1) having a viscosity of 55,000 cP/25° C. The polyester urethane elastomer is synthesized from 2195 parts by weight (1.0 mol) of a polyester of butane-1,4-diol and adipic acid having a hydroxyl number of 50.6 and an acid number of 0.5; 186.21 parts by weight (3.0 mol) of ethylene glycol and the equivalent quantity (1000 parts by weight) of 4,4'-diphenylmethane diisocyanate. A polyurethane film prepared from the fresh solution was found to have the following physical properties:
______________________________________Tensile strength 48.8 MPaElongation at break 500%100% modulus 5.2 MPaMicro hardness 80Melting range 180°-190° C. (Kofler bench)Pressure deformationafter 2'/160° C. 4%Permanent pressuredeformation 0%______________________________________
After a storage time of 48 hours, the polyurethane solution (H 1) had been completely converted into a paste and could no longer be processed.
EXAMPLE 1b
Adhesive coat solution H 2 is a 35% solution of a polyester urethane in DMF/MEK (1:1) having a viscosity of 41,000 cP/25° C. The polyester urethane was in this case synthesized from 2,195 parts by weight (1.0 mol) of the same polyester as in adhesive coat solution H 1, 155.18 parts by weight (2.5 mol) of ethylene glycol, 45.06 parts by weight (0.5 mol) of butane diol and the equivalent quantity (1000 parts by weight) of 4,4'-diphenylmethane diisocyanate. A polyurethane film formed from this solution had the following physical properties:
______________________________________Tensile strength 62.5 MPaElongation at break 620%100% modulus 3.9 MPaMicro hardness 83Melting range 165°-180° C. (-) (Kofler bench)Pressure deformation after2'/160° C. 65% (-)Permanent pressuredeformation 45% (-)______________________________________
Polyurethane solution (H 2) shows no tendency to become pasty and is still in good condition for processing after several weeks of storage. However, the resistance of the polyurethane to ironing (high permanent pressure deformation) is unsatisfactory; moreover, the polyurethane has a substantially lower melting range.
EXAMPLE 1c
Adhesive coat solution H 3 is a 35% solution of a polyester urethane in DMF/MEK (1:1) having a viscosity of 48,500 cp/25° C. It has been synthesized from 2,195 parts by weight (1.0 mol) of the same polyester as in adhesive coat solution H 1, 155.18 parts by weight (2.5 mol) of ethylene glycol, 30.54 parts by weight (0.5 mol) of ethanolamine and the equivalent quantity (1000 parts by weight) of 4,4'-diphenylmethane diisocyanate. A polyurethane film prepared from this solution is found to have the following physical properties:
______________________________________Tensile strength 51.2 MPaElongation at break 660%100% modulus 3.8 MPaMicro hardness 74Melting range 190°-200° C. (Kofler bench)Pressure deformationafter 2'/160° C. 10%Permanent pressuredeformation 0%______________________________________
Polyurethane solution (H 3) shows no tendency to become pasty and can easily be processed after several weeks of storage; the polyurethane shows good resistance to ironing (no permanent pressure deformation).
EXAMPLE 1d
Adhesive coat solution H 4 is a 35% solution of a polyester urethane in DMF/MEK (1:1) having a viscosity of 64,000 cP/25° C. It was synthesized from 2,195 parts by weight (1.0 mol) of the same polyester as that used for adhesive coat solution H 1, 93.10 parts by weight (1.5 mol) of ethylene glycol, 91.62 parts by weight (1.5 mol) of ethanolamine and the equivalent quantity (1000 parts by weight) of 4,4'-diphenylmethane diisocyanate. A polyurethane film prepared from this solution is found to have the following physical properties:
______________________________________Tensile strength 51.9 MPaElongation at break 500%100% modulus 3.9 MPaMicro hardness 85Melting range 188°-198° C. (Kofler bench)Pressure deformationafter 2'/160° C. 0%Permanent pressuredeformation 0%______________________________________
The polyurethane coat obtained from adhesive solution H 4 has excellent resistance to ironing (no pressure deformation at 160° C.). In spite of the slight cloudiness occurring after several weeks in storage, the solution (H 4) is still perfectly suitable for processing after 3 months.
EXAMPLE 1e
Adhesive coat solution H 5 is a 35% solution of a polyester urethane in DMF/MEK (1:1) having a viscosity of 66,000 cP/25° C. The polyurethane is composed of 2,195 parts by weight (1.0 mol) of the same polyester as that used for adhesive coat solution H 1, 31.04 parts by weight (0.5 mol) of ethylene glycol, 152.70 parts by weight (2.5 mol) of ethanolamine and the equivalent quantity (1000 parts by weight) of 4,4'-diphenylmethane diisocyanate. A polyurethane film formed from this solution is found to have the following physical properties:
______________________________________Tensile strength 52.2 MPaElongation at break 590%100% modulus 6.4 MPaMicro hardness 85Melting range 192°-200° C. (Kofler bench)Pressure deformationafter 2'/160° C. 0%Permanent pressure deformation 0%______________________________________
Adhesive coat solution H 5 also gives rise to a polyurethane coat which has excellent resistance to ironing but it shows slight cloudiness after a short time in storage and distinct signs of becoming pasty after about 3 months.
EXAMPLE 1f
Adhesive coat solution H 6 is a 35% solution of a polyester urethane in DMF/MEK (1:1) having a viscosity of 69.600 cP/25° C. The solution was in this case synthesized from 2,195 parts by weight (1.0 mol) of the same polyester as that used for adhesive coat solution H 1, 155.18 parts by weight (2.5 mol) of ethylene glycol, 37.56 parts by weight (0.5 mol) of 1-amino-3-propanol and 1000 parts by weight of 4,4'-diphenylmethane diisocyanate. A film obtained from this solution is found to have the following physical properties:
______________________________________Tensile strength 51.7 MPaElongation at break 620%100% modulus 3.5 MPaMicro hardness 80Melting range 190°-200° C. (Kofler bench)Pressure deformationafter 2'/160° C. 14%Permanent pressuredeformation 0%______________________________________
Polyurethane solution (H 6) shows no tendency to become pasty. It can be processed after prolonged storage, giving rise to a polyurethane film which has high resistance to ironing (no permanent pressure deformation).
EXAMPLE 2a
A high melting polyester urethane (D 1) for producing top coats is composed of 2,195 parts by weight (1.0 mol) of a polyester of butane-1,4-diol and adipic acid having a hydroxyl number of 50.6 and an acid number of 0.5 297.94 parts by weight (4.8 mol) of ethylene glycol and the equivalent quantity (1450 parts by weight) of 4,4'-diphenylmethane diisocyanate.
The solid polyurethane (D 1) prepared in known manner is distinguished by its highly reduced solubility. When attempts are made to dissolve it in a solvent mixture of DMF/MEK (4:1) either in laboratory flasks equipped with stirrers or in the usual industrial dissolvers (e.g. "Spangenberg"), only highly viscous, gel-like solutions can be obtained, which cannot be processed on coating machines. It is only when special high-power mixers operating with very high shear forces (e.g. "Papenmeier") are used that a spreadable solution can be obtained. This solution has a solids content of 25% in DMF/MEK (4:1) and a viscosity of 8400 cP/25° C.
After only several days in storage, the solution shows a strong blocking effect which causes difficulties in coating installations operating at high speed. A film prepared from the fresh solution is found to have the following physical properties:
______________________________________Tensile strength 55.0 MPaElongation at break 480%100% modulus 9.3 MPaMicro hardness 89Melting range 202°-206° C. (Kofler bench)Pressure deformationafter 2'/170° C. 0%Permanent pressuredeformation 0%______________________________________
EXAMPLE 2b
A top coat polyester urethane (D 2) was obtained from 2,195 parts by weight (1.0 mol) of the same polyester as that used for top coat (D 1), 279.32 parts by weight (4.5 mol) of ethylene glycol, 27.04 parts by weight (0.3 mol) of butane diol-(1,4) and 1450 parts by weight of 4,4'-diphenylmethane diisocyanate. The polyurethane solid has normal solution properties and dissolves in DMF/MEK (4:1) to form a 25% solution which has a viscosity of 10,000 cP/25° C. and is stable in storage.
A film obtained from this solution is found to have the following physical properties:
______________________________________Tensile strength 63.9 MPaElongation at break 520%100% modulus 8.9 MPaMicro hardness 82Melting range 185°-190° C. (Kofler bench)Pressure deformationafter 2'/160° C. 10%Permanent pressuredeformation 3%______________________________________
Compared with top coat (D 1), top coat (D 2) has a distinctly lower melting range and weaker resistance to ironing (slightly permanent pressure deformation).
EXAMPLE 2c
A top coat polyester urethane (D 3) was obtained by polyaddition of 2,195 parts by weight (1.0 mol) of the same polyester as that used for top coat (D 1), 270.32 parts by weight (4.5 mol) of ethylene glycol, 18.32 parts by weight (0.3 mol) of ethanolamine and 1450 parts by weight of 4,4'-diphenylmethane diisocyanate. The solid polyurethane has normal solution properties and dissolves in DMF/MEK (4:1) to form a 25% solution having a viscosity of 15,700 cP/25° C. which is stable in storage.
A film prepared from this solution has the following properties:
______________________________________Tensile strength 66.8 MPaElongation at break 550%100% modulus 8.6 MPaMicro hardness 86Melting range 196°-208° C. (Kofler bench)Pressure deformationafter 2'/160° C. 1%Permanent pressuredeformation 0%______________________________________
This top coat (D 3) has practically the same melting range as top coat (D 1) and equally good resistance to ironing and is at the same time distinguished by the solubility of the solid and ease of processing.
EXAMPLE 3a
A conventional top coat solution D 4 consists of a polyester urethane in DMF/MEK (3:2) having a viscosity of 10,500 cP/25° C. in which the polyurethane has been synthesized from 1000 parts by weight (0.5 mol) of hexane diol-1,6-polycarbonate and a hydroxyl number of 56.0 and an acid number of 0.1, 1098 parts by weight (0.5 mol) of a polyester of butane diol-(1,4) and adipic acid having a hydroxyl number of 50.6 and an acid number of 0.5; 270.36 parts by weight (3.0 mol) of butane-1,4-diol as chain-lengthening agent and the equivalent quantity (1000 parts by weight) of 4,4'-diphenylmethane diisocyanate.
The polyurethane is found to have the following properties as film:
______________________________________Tensile strength 59.4 MPaElongation at break 480%100% modulus 10.7 MPaMicro hardness 93Melting range 171°-178° C. (Kofler bench)Pressure deformationafter 2'/160° C. 69%Permanent pressuredeformation 52%______________________________________
When the top coat (D 4) is laminated to a textile substrate by means of a two-component polyurethane comprising an adhesive coat solution (H 7) which has a low DMF content, the so-called frosting effect well known to be undesirable in coating processes occurs because the top coat does not dissolve sufficiently. The adhesive coat solution (H 7) is a 30% solution of a polyester urethane in DMF/MEK (1:3) having a viscosity of 25000 cP/25° C. The polyester urethane was synthesized from 500 g of a polyester of ethylene glycol and adipic acid (molecular weight approximately 2000), 500 g of a polyester of diethylene glycol and adipic acid (molecular weight approximately 2000) and 87.0 g of a mixture of 2,4- and 2,6-tolylene diisocyanate isomers. Before the adhesive coat solution is applied, 5.0 g of a 75% solution in ethyl acetate of a polyisocyanate (10.5% NCO) which has been prepared from 1.0 mol of trimethylolpropane and 3.0 mol of 2,4 -tolylene diisocyanate and 5.0 g of a catalyst consisting of a 10% solution in ethylene dichloride/ethyl acetate (1:1) of a reaction product of 1.0 of N-methylethanolamine and 2.0 mol of phenyl isocyanate are added per 100 g of solution.
EXAMPLE 3b
A top coat solution D 5 modified in accordance with German Offenlegungsschrift No. 2,402,799 consists of a 25% solution of a polyester urethane in DMF/MEK (3:2) having a viscosity of 9,800 cP/25° C. The polyurethane in this solution has been synthesized in the same way as that used for the top coat (D 4) but contains a mixture of 225.30 parts by weight (2.5 mol) of butane diol-(1,4) and 59.09 parts by weight (0.5 mol) of hexane diol-(1,6) as chain-lengthening agent. A film obtained from this solution is found to have the following properties:
______________________________________Tensile strength 44.8 MPaElongation at break 470%100% modulus 9.9 MPaMicro hardness 92Melting range 156°-168° C. (Kofler bench)Pressure deformationafter 2'/160° C. 91%Permanent pressuredeformation 62%______________________________________
No frosting effect occurs when the top coat (D 5) is applied by means of adhesive coat solution (H 7) but the top coat does suffer some loss in dimensional stability at elevated temperature (see pressure deformation test).
EXAMPLE 3c
Top coat solution D 6 is a 25% solution of a polyester urethane in DMF/MEK (3:2) having a viscosity of 11,500 cP/25° C. The polyester urethane has been synthesized in the same way as those used in top coat solutions (D 4) and (D 5) but with a chain-lengthening agent consisting of a mixture of 225.3 parts by weight (2.5 mol) of butane diol-(1,4) and 30.54 parts by weight (0.5 mol) of ethanolamine.
This polyurethane has the following properties as film:
______________________________________Tensile strength 52.9 MPaElongation at break 540%100% modulus 9.2 MPaMicro hardness 90Melting range 165°-175° C. (Kofler bench)Pressure deformationafter 2'/160° C. 45%Permanent pressuredeformation 19%______________________________________
The top coat (D 6) can be applied with the aid of adhesive coat solution (H 7) without a frosting effect being produced, and compared with the original top coat (D 4) it has a higher dimensional stability at elevated temperature.
EXAMPLE 4a
Adhesive coat solution H 8 is a 35% solution of a polyurethane (D 4) in DMF/MEK (1:1) having a viscosity of 63,500 cP/25° C. With this low concentration of DMF, the solution is not stable for very long and tends to gel. A film prepared from the fresh solution is of the same quality as that obtained in Example 3a.
EXAMPLE 4b
Adhesive coat solution H 9 is a 35% solution of polyurethane (D 5) in DMF/MEK (1:1) having a viscosity of 58,600 cP/25° C. The solution is stable in storage but the polyurethane film obtained from it has a lower dimensional stability at elevated temperature as in Example 3b.
EXAMPLE 4c
Adhesive coat solution H 10 is a 35% solution of polyurethane (D 6) in DMF/MEK (1:1) which has viscosity of 70,900 cP/25° C. and is stable in storage. The polyurethane film obtained from it resembles that of Example 3c in its improved dimensional stability at elevated temperature.
Although the invention has been described in detail for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
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The present disclosure is concerned with an improved method of reverse coating textile sheets with storage stable polyurethane top and adhesive coats which are formulated to have improved resistance to deformation under heat and pressure. At least one of the coats is formulated from a diisocyanate, a high molecular weight dihydroxy compound and a mixture of at least one low molecular weight diol with a low molecular weight monoalkanolamine. The coatings are applied in the usual reverse coating manner, i.e. the top coat is applied to a release substrate from solution; dried; the adhesive coat is applied from solution onto the dried top coat; and the textile substrate is laminated to the adhesive coat.
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REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application Ser. No. 11/865,731, filed on Oct. 2, 2007 and entitled “Protective Fiber Optic Union Adapters”, and is continuation-in-part of U.S. patent application Ser. No. 11/307,688, filed on Feb. 17, 2006 and entitled “Isolated Fiber Optic Union Adapters”.
FIELD OF THE INVENTION
[0002] This invention relates to optical systems using fiber optic cables to transmit illumination and/or signals, and more particularly, to devices enabling low insertion loss and low back reflection connections between fiber optic cables while also preventing the propagation of connector end face damage between cables.
BACKGROUND OF THE INVENTION
[0003] Fiber optic cables are terminated with polished connectors that interchangeably interconnect with low optical insertion loss to other patchcords or fiber optic devices having compatible connectors. These connectors include an optical fiber, one end of which is stripped to expose the bare glass and bonded within a precision, close tolerance hole of a ferrule. The fiber and ferrule end faces are made co-planar and optically smooth by cleaving or subsequent polishing of the end face. In the common male-type fiber optic termination, a length of polished ferrule containing the optical fiber extends outside of the connector housing.
[0004] Male-type connectorized fibers may be interconnected to one another with low optical loss (<0.25 dB) in transmission by inserting the connectors into opposite ends of a fiber optic union adapter. Union adapters typically consist of a housing with opposing receptacles that surround a hollow, precision split sleeve whose nominal inner diameter is slightly less than the outer diameter of connectors' ferrules. The mating of the ferrules within the union adapter elastically deforms the semi-tubular wall of the split sleeve to slightly enlarge the inner diameter of the sleeve. The sleeve produces an opposing compressive force on the ferrules which aligns the ferrules concentrically. Precision manufacturing ensures that the optical fiber core is concentric with the optical fiber outer diameter, and the hole within the ferrule is concentric with the ferrule outer diameter at one end of the ferrule. Consequently, the two fiber cores are repeatedly aligned concentrically to micron or sub-micron tolerances. A slight axial force on the ferrules is produced once the spring-loaded bodies of the connector assemblies are attached to the housing of the union adapter, ensuring that the domed, polished end faces of the fiber/ferrule assemblies of the two different cables are mechanically and optically contacted within the split sleeve.
[0005] The polished ferrule contact areas are highly susceptible to scratching caused by repeated mating and demating cycles in the presence of contaminants trapped on or in the vicinity of the contact area. Surface damage to the fiber endface in the vicinity of the optical fiber's core degrades optical performance. In particular, the increased excess loss and reduced return loss can seriously compromise the network's performance. With broadcast-type access networks, in which the optical signal is power split between as many as thirty-two users, the optical power budget of the network has low margin and the impact of such damage is particularly significant. This problem is exacerbated by the fact that a single contaminated or damaged fiber/ferrule, if connected to other clean and undamaged fiber terminations, can degrade these other fiber terminations and propagate connector damage throughout the network.
[0006] In the past, the primary users of fiber optic telecommunications equipment have been service providers such as telephony and cable operators delivering data, video and telephone transmission. Their optical networking equipment has historically been centrally located within specialized facilities maintained and operated by highly experienced engineers. A growth in applications of fiber optic technology is occurring as fiber is increasingly being deployed in local area networks (LANs) located in the end users' facilities. In this decentralized architecture, the cost to diagnose and repair damaged terminations increases considerably depending on the physical location of the termination within the network. For instance, damage to an inaccessible connectorized drop cable originating from within a customer's wall or damage at the connector interface of a populated, high-density fiber patch panel requires a costly service call and repair by an experienced technician. These are two examples of “back-side” fiber optic terminations which are difficult to repair by virtue of their inaccessibility.
[0007] Fiber optic access networks may incorporate large numbers of reconfigurable connection interfaces as the fibers branch out from a central closet to each access location. For instance, fiber optic patch cables attach at one end to connectors at wall or desk mount interface plate and at the other end to fiber optic modems or gigabit Ethernet transceivers. Typically, the ends of the fiber optic drop cable within the customer's premises are terminated using highly specialized and costly fiber optic termination equipment. Once the fiber build-out is complete, proper handling of the fiber cable and connectors must be diligently maintained to preserve the performance of the network. Fiber optic cable is particularly susceptible to cracking due to excessive bends and polished fiber optic terminations are susceptible to scratching if contacted with dirty and contaminated connectors. Repair and debugging requires skilled fiber optic technicians, adding significant cost and overhead to maintain the network. As a consequence, present day fiber optic systems lack the robustness commonly found in electronic networking systems.
[0008] Recent advances in the design of union adapters for various standard connector styles (FC, SC, ST, LC, MTRJ) have focused on approaches to prevent contamination from entering the critical split sleeve area. This includes the development of various shields and covers to help prevent contamination from entering the front side union adaptor body. U.S. Pat. No. 5,887,098 by Ernst et al. discloses an FC-type fiber optic union adapter with a two-part shield assembly to cover the end of the receptacle when a cable is not attached. U.S. Pat. No. 6,863,445 by Ngo describes an alternate cap design for SC type fiber optic union adapters. However, these approaches do not prevent a damaged or contaminated connector ferrule from damaging the mating connector.
[0009] In addition, an alternate type of fiber optic adapter is designed to produce substantial signal attenuation by introducing an air gap or misalignment between opposing connector ferrules or by inserting a lossy optical element between the mating ferrules are available. For example, U.S. Patent Application 2003/031423 by Zimmel describes an SC-type fiber optic adapter that includes a sheet of attenuator glass embedded at the longitudinal center of the alignment split sleeve and U.S. Pat. No. 5,267,342 by Takahashi et al. introduces an air gap between connector ferrules to cause light to escape from the central waveguide. This adapter produces significant insertion loss (>=5 dB) since it is designed to produce attenuation. These attenuators interrupt the longitudinal continuity of the central waveguide cores attached to either side of the attenuator housing and thereby introduce a significant amount of loss and optical backreflection. These devices rely on a non-adiabatic or abrupt discontinuity in the waveguide core as is passes through the attenuating union adapter.
[0010] A low loss, low backreflection, low cost and compact device to prevent polished surface damage (PSD) from propagating to other fiber optic connectors and fiber optic devices is therefore of particular importance, much like its analog, the electrical fuse, which is also a sacrificial element protecting costly electronic systems from damage and which can be inexpensively and easily replaced.
BRIEF DESCRIPTION OF THE FIGURES
[0011] FIG. 1 illustrates a front view (A) and a side cutaway view (B) of an isolated fiber optic union adapter attached to a wall mounted interface plate;
[0012] FIG. 2 illustrates a cross sectional view of an SC-UPC type isolated fiber optic union for joining two male connector ends, including the adiabatic waveguide core transition;
[0013] FIG. 3 illustrates an exploded view of an SC-UPC type isolated fiber optic union for joining two male connector ends;
[0014] FIG. 4 illustrates a cross sectional view (A) and front view (B) of an FC-APC type isolated fiber optic union for joining two male connector ends;
[0015] FIG. 5 illustrates a cross sectional view (A) of an FC-APC type union attached to a pair of fiber optic cables and a magnified view (B) of the adiabatic transition of waveguide cores through the device;
[0016] FIG. 6 illustrates a cross sectional view of a fiber optic male-to-female union adapter for joining male to female fiber optic connectors;
[0017] FIGS. 7A and 7B illustrate a fiber optic transmission module including integrated isolated union adapters;
[0018] FIG. 8 illustrates a cross sectional view of a fiber stub with an adiabatic waveguide core transition between connectorized bend insensitive fiber and standard single mode fiber;
[0019] FIG. 9 illustrates the process of producing the adiabatic taper by electrical arcing;
[0020] FIG. 10 depicts a flow diagram outlining the steps of producing a fiber stub including an adiabatic tapered core transition;
[0021] FIGS. 11A and B illustrate a protective union adapter for mating angle polished connector to non-angle polished connector through an adiabatic waveguide transition;
[0022] FIG. 12 details a fiber stub for angle polished connectors and alignment features to properly orient the angled stub within union adapter, and
[0023] FIGS. 13A and B illustrate a protective union adapter which switches between adiabatic and non-adiabatic transmission when one cable is removed from the adapter.
SUMMARY OF THE INVENTION
[0024] This invention discloses compact, protective, and sacrificial fiber optic union adapters incorporating an internal adiabatic waveguide core transition section to reconfigurably interconnect two fiber optic cables with low insertion loss and low back reflection. The deployment of these union adapters within fiber optic networking systems reduces the potential for damage to “back-side”, or partially inaccessible fiber optic cable spans, thereby minimizing networking downtime and reducing maintenance costs. These adapters include a miniature internal fiber stub element within a precision alignment sleeve to prevent direct physical contact between the polished end faces of connectorized fibers, while providing highly efficient optical coupling between the two mating fiber optic cables through an adiabatic waveguide core transition. The term “adiabatic” refers to the slow variation of waveguide core optical propagation characteristics across the mating fiber interface. The slow variation ensures that the optical signal is not coupled into other forward, backward, or scattering optical modes, all of which contribute to optical loss downstream of the union adapter and backreflections upstream of the union adapter. The internal fiber stub element comprises length(s) of single mode or multi-mode fiber(s) bonded within a precision ferrule and precisely polished on opposite end faces. The optical fiber and polished end face characteristics are selected to be nominally identical to the connectorized fibers attached thereto.
DETAILED DESCRIPTION OF THE INVENTION
[0025] In accordance with the invention, FIG. 1A illustrates a front view and FIG. 1B a side cutaway view of a low loss, low backreflection, compact and protective fiber optic union adapter 20 mounted behind an interface plate 16 attached to an interior wall 26 of an office or home, for example. The connectorized end 17 - 2 of a front-side fiber optic patchcord 10 - 2 is inserted into the front receptacle 21 of union adapter 20 to optically interconnect this patchcord 10 - 2 to a back-side fiber optic drop cable 10 - 1 originating from an inaccessible or difficult to access area 62 behind wall 26 . The front-side cable lies within an accessible field 60 and can be easily replaced and removed. The back-side terminated and connectorized end 17 - 1 of fiber 10 - 1 is inserted into the back receptacle 21 ′ of union adapter 20 . During installation of the fiber optic cabling, the end of the back-side drop cable 10 - 1 is terminated with the polished connector 17 - 1 . This polished connector is produced either by an on-site cleaving and/or polishing process or by fusion splicing a polished, pre-manufactured connector pigtail to the drop cable 10 - 1 . The cleaving, polishing and fusion splicing processes each require considerable skill and costly equipment to perform. Therefore, the subsequent protection of back-side connector 17 - 1 from polished surface damage (PSD) during routine plugging and unplugging of fiber optic connectors into receptacle 21 over the service life of the network is of significant value.
[0026] Such PSD protection is provided by the union adapter of the present invention by preventing direct physical contact between the front side and back side cables. FIG. 2 details in cross section an SC simplex bulkhead type isolated union adapter with fiber stub 9 including a length of single mode (e.g., SMF-28e fiber from Corning Inc.) or multimode (e.g., 50/125 micron Infinicor from Corning Inc.) fiber 10 - 4 along the longitudinal axis with ultra-physical polish (UPC) endfaces 4 ′. The endfaces have a slight radius of curvature (dome) to provide physical contact. The “V number” (see Snyder and Love, Optical Waveguide Theory, 1995 Chapman and Hall, Sections 18-5 and 19-2) at either end of fiber 10 - 4 are selected to be nominally identical to the V numbers of mating fiber optic cables 10 - 1 and 10 - 2 to provide a low loss, low backreflection adiabatic waveguide interface.
[0027] The angles and curvatures of the polished surfaces 4 ′ are provided in accordance with the standards developed for PC (physical contact), UPC (ultra-physical contact) or APC (angled physical contact) type fiber optic connectors. The surfaces 4 ′ typically have a large radius of curvature (˜20 mm) to produce a slight “dome” on the end face. On the scale of FIG. 2 , this radius is sufficiently large that the dome is not apparent. The end faces typically have a slight circumferential bevel that extends in about 100 to 300 microns radially from the outer diameter of the stub to guide the connector ferrule into the union adapter split sleeve during cable mating. Within housing parts 11 - 1 , 11 - 2 lies the precision split sleeve 8 loosely constrained longitudinally and radially by a transversely divided outer sleeve 7 - 1 and 7 - 2 with inner diameter 101 . The fiber stub 9 with outer diameter 100 , including embedded fiber 10 - 4 , is epoxied or compression fit within split sleeve 8 . While FIG. 2 depicts a union adapter for simplex SC type connectors, this approach is scaleable to duplex or multi-fiber type connectors.
[0028] FIG. 2 illustrates the protective union adapter wherein an internal, adiabatic waveguide core transition achieves low optical loss and back reflection when interconnecting cables. If a patchcord 10 - 2 with connector 17 - 2 containing a damaged or dirty ferrule tip 5 - 2 is inserted into the front receptacle 21 of union adapter 20 , the replaceable, isolated union adapter 20 , the non-absorbing, adiabatic fiber stub 9 would prevent the transfer of damage to the polished ferrule tip of back-side termination connector 17 - 1 . Damage to the union adapter 20 is a less costly problem than damage to the back-side termination. Drawing an analogy to electrical systems, it is preferable to replace an electrical fuse rather than the piece of equipment it was designed to protect. Therefore, the protective union adapter disclosed here is a sacrificial element designed to be sufficiently low cost, so that it can be replaced by a simple, inexpensive procedure. Removal and replacement of isolated union adapter 20 is also facilitated by use of a clip mechanism 17 or screws to attach to interface plate 15 , for example. The restoration of network functionality simply requires that front-side cable 10 - 2 and fiber stub 9 of isolated union adapter 20 be replaced in a simple exchange of relatively inexpensive components. This avoids a costly on-site visit by a repair technician.
[0029] The unique advantages of the union adapter disclosed herein are achieved by transmitting the optical signal between cables through an intermediately positioned, low loss fiber stub that provides longitudinally uninterrupted, optically continuous, adiabatic optical signal exchange between the waveguide cores of the front-side and back-side cables. The fiber stub includes a central optical waveguide core, substantially matched in geometry and optically contacted to opposite ends to the waveguide cores of the mating cables. Light propagates adiabatically from one cable to the other cable through a fiber waveguide intermediary, while longitudinal perturbations to the effective modal indices of refraction are kept small such that little or no energy is coupled into lossy modes. Furthermore, the optical waveguide effective modal indices of refraction at either end of the stub are matched to those indices of the mating cables.
[0030] The split sleeve is typically fabricated of ceramic, plastic or phosphor bronze and the housing 11 is typically fabricated of injection molded plastic. An exploded view of this protective union adapter is illustrated in FIG. 3 , comprising the stub 9 which is press fit into sleeve 8 , this assembly floating within the cavity formed by outer sleeves 7 - 1 and 7 - 2 , which are retained within housing shells 11 - 1 and 11 - 2 which are adhesively or ultrasonically bonded.
[0031] FIG. 3 also depicts an external, spring loaded shutter feature 11 - 3 . In general, an external or internal beam shutter may be added to the union adapter and consists of a spring-loaded plastic or metallic element which physically blocks the light escaping when a cable transmitting an optical signal is inserted into the union adapter receptacle 21 ′. That element 11 - 3 is, for example, a miniature rectangular door with a pivot or hinge on one edge and attached to the union adapter receptable housing 11 - 2 . The shutter enhances eye safety by preventing stray light from disconnected fiber optic cables and equipment from being focused to high intensity within the eye. This shuttered union adapter can additionally include an integrated electronic micro-switch whose electrical state changes should the shutter be open or closed while the fiber optic connection is un-terminated. For example, the laser source input into the fiber at some local or downstream location can be turned off if the union adapter is un-terminated and the shutter is open. This can be particularly relevant for photonic power delivery systems, in which optical fiber is used to transmit relatively high optical powers for conversion into electricity by a photoconductive conversion method at some remote location.
[0032] The union adapter of the present invention may further include an integrated photodetector (e.g., silicon, GaAs or InGaAs) that generates sufficient power to turn on a visible wavelength light emitting diode incorporated into the housing of the union adapter. While typical optical power levels in communications applications are 1 mW, they can exceed 1000 W for high power fiber optic beam delivery systems.
[0033] Optically polished fiber end faces must interface with low loss and backreflection even after substantial numbers of mating and de-mating cycles. Since the optical fibers are typically fabricated of silica or Germanium doped silica glass, the hardnesses of these mating surfaces are substantially identical. A drawback of this construction is that excessive surface roughness on one fiber end face can transfer damage on the mating surface and such connections have a tendency to degrade. The wear-out problem is mitigated by interfacing the two cables through a longitudinally intermediate fiber stub element, whereby at least the surface of the fiber stub 9 waveguide end faces 4 , 4 ′ contacting the front-side cable 10 - 2 is of a material or coated with a material which is of substantially higher material hardness than that of the mating surface material of the front-side cable. This feature further increases the service lifetime of the protective union adapter 20 .
[0034] In particular, the fiber stub material may be silica while the front side and back side optical fibers are constructed of a highly transmissive plastic such as methyl-methacrylate. Since silica exhibits substantially higher material hardness than plastic, the protective stub will be immune to damage from the surface imperfections of the plastic optical fiber end face. Additionally, to interconnect glass optical fibers, a silica glass fiber stub is utilized, wherein additional polished surface protection is provided by coating one or both stub 9 end faces 4 or 4 ′ with a ¼ wave thick layer of hard thin film (e.g., diamond). The ¼ wave thickness is adequate for protection while also serving as an antireflection coating to minimize back reflections and excess optical loss. Hard, durable coatings may be applied after polishing to the end of the fiber stub 9 by evaporation or sputtering, for example, and typically utilize a relatively low temperature process (<120 C) to prevent degradation of the epoxy used to bond the optical fiber core within the fiber stub ferrule. This use of dissimilar hardnesses is similar to mechanical techniques to prevent galling between metal contact points.
[0035] In an additional example, reflective thin film coatings on the fiber stub 9 endfaces produce optical reflections from the back and/or front side fiber stub surfaces. The coatings may exhibit either a narrow-band or broad-band wavelength response and are typically multilayer dielectric coatings produced by evaporation or sputtering. Alternately, the fiber stub may include a fiber Bragg grating element recorded within the optical fiber segment, providing a narrow band reflection spectrum. Such a protective union adapter introduces wavelength dependent optical filtering into the fiber optic transmission path and finds application to wavelength division multiplexed (WDM) communication and sensor systems.
[0036] In a further embodiment, the union adapter features angle polished surfaces to reduce back reflection. As illustrated in the cross section of FIG. 4A , the flange of connector housing 11 allows the union adapter to be mounted to a wall plate or panel mount. Inside housing 11 is the precision split sleeve 8 within two-piece split sleeve retaining elements 7 - 1 and 7 - 2 . Element 7 - 2 is fixed within body 11 by a friction fit, for example. The fiber stub is retained within split sleeve 8 . The ends of fiber stub 9 are prepared with parallel, angle polished faces 4 . The use of angled surfaces reduced back reflections to <−65 dB. As illustrated in FIG. 4B , the key 6 - 3 in connector receptacle 21 ensures that the angled ferrules are inserted with the proper azimuthal orientation so that all angled fiber surfaces are parallel to one another. This performance is necessary for transmitting analog video signals or for access networks in which a signal is split and distributed to several users.
[0037] FIG. 5A illustrates a cross sectional view of this FC-APC fiber optic union adapter 20 including connectorized fiber 10 - 1 inserted into receptacle 21 ′ and connectorized fiber 10 - 2 inserted into receptacle 21 . Fiber 10 - 1 is terminated at ferrule 5 - 1 within connector body 17 - 1 with a screw on cap 19 - 1 that maintains the connector attached to union housing 11 - 1 . Fiber 10 - 2 is terminated at ferrule 5 - 2 within connector body 17 - 2 with a screw-on cap 19 - 2 that attaches the connector to union housing 11 - 2 . The ferrules 5 - 1 and 5 - 2 achieve continuous, uninterrupted optical contact with fiber stub 9 at the central waveguide core region of the ferrules.
[0038] The magnified view of FIG. 5B details the geometry of the waveguide cores across the adiabatic transition region of the fiber stub. The waveguide cores 12 - 1 , 12 - 3 at the endfaces of cables 10 - 1 and 10 - 2 , respectively, and the core 12 - 2 within stub 9 , are characterized by a mode field diameter (MFD), which is a measure of the diameter of the optical beam propagating through the fiber, and V number, which is a measure of the number of modes which can be supported by the waveguide core. Furthermore, the relative positional offset errors of the optical fiber cores at transition interface 1 and interface 2 are denoted by δ 12 and δ 23 , respectively. Low loss and back reflection follows if the following adiabaticity requirements are meet:
[0000] δ 12 /(MFD 1 +MFD 21 )<0.1, Eq. 1
[0000] δ 23 /(MFD 22 +MFD 3 )<0.1, Eq. 2
[0000] 0.9<V 1 /V 21 <1.1, Eq. 3
[0000] 0.9<V 22 /V 3 <1.1. Eq. 4
[0000] Equations 1 and 2 ensure that there is minimal non-adiabatic positional offset of the two optical modes at the interconnection interfaces and equations 3, 4 ensure that the waveguide structural characteristics undergo a negligibly small change at the interfaces. By maintaining sub-micron concentricity of the core of fiber 10 - 4 with the outer diameter of fiber 10 - 4 , and sub-micron concentricity of the ferrule 9 inner diameter and outer diameter, adiabaticity is maintained so that the excess insertion loss due to this isolated union adapter is typically less than 0.25 dB. For highly concentric fiber stubs (<1 micron for single mode stubs and <3 micron for multimode stubs), the insertion loss may actually be lower than standard union adapters. Insertion loss increases approximately quadratically with waveguide core concentricity error because the abrupt misalignment is non-adiabatic. Therefore, a stub with concentricity error less than that of the mating ferrules of the cable connectors can actually produce lower loss than directly mating the two ferrules. For example, if one ferrule has a δ 12 =+1 micron error in x direction and the other has a δ 23 =−1 micron error in x, while the fiber stub has an error of 0 microns, the excess loss of a standard union adapter would be two times larger than the excess loss of this adiabatic, protective union adapter. Therefore, the protective union adapter has the potential to reduce the net loss by a factor of 2 if its concentricity error tolerances are superior to that of the mating ferrules. For example, fiber stubs using ferrules with single mode tolerances (<1 micron) can be used to give superior insertion loss for multimode union adapters.
[0039] The fiber stub ferrule is typically fabricated of zirconia, ceramic or fused silica, with an embedded fused silica optical fiber of 125 microns or 80 microns outer diameter. The length of the fiber stub is typically 2.5 mm to 4.5 mm long for the 2.5 mm diameter stub. The core of optical fiber 10 - 4 is typically 10 microns in diameter and propagates single spatial mode radiation at wavelengths of 1550 or 1310 nm with extremely low optical loss, or core diameter is typically 50, 62.5 microns for propagation of multi-mode radiation in the range of 800 nm to 1600 nm. The split sleeve 8 is typically fabricated of zirconia, ceramic, plastic or phosphor bronze that conforms to the 2.5 mm or 1.25 mm outer diameter of the fiber stub.
[0040] In an alternate example, the waveguide core of the fiber stub 9 may produce a non-adiabatic, but low absorption waveguide core transition to provide wavelength dependent transmission and reflection responses. The waveguide core within the fiber stub may have a larger diameter than the waveguide cores of the mating back-side and front-side optical fibers. By virtue of its larger diameter, the fiber stub core has a V number greater than 2.4 and therefore supports the low loss propagation of multiple optical models. Each mode is characterized by a different modal index of refraction and different group velocity. A single mode core of the front-side cable will excite higher order modes within the multimode core due to the non-adiabatic interface. These modes will interfere or beat with one another within the multimode core as the relative phases between each of the modes vary with longitudinal distance through the stub. Only a fraction of optical power in each of these modes will couple back into the single mode core of the back-side fiber. The resulting non-uniform mode coupling translates into a non-uniform wavelength-dependent transmission response. The length of fiber stub and its effective modal indices of refraction are selected to give a predefined wavelength dependent transmission and reflection. This wavelength dependent transmission can be utilized for filtering and/or sensing applications. For example, if the temperature of the fiber stub changes, the phase difference between the various modes supported by the stub and its transmission at any particular wavelength will cycle between constructive and destructive interference as a function of this phase difference. Such an element may provide fiber optic sensing or filtering functionality. In a particular example, the front-side and back-side cables have a 9 micron diameter core, while the fiber stub includes a 50 micron diameter core with 4.0 mm length.
Male-to-Female Protective Union Adapters
[0041] In an alternate embodiment, a union adapter can be provided to interconnect a male-to-female fiber optic termination. FIG. 6 illustrates a cross sectional view of the fiber stub-ferrule subassembly for a fiber optic male-to-female union adapter. The housing is not shown in this view. This configuration enables the union adapter to be inserted between the male end of a fiber optic cable and a female termination incorporated in the housing of an optical transceiver, for example. The union adapter introduces low excess loss by utilizing low optical attenuation single mode or multi-mode fiber within the isolating fiber stub and an adiabatic transition of the waveguide core. In this particular example, the union adapter includes a split sleeve 8 within retaining sleeve 7 - 2 . The retaining element 7 - 3 is attached to fiber stub 9 . Fiber stub 9 has polished end faces 4 and embedded optical fiber 10 - 4 , one end of which is internal to split sleeve 8 . End faces 4 may optionally be antireflection coated to minimize any transmission ripple. Optical fiber 10 - 4 may exhibit single mode or multi-mode propagation characteristics. The housing body (not shown in FIG. 6 ) may be of the FC, ST, SC, LC, MTRJ or other industry standard connector styles, in a simplex or duplex configuration. The polished end faces 4 can be the APC, PC, UPC or other industry standard types.
Example
Optical Signal Processor with Replaceable Receptacles
[0042] In a particular example, the male-to-female isolating union adapters are used to isolate the fiber optic ports of an optical signal processor. More specifically, the optical signal processor may be in the form of a duplex fiber optic transceiver module, an example of which is illustrated in FIGS. 7A and 7B . This module may be transmit optical Ethernet-formated data at rates up to 10 Gbit/sec and include electrical signal conversion or communication. The transceiver module 33 is packaged within a housing 32 and includes integrated duplex, female-type fiber optic receptacles 31 . In FIG. 7 these receptacles 31 are of the SC-UPC type with either multi-mode or single mode fiber interfaces, for example, and with alignment channels 35 . Alternate receptacle types include LC, ST and MTRJ. Damage to the internal fiber interfaces within receptacle 31 is difficult or impractical to repair. To protect this interface from damage, this transceiver unit includes an integrated isolating union adapter 20 which inserts into a mating cavity within transceiver housing 32 . The internal structure of union adapter 20 includes a fiber stub 9 and alignment sleeve 8 . The union adapter 20 prevents the ferrules 5 of external terminated fiber optic cables with connector 17 - 2 from contacting the receptacles 31 in the transceiver unit 33 . In this way, should a cable 10 - 2 with damaged or contaminated ferrule 5 be inserted into 20 , damage is restricted to the inexpensive, replaceable union adapter 20 rather than the transceiver 33 . The union adapter is attached to the housing by semi-permanent means, such as screws 34 which hold union adapter 20 to enclosure 32 . This attachment prevents the user from exposing the receptacles 31 during routine use. Repair of transceiver 33 requires a simple replacement of union adapter 20 . This approach protects the fiber optic interface ports of other high value optical signal processors from damage, such as optical switches and multiplexers/demultiplexers.
Union Adapter for Dissimilar Fiber Types
[0043] Bend insensitive fiber may be preferable within the customer's premises because fiber optic patchcords incorporating this fiber are more robust under bending and routine handling. However, in many cases the fiber drop cable 10 - 1 entering the customer's premises is standard single mode optical fiber. Directly interfacing connectorized single mode fiber and connectorized, bend insensitive fiber can result in relatively high insertion loss (>0.5 dB) and signal degradation. Therefore, in accordance with this invention, low loss interconnection between dissimilar fiber types is provided by utilizing a fiber stub element within a union adapter including an adiabatic waveguide core transition. A low optical loss transition between fibers with dissimilar core diameters, as is the case for standard and bend insensitive fiber, or multimode 50/125 micron and 62.5/125 micron multimode fibers, can be achieved by utilizing an adiabatic taper of the core diameter and MFD to smoothly and continuously transition from one fiber diameter to the other within a longitudinal distance greater than the beat note length, determined from the difference in propagation constants between the two fibers. This distance is typically between 10 and 1000 microns, depending on the fiber core diameters and wavelength of operation. This range of lengths enables the adiabatic core transition to be packaged within the stub in a compact fashion. The stub length is typically 4 mm.
[0044] The adiabatic taper within the isolating fiber stub may be fabricated by partially diffusing out the core at one end of a bend insensitive fiber to match the mode field diameter of a particular single mode fiber and fusion splicing this end to the particular single mode fiber. The adiabatic taper is formed longitudinally adjacent to the fusion splice and is part of a continuous length of fiber which can be epoxied into a ferrule to produce a fiber stub with different core diameters at the opposite end faces. This fiber stub is fixed at the center of the union adapter. In this case, a standard single mode fiber cable termination can be attached to a bend insensitive, single mode fiber cable with low insertion loss (<0.10 dB).
[0045] In a particular example, FIG. 8 details the fiber stub and illustrates the internal fusion-spliced optical fibers joined by an adiabatic taper. Bend insensitive fiber 10 - 5 has a core 112 - 1 of generally smaller diameter than standard single mode fiber 10 - 6 with core 112 - 2 . The diameter of core 112 - 1 is typically 6 to 8 microns and the diameter of core 112 - 2 is typically 9-10 microns. In the taper region, the core diameter monotonically varies while maintaining a minimal slope of the waveguide walls.
[0046] In a particular example of the adiabatic taper manufacturing process ( FIG. 9 ), the adiabatic waveguide taper within the bend insensitive fiber is formed by using a fusion splicer's electrical arc 15 , for example, to heat the end of the bend insensitive fiber 10 - 5 and diffuse out the core 112 - 1 to enlarge the mode field diameter locally and match the core 112 - 2 of second fiber 10 - 6 . Pre- or post-arcing functionality is available on standard fusion splicers such as the Alcoa-Fujikura Model 50FS. Typical fabrication steps are disclosed in the flow chart of FIG. 10 . Alternate approaches to diffusing the core include localized heating with a CO 2 laser emitting at a wavelength of 10.6 microns or with mini-torches such as the hydrogen gas-type used to fabricate fused couplers. Fiber cleaving can be provided by use of standard precision cleavers manufactured by Alcoa-Fujikura or Sumitomo. The two fibers are contacted and heated to form a fusion splice with interface 13 and adiabatic taper 112 - 3 . The fibers 10 - 5 and 10 - 6 are subsequently inserted and bonded into a ferrule to form a fiber stub 9 assembly. The end faces 4 of the fiber stub 9 are polished to mate with standard angle polished or flat polished connectors.
Union Adapter for Dissimilar Polish Types
[0047] In an alternate example, the union adapter may serve as an adaptive interface between dissimilar terminations, such as UPC and APC. As illustrated in FIGS. 11A and 11B , the fiber stub is provided with UPC polish at one end 4 and APC polish at the other end 4 ′. While the UPC polished surface 4 is normal to the beam propagation direction, the incidence angle to the APC polished surface 4 ′ is typically eight degrees. This union adapter enables a UPC terminated cable connector 17 - 1 to be interfaced thru the intermediate stub to an APC terminated cable connector 17 - 2 while retaining the protective aspects disclosed herein. In this configuration, the angled surface of the fiber stub must be aligned relative to the connector alignment key of the mating cable. As detailed in FIG. 12 , this is achieved by azimuthally aligning the radial extension 40 of fiber stub 9 relative to the gap 8 - 1 in the outer split sleeve 8 , and aligning the split sleeve gap relative to the union adapter housing 6 - 1 . For example, the cavity in the union adapter housing 11 - 1 may include a key 36 to engage the split sleeve gap 8 - 1 and maintain proper azimuthal orientation of the split sleeve-fiber stub assembly. The ferrule may include a longitudinal slot 92 into which a ceramic, metal or plastic extension is bonded. The thickness of this extension is less than the split sleeve gap 8 - 1 so the stub can slide within the split sleeve without rotating.
[0048] APC terminations serve to reduce the impact of back reflections on optical network performance. For example, the back reflection of optical signals from un-terminated connectors degrade overall optical network performance in broadcast type networks in which an optical signal is split and distributed to several different users via unique fiber paths or in analog video links. For single mode fiber transmission, the level of attenuation of back reflections, or return loss, should typically exceed 50 dB to prevent undesirable crosstalk. Un-terminated PC and UPC cables, whether disconnected or attached to union adapters, provide a return loss of only 14 dB. Therefore, in accordance with this invention, this union adapter example has the further advantage of providing low back reflection termination from a UPC terminated cable inserted into the back side cable receptacle, even when no mating connector is inserted into the front side cable receptacle.
[0000] Union Adapter Providing Low Back Reflection/Low Transmission while Unterminated
[0049] In a further example, the protective union adapter may include two in-line fiber stubs, a front-side stub and a back-side stub, in series and concentrically aligned within a single outer split sleeve ( FIGS. 13A and 13B ). The surfaces of the two stubs 9 - 1 and 9 - 2 , which contact each other at the center of the split sleeve 8 , are angle polished and azimuthally aligned to provide low loss physical contact. The edges of the stub end faces may be fabricated with a circumferential step rather than angled bevel as illustrated here. A compression spring or elastomer element 50 lies inside or outside the spit sleeve to engage the raised stub extensions 40 ′ and 40 ″. This spring element longitudinally separates the two angle polished surfaces 4 ′ when one of the mating cables 17 - 2 is removed. In the absence of the longitudinal compressive force provided by the spring-loaded ferrules of the mating cable 17 - 2 , the fiber stubs separate within the precision split sleeve to produce an air gap 52 there between. Reinsertion of the mating cable 17 - 2 recompresses the spring element 50 so the gap between the two stub elements 9 - 1 , 9 - 2 vanishes. This design has the advantage that when only one cable 17 - 2 ′ is attached to the union adapter, an angled air gap 52 is present. This geometry provides low back reflection, because the inner surfaces of the fiber stub are angled, and also substantially prevents light from escaping from the fiber stub facing the front-side receptacle. The width of air gap 52 is large enough that light emanating from the back-side stub 9 - 2 is blocked by the opaque ferrule used in the front-side stub 9 - 1 . An additional feature of the protective union adapter described above is therefore an automatic shuttering functionality with low unterminated back reflection.
[0050] When the front side cable connector 17 - 2 is installed into the union adapter, the longitudinal, extension spring force on the connector ferrule produced when inserting the cable connector body into the union adapter receptacle is adequate to compress the spring or elastomer element 50 between the front-side 9 - 1 and back-side 9 - 2 stubs and eliminate the central air gap. The high concentricity of the stub pair and split sleeve enables one or both stubs to longitudinally piston within the split sleeve while maintaining precise radial or transverse alignment even during repeated cycling of connection and disconnection. The central air gap region is also shielded from environmental contamination by the surrounding split sleeve 8 and union adapter housing. As a result, low loss and repeatable light transmission between the front-side and back-side cables is achieved.
[0051] The force required to separate the two stubs 9 - 1 , 9 - 2 within the split sleeve 8 under the compressive/frictional force of the split sleeve is determined by the diameter increase of the split sleeve when the stubs are installed, as well as the material used to construct the sleeve. For zirconia sleeves, the typical force to longitudinally displace the stub is 200 gram-force (gf) to 600 gf for SC, FC and ST type terminations and 100 gf to 300 gf for MU and LC type terminations. Therefore, the spring or elastomer element should produce adequate outward longitudinal force to separate the stubs when one or both fiber optic cables are removed from the union adapter. The spring element may be constructed of metal, plastic or rubber, in the form of a compression spring, Bellville washer, or tube, for example.
[0052] In summary, fiber optic networking equipment and optical signal processors such as transceivers, switches, amplifiers, multiplexers/demultiplexers, modems and patch panels typically include large numbers of fiber optic union adapters to mate connectorized fiber optic cables. These unions join fibers in locations where permanent fusion splices are inappropriate because of the need to periodically reconfigure or replace fiber optic cables. A great limitation in prior art approaches is the fact that if one cable's ferrule is dirty or damaged, it will likely transfer damage to the mating ferrule because the union physically contacts the polished endfaces of both ferrules to one another. In many cases, the damaged mating ferrule is part of a back-side cable deeply embedded within the fiber optic plant. Replacing such a cable is a costly process. To eliminate this damage, we have disclosed an inexpensive component providing a low loss and potentially low back reflection by introducing an adiabatic waveguide transition between the cores of two mating optical fibers through a fiber stub element within the union adapter.
[0053] Those skilled in the art will readily observe that numerous modifications and alterations of the device may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.
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Devices to enhance the reliability of optical networks and to reduce the cost of repair are disclosed in this invention. In particular, compact and inexpensive fiber optic union adapters with built-in protective isolation prevent the transfer of damage from one connectorized fiber optic cable to another. The fiber optic union includes a split sleeve with an interior channel and a fiber stub centrally located within the interior channel. The fiber stub makes direct optical contact with the cable endfaces to enable efficient optical transmission between interconnected cables while providing a low loss, low back reflection adiabatic transition between the waveguide cores of the two cables.
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This application is a continuation of application Ser. No. 08/230,142, filed Apr. 13, 1994, now abandoned.
This invention, in general, relates to protection of the environment, and more particularly to an apparatus and method for treatment of media, such as waste or sea water or contaminated soil, to remove therefrom one or more unwanted substances contained therein.
BACKGROUND OF THE INVENTION
One of the most serious problems facing the world today is the availability of clean fresh water for the well being and survival of mankind. Disposal into sewers and storm drains, or into the soil, of petroleum-based waste products, as well as waste water containing those and a variety of other contaminants, has become a major source of ground water contamination. Wells which supplied drinking water for thousands of people have become contaminated and unusable. This has given rise to numerous community, state and federal regulations setting standards for the protection of the environment, including standards for contaminant content of waste disposed of in local sewers, water courses and elsewhere.
In their zeal for environmental protection, some communities have set standards requiring the contaminant content of such waste waters to be so low that they could not be met by the use of presently available technology. As a result, some of these community standards have been reluctantly amended to permit higher levels of contaminant content which can be met with available technology.
There are many contaminants from numerous sources which are capable of polluting ground water and thereby threatening the environment, as well as the health of the populace. Some of such contaminants and sources thereof include lubricating oil, diesel fuel and grease from the auto and truck servicing industry; surfactant or soap laden waste water from laundry and dishwashing equipment; and ethylene glycol from the auto, truck and aircraft servicing industries, as well as from other industries where ethylene glycol is used in day to day operations.
Other sources of environmental pollution include agricultural run-off containing insecticides or other agricultural chemicals washed by rain or irrigation sprays from crops on which they were sprayed. Waste water from the photographic processing industry is a source of polluting metal salts, as is the electronic component manufacturing industry. An additional source of pollution is that resulting from backwashing of swimming pool filters in which the filtering medium is diatomaceous earth. Community standards in some areas of the country are presently so restrictive that the effluent from such back washing cannot be discharged into local sewers.
Because of the unavailability of any quick and efficient means for separating petroleum hydrocarbons, such as lubricating oil, grease and diesel fuel, as well as other contaminants from waste water containing the same, resort has been had by the automobile and truck service industry to the use of clarifiers. These commonly comprise a series of four open settling tanks, each of about 400 gallon capacity, disposed at different levels. Contaminated waste water is fed into the highest tank, and the overflow therefrom is fed into the second highest tank. With the exception of the lowest tank, the overflow from each tank is fed into the next lower tank in the series.
Much of the heavy oil, grease and solids in the waste water fed to the clarifier collect in the first and second tanks, and is periodically removed therefrom in the form of a sludge which is hauled away by licensed disposal services. For a period of time, the effluent from the lowermost tank is of a quality which meets local environmental standards. Eventually, however, the third tank in the series collects a significant amount of sludge and must be cleaned out along with the first two tanks, in order for the clarifier to continue to produce acceptable quality effluent.
Unfortunately a clarifier as just described produces additional environmental pollution, namely air pollution. More particularly, the waste water in the clarifier tanks tends, over time, to promote the generation of a foul smelling gas having an odor similar to that of sewer gas, which odor permeates the surrounding neighborhood.
SUMMARY OF THE INVENTION
In contrast to the aforementioned slow, malodorous and inefficient settling tank procedure, the present invention provides a means for removing or rendering innocuous a wide variety of contaminants from media, such as waste water or soil containing the same, doing so quickly, easily and inexpensively. The forms of the invention disclosed and claimed herein are capable of removing from waste water, unwanted contaminating petroleum based products, such as gasoline, grease, lubricating oil, diesel fuel, brake fluid and transmission fluid, as well as numerous other substances, such as ethylene glycol, heavy metals and hazardous organic solvents.
By the present invention, waste water can be treated so that it is not only of a quality which meets or exceeds the most rigid community, state and federal standards for disposition into local sewer systems, but it can also be treated so that it is fit for human consumption.
Surprisingly, the invention can have great application in arid countries which presently rely on expensive desalinization operations for their water supply. To this end, the invention is effective to quickly and inexpensively remove unwanted salt from sea water, as well as from brine or salt impregnated soil. In addition, the invention is effective to remove unwanted polluting metal salts from waste water of the photographic processing and other industries, such as the electronic component manufacturing industry, whose waste water includes polluting metal salts.
The apparatus of the present invention can be effectively used in place of diatomaceous earth type swimming pool filters to maintain the quality of the swimming pool water in a manner which is in compliance with all presently known environmental standards. Moreover, the method of the invention can also be used effectively to prevent the formation of foul smelling gas in clarifier settling tanks containing waste water of the type mentioned earlier herein.
The illustrated embodiments of the invention comprise one or more modular system components or tanks through which waste water, fresh water or sea water, as the case may be, is passed, usually after dilution with fresh water. In each of these tanks the influent water contacts a quantity of zeolite in the presence of a surfactant. The tanks may advantageously also contain a quantity of cellulose, which is preferably hydrophobic, and with which the water passing therethrough also comes in contact.
If the influent waste or sea water is known to contain a surfactant, the amount thereof may be sufficient for effective operation of the invention, without the need for additional surfactant.
Waste water from automobile and truck washing operations usually contains significant quantities of surfactant and is typical of the type of waste water which is advantageously diluted with fresh water in order for the invention to work most efficiently thereon. Contaminants in such waste water can include such unwanted substances as oil and grease, lubricating oil, brake, transmission and power steering fluid, engine coolant and battery acid or the like which are washed-off of automobiles and trucks.
In the situation in which the waste water is known to not contain any significant amount of surfactant, an effective amount thereof is added to the waste water and/or the treatment tank. This situation is likely to occur when the waste water to be treated comes from an automobile or truck repair center, as distinguished from an automobile or truck washing establishment.
Another situation which would require the addition of surfactant would be where the water to be treated is sea water contaminated with oil from an oil spill. In such a case, the invention is effective to remove both the oil and the salt from sea water.
While the invention may find its greatest application in the removal of substances from waste water, sea water and the like using the apparatus described, another application which may have great environmental implications, and which does not involve the use of such apparatus, involves the decontamination of soil which has become impregnated with petroleum hydrocarbons or has been rendered agriculturally useless because of impregnation with salt. To decontaminate such soil, zeolite in powder form and surfactant in powder form are mixed with the soil along with water. After the mixing is complete, the soil is then washed with fresh water to remove the innocuous by-products of the process and thereby return the soil to its original useful state.
BRIEF DESCRIPTION OF DRAWINGS
The invention can best be understood by reference to the drawings accompanying and forming a part of this application, wherein
FIG. 1 is a side elevational view of a modular system component of the presently preferred form of the invention, which component is in the form of a compartmented tank;
FIG. 2 is a vertical sectional view taken along the line II--II of FIG. 1;
FIG. 3 is a plan view of the modular system component shown in FIG. 1, parts being broken away;
FIG. 4 diagrammatically illustrates a mobile waste water treatment system including three modular system components of the type shown in FIGS. 1 to 3 connected in series;
FIG. 5 illustrates in vertical section another form of modular system component of the present invention; and
FIG. 6 is a vertical sectional view similar to FIG. 2 of a modified form of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1 to 3 of the drawings, the modular system component illustrated therein comprises a tank formed of four stacked coaxial cylindrical compartment members 11, 12, 13 and 14, a cover member 15, and a cylindrical base member 16.
As best shown in FIG. 2, the compartment members 11 to 14 are formed at their upper ends, respectively, with radially outwardly projecting annular flanges 17, 18, 19 and 20. The base member 16 is formed at its upper and lower ends, respectively, with radially outwardly projecting annular flanges 21 and 22. The cover 15 is similarly formed with a radially outwardly projecting annular flange 23. The compartment members 11 to 14 are formed at their lower ends, respectively, with radially outwardly projecting annular flanges 24, 25, 26 and 27. The compartment members 11 to 14 are also formed at their lower ends with perforated horizontal bottom walls 28, 29, 30 and 31, respectively. The perforations in the bottom walls 28 to 31 may be in the form of closely spaced apertures of about 1/4 inch across.
The cover 15 is provided on the interior thereof with a spray head 32 which has an external connection fitting 33, which may incorporate a shut off valve 72, and has means (not shown) for providing a readily releasable connection to piping system 66 to be described hereinafter, which system may be connected to a source of waste water to be treated. Alternatively, the piping system aforementioned may provide a connection of fitting 33 to the outlet of another like modular system component and provide a series connection of multiple components as shown in FIG. 4.
The base member 16 is formed with an internal sloping drain pan 46, at the lower end of which the side wall of base member 16 is provided with a tubular drain fitting 34. The fitting 34 may be of any suitable type providing a readily releasable connection to the aforementioned piping system 66, to a drain line or to conduit means extending to the inlet connection 33 of a like modular system component with which it is serially connected.
Interposed between the coaxial annular flanges 23 and 17 of the cover 15 and compartment member 11, respectively, is a flat annular sealing gasket 35. The gasket 35 may have an inner diameter somewhat smaller than that of compartment member 11, for a purpose which will become apparent hereinafter. Interposed between the coaxial flanges 24 and 18 of the compartment members 11 and 12, respectively, is a flat annular sealing gasket 36. Interposed between the coaxial annular flanges 25 and 19 of compartment members 12 and 13, respectively, is a flat annular sealing gasket 37. Interposed between the coaxial annular flanges 26 and 20 of compartment members 13 and 14, respectively, is a flat annular sealing gasket 38. Interposed between the annular flanges 27 and 21 of the compartment member 14 and base member 16, respectively, is a flat annular sealing gasket 39.
The cover 15 is held in coaxial sealing relationship with the upper compartment member 11 and sealing gasket 35 by an annular tension band 40 having a channel shaped cross section. The tension band 40 engages the flanges 23 and 17 and biases the same toward each other into sealing engagement with the gasket 35 under the tensioning effect of an adjustable screw connection 41 shown in FIG. 3, in a manner well known in the art.
A similar tension band 42 holds the compartment members 11 and 12 in coaxial sealing relationship with gasket 36, and the same type of band 43 holds the compartment members 12 and 13 in coaxial sealing relationship with gasket 37. An annular tension band 44 similarly holds the compartment members 13 and 14 in coaxial sealing relationship with gasket 38, whereas a like annular tension band 45 holds the compartment member 14 in coaxial sealing relationship with gasket 39. The cover 15 may be provided with a pressure relief valve 47 as shown in FIG. 2.
The size of the modular system component 10 is not narrowly critical. However, it is preferably of a size which can be readily handled. The diameter of component 10 may be of the order of about 36 inches, and each of the cylindrical compartment members 11 to 14 may have an axial dimension of the order of about 8 inches. The base 16 may have an axial dimension of the order of about 24 inches.
Suitably mounted transversely within the cover 15 near the lower edge thereof is a circular prefilter 48 which may be formed of glass fiber and which is approximately 1/8 inch thick. In FIG. 2 the perimeter of the prefilter 48 rests on the inner margins of the gasket 35.
Overlaying the perforated bottom wall 28 of the topmost cylindrical compartment member 11 is a circular pad 49 which is preferably in the form of a multilayer laminate of nonwoven, preferably hydrophobic, cellulose fibers. Overlaying the pad 49 is a bed 50 of, preferably hydrophobic, cellulose pellets, said pellets being retained within a perforated enclosure (not shown) which may take the form of a plastic mesh bag. Overlaying the bed 50 is a bed 51 of zeolite pebbles which are also retained within a perforated enclosure (not shown) such as a plastic mesh bag. The beds 50 and 51 are of the order of about 2 inches thick, and each, as well as the pad 49, extends into snug contact with the inner surface of the sidewall of the compartment member 11 throughout the periphery thereof. It will be observed that there is a significant cylindrical header space above the zeolite bed 51 and below the prefilter 48, which space may be of the order of about 4 inches.
Overlaying the perforated bottom walls 29 and 30 of cylindrical compartment members 12 and 13, respectively, are cellulose pads 52 and 53 which may be the same as the pad 49 in compartment member 11. Overlaying the cellulose pads 52 and 53, respectively, are beds 54 and 55 of, preferably hydrophobic, cellulose pellets. The beds 54 and 55 are preferably the same as the bed 50 in compartment member 11. Overlaying the respective beds 54 and 55 are beds 56 and 57 of zeolite pebbles which are preferably the same as the bed 51 in compartment member 11.
Overlaying the perforated bottom wall 31 of the cylindrical compartment member 14 is a cellulose pad 58 which is preferably the same as the cellulose pads 49, 52 and 53. Overlaying the cellulose pad 58 is a bed 59 of activated charcoal beads which are retained within a perforated enclosure (not shown) which may take the form of a plastic mesh bag. A bed 60 of cellulose pellets which is preferably the same as the beds 50, 54 and 55, overlays the bed 59, and a bed 61 of zeolite pebbles which is preferably the same as the beds 51, 56 and 57, overlays the cellulose bed 60.
One reason hydrophobic cellulose is preferred for use in the beds 50, 54, 55 and 60 and pads 49, 52, 53 and 58 is the fact that it is not absorptive of water. Experience has shown that when hydrophilic cellulose is used in the apparatus of the present invention, such cellulose tends to disintegrate because of absorption of water. The fact that hydrophobic cellulose tends to adsorb petroleum hydrocarbons may also be an advantage inherent in the use thereof.
It will be observed that each of the compartment members 12 and 13 has a header space above the zeolite bed therein which approximates that in the compartment 11. Due to the addition of bed 59 to the compartment member 14 below the beds 60 and 61, the header space above the bed 61 therein is shown reduced by the amount of the thickness of the bed 59. However, the invention also contemplates the use of uniform header spaces, if such is required for maximum efficiency.
The size of the zeolite pebbles, cellulose pellets and activated charcoal is not narrowly critical. Zeolite pebbles of the order of 1/3 inch across, cellulose pellets of the order of 1/4 inch across, and activated charcoal beads of the order of 1/8 inch across have been found to perform very well. The plastic mesh enclosures or bags (not shown) have a mesh size small enough to contain the pebbles, pellets or beads enclosed therein, yet large enough to permit free flow of liquid therethrough. A mesh size of 1/32 inch has been found to work very well for this purpose.
FIG. 6 illustrates a modified form of the modular component shown in FIG. 2 in which the compartments 11, 12, 13 and 14 contain beds which are different in thickness, as well as different in arrangement, from that shown in FIG. 2. In FIG. 6 the parts common to FIG. 2 are indicated by the same reference characters as those used in FIG. 2.
In FIG. 6 the compartments 11, 13 and 14 have beds of zeolite pebbles 119, 120 and 121, respectively, therein, and compartment 12 has a bed 118 of preferably hydrophobic cellulose pellets disposed therein. The zeolite pebbles and cellulose pellets used in the respective beds are similar in size and content to those used in the form of the invention shown in FIG. 2, and the operation of the FIG. 6 embodiment is also similar to that of the embodiment of FIG. 2. In FIG. 6 the respective beds of zeolite and cellulose are disposed within open topped cylindrical, preferably metal, containers (not shown) said containers having perforated bottom walls (not shown) to permit fluid flow therethrough. Such containers, together with the respective beds therein, function as removable and replaceable cartridges. The beds 118 to 121 may have an axial dimension of the order of six inches, leaving a headspace thereabove of the order of two inches.
The zeolite used in the practice of the invention is preferably of the natural type. Synthetic zeolites can be used effectively, but are not preferred because of their cost and because they are not as long lasting as the natural zeolites. In contrast to the synthetic zeolites, natural zeolites appear to harden with use. Because of the great variation in the specific chemical content of zeolite found within a given source area, the chemical formula therefor must be considered to be approximate only. The zeolite presently preferred for use in the invention is readily available and falls within the class of clinoptilolite, which has the general formula Na 4 K 4 [Al 8 Si 40 O 96 ]. 24H 2 O. This zeolite is stated to have an Al 2 O 3 /SiO 2 ratio of about 70/12 percent and has dominant cations of sodium and potassium. This zeolite, which occurs naturally in the area of Tecopa, Calfi., has been found to work very well. It can be obtained from B.F.M. Specialty Minerals, 17092 D Street, Victorville, Calif. 92392.
A wide variety of other natural zeolites also works very well in the practice of the invention. Among such zeolites are members of the class of heulandite which fall within the general formula
(Na,Ca).sub.4-6 Al.sub.6 (Al,Si).sub.4 Si.sub.26 O.sub.72. 24H.sub.2 O.
In the mineralogical scientific literature it is stated that heulandite and clinoptilolite have the same aluminosilicate framework with only slight differences in those with high-silica or divalent cations. A continuous series between the calcium dominated low silica heulandite and potassium-sodium high-silica clinoptilolite has been well established, and it appears to be unsettled as to whether or not clinoptilolite should be characterized as a heulandite for this reason. The International Mineralogical Association recognizes both heulandite and clinoptilolite as separate species. The dominant cations of sodium and potassium in the high-silica clinoptilolite make it particularly desirable for use in the present invention.
The following tabulation sets forth semi-quantitative analyses of three samples of heulandite type zeolite which work satisfactorily in this invention. All of these zeolites were from the same area and they illustrate the variation in content thereof which is typical in natural zeolites. The tabulation includes only those elements which are present in amounts of about one percent or more.
______________________________________Heulandite Zeolite Analyses Sample Sample Sample No. 1 No. 2 No. 3 Percent Percent Percent______________________________________Silicon 26.0 26.0 29.0Potassium 4.5 3.8 4.0Aluminum 7.3 11. 9.0Iron 2.0 1.8 2.6Calcium 9.9 3.0 1.3Sodium 3.8 5.8 3.7Magnesium 1.3 0.99 1.2______________________________________
The heulandite type natural zeolites of which the above tabulation is exemplary are found in the area of Ash Meadows, Calif. and can be obtained from American Borate Company, 55515 Dunn Road, Newberry Springs, Calif. 92365.
Other zeolites which are useful in the invention are found in the classes of chabazite and phillipsite. Chabazite has the formula (Ca, Na 2 , K 2 , Sr, Mg) [Al 2 Si 4 O 12 ].6H 2 O and has a wide variation in the exchangeable cations calcium, sodium, potassium, strontium and magnesium. There is a complete series between calcium-rich and sodium-rich chabazites without any correlation to crystal morphology. Because of the dominant cations of sodium therein, the sodium-rich chabozites are the preferred chabozites.
Some zeolites of the phillipsite class are also useful in the invention and have the general formula (K 2 , Ca, Na 2 , Ba) 2 .5 (Al 5 Si 11 O 32 ). 13H 32 O. Phillipsite, wellsite, and harmotone have the same framework structure and represent a continuous chemical series in exchangeable cations from calcium to barium. Considerable potassium and sodium are commonly present. Phillipsite is defined as the member of the phillipsite structural group with less than 50 percent of the exchangeable cations being barium. Crystals with considerable sodium and potassium, but with less than 50 percent barium are potassium-sodium-barium phillipsite useful in the invention.
Another zeolite useful in the invention is analcime, which has the formula (Na 2 , Ca, Cs 2 , Mg) 2 [Al 2 Si 4 O 12 ]. 2H 2 O. Analcime has a wide variation in calcium, sodium, cesium and magnesium and is classed in several crystal systems. One form of analcime has greater than 50 percent sodium and is useful in the invention.
The surfactant used in the practice of the invention is not narrowly critical. Surfactants which work very well are those useful in the car and truck washing industry. These surfactants are commercially available and include one or more of such active ingredients as sodium metasilicate, sodium sulfate, sodium tripolyphosphate, sodium dodecylbenzene sulfonate, and trisodium phosphate.
In the practice of the invention, the modular system component 10 shown in FIGS. 1 to 3 preferably forms part of a water treatment system which comprises a plurality, for example three, such modular components which are readily removably connected into a suitable piping system, such as the piping system 66 to be described hereinafter, which may be part of a stationary installation (not shown). However, the modular components and said piping system may alternatively, and very advantageously, be part of a mobile installation which can be readily moved from the one location to another.
FIG. 4 diagrammatically illustrates a mobile installation in which a water treatment system embodying the invention is mounted on a wheeled support such as a trailer 62. Three of the modular system components 63, 64 and 65, which may be identical with the component 10 shown in FIGS. 1 to 3, are readily releasably connected in serial fashion into a piping system 66 carried by the trailer 62.
The piping system 66 is provided with power driven pump means which can take a number of forms, each of which is effective to pump water to be treated serially through the modular components 63, 64 and 65. In one arrangement the piping system may include a pump at the outlet of each modular component, such as the pump 67 shown in FIG. 2, and may also include a related shut off valve 68. Alternatively, the piping system may instead include one or more pumps located externally of the serially connected modular components, such as the pumps 69 and 73 shown in FIG. 4.
The piping system 66 shown in FIG. 4 connects the inlet of the component 63 with the outlet of pump 73, the inlet of said pump being connected to a source of waste water, such as a holding tank 70 or other source of a feed stream of water to be treated in the installation to remove therefrom unwanted substances. Such substances usually include at least one of the many and varied constituents which are subject to industrial effluent limitations under applicable environmental laws. A typical feed stream is the effluent from a car or truck washing installation.
The pump 73 has the primary function of propelling a feed stream from the tank 70 to the inlet of the component 63, whereas the principal function of the pump 69 is to pump effluent from the outlet of component 65 to a holding tank 71 or other receptacle suitable for receipt of treated water, or to an on-site piping system (not shown) for receipt of the water treated in the installation. In another arrangement only one of the pumps 69 and 73 may be used to pump the feed stream through the system.
The mobile type of system advantageously may also comprise an internal combustion engine driven electric power generator (not shown) also mounted on the trailer 62, for powering the pump or pumps in the piping system 66 and any other electrically powered equipment carried by trailer 62.
In a stationary installation, the piping system and holding tanks, if used, are permanently installed at selected on-site locations. As in the mobile installation, suitable readily releasable connections (not shown) are provided by which modular components such as the components 63, 64 and 65, can be quickly and easily connected into and removed from operating positions in the piping system 66 as needed or desired. In both the stationary and mobile types of installations, the pumps and piping system 66 cause the feed stream of waste water to flow successively from top to bottom through the respective modular system components from the inlet of component 63 to the outlet of component 65.
If the feed stream of waste water to be treated is known to contain no or very little surfactant, then prior to the securement of the cover 15 of each of the components 63 to 65 in operative position, a quantity of surfactant, for example up to about 4 ounces of dry powdered surfactant, is sprinkled over the top zeolite bed 51 therein. Care must be taken in order to avoid using a quantity of surfactant which would produce undesirable foaming within any modular component.
Prior to placing the water treatment apparatus of the invention into operation, each of the modular components is filled with fresh water to thereby thoroughly soak the contents thereof. After the soaking step, the fresh water is pumped from the components to ready the apparatus for operation.
The feed stream of waste water or the like to be treated in the apparatus is then introduced, preferably in diluted form, into the inlet of the first modular component in the series, i.e., the component 63 shown in FIG. 4. Referring to FIGS. 1 to 3, the waste water enters the top of the first component in the series through fitting 33 and spray head 32 which distributes said water over the upper surface of the glass fiber prefilter 48 shown in FIG. 2. Prefilter 48 traps any solid particles in the feed stream as it passes therethrough. The waste water then flows down onto the zeolite bed 51, flowing therethrough, as well as through the cellulose bed 50 and through the cellulose pad 49.
The feed stream then flows downwardly through the perforated bottom wall 28 of compartment 11 and onto and through the zeolite bed 56, cellulose bed 54 and cellulose pad 52 located in compartment 12. As the feed stream flows out of the compartment 12 through the perforations in the bottom wall 29 thereof, it flows downwardly onto and through the zeolite bed 57, cellulose bed 55 and cellulose pad 53 located in compartment 13, flowing out of said compartment through the perforated bottom wall 30 thereof.
The feed stream continues its downward flow through the zeolite bed 61, cellulose bed 60, activated carbon bed 59 and cellulose pad 58 in compartment 14, and leaves said compartment through the perforated bottom wall 31 thereof. As the feed stream enters the base compartment 16, it drops onto the sloping drain pan 46 therein and is directed thereby toward the outlet 34.
The effluent stream leaving the outlet 34 of modular component 63, is propelled by the pump or pumps through the piping system 66 to the inlet 33 of modular component 64, becoming the influent stream for said component. This influent stream flows downwardly through the component 64 and through the prefilter, zeolite beds, cellulose beds, activated carbon bed and cellulose pads therein just as the feed stream did through the modular component 63. Upon reaching the outlet 34 of the component 64, the effluent stream is propelled by the pump or pumps through the piping system 66 to the inlet 33 of the modular component 65, where it becomes the influent stream for said component.
This influent stream flows downwardly through the modular component 65 as it did through the components 63 and 64, flowing through the prefilter, zeolite beds, cellulose beds, activated carbon bed and cellulose pads therein. Upon reaching the outlet 34 of modular component 65 it becomes an effluent stream therefrom which is propelled by the pump or pumps through the piping system 66 to a holding tank 71 or other receptacle, or to a suitable on-site piping system (not shown) for receipt thereof.
As the waste water flows through the modular components 63, 64 and 65, surprising results are produced for reasons which are not completely understood. It appears that during transit through the modular components the water therein becomes involved in a complex process. This process is believed to involve chemical reaction, physical filtering and containment, adsorption and ion capture or exchange.
Petroleum hydrocarbons in the feed steam are mechanically filtered in the cellulose beds and pads and also appear to be altered chemically by the presence of the surfactant in the feed stream. It has been suggested that when a surfactant reacts with a neutral organic molecule, two actions can be considered to take place. Initially, there is a partial solvation of the organic molecule into the surfactant, and once this occurs, the resultant species contains an ionic functional group. When the ionized species passes into contact with the zeolite mineral, either ion-exchange or ion-capture processes occur, and the organic molecule is removed from the water stream. Any organic molecules which do not react with the surfactant are selectively filtered by the hydrophobic cellulose, and any particulate matter which is inert to the surfactant is physically trapped in said cellulose.
If soluble heavy metal ions or other organic species are present in the waste water, chemical reactions can occur between these and the surfactants as well. This interaction renders the subsequent species more susceptible to the ion exchange/ion capture processes within the zeolite. In addition, the subsequent inorganic ion/surfactant complex is more readily adsorbed by the hydrophobic cellulose.
Although specific chemical reactions occurring in the modular components 63, 64 and 65 have not been identified because of the extremely complex nature of waste water, it is probable that several reactions take place. These could include single displacement, double displacement, hydration and ion exchange. Depending upon the solubility of the resultant products, they may be filtered or reacted further with the zeolite mineral and surfactant in additional modular system components of the type described herein.
In the development of the invention, numerous prototypes were tested which demonstrated the surprising results which are achieved by the invention. The following tables set forth certain analytical specifics regarding both the feed streams treated in a particular apparatus and the after treatment effluent produced thereby.
All such analyses were carried out by a reputable laboratory specializing in analytical and environmental services. The laboratory was given no information about the treatment method which was productive of the effluent samples as the feed streams were flowed through the apparatus. The tables also provide the identifying numbers of the particular EPA or other tests which were carried out to produce the respective analytical data in the tables.
Table 1 illustrates the results of passing a feed stream of waste water through a 32 gallon plastic drum (not shown) having an upper inlet and a lower outlet. A perforated enclosure (not shown) in the bottom of the drum accommodated therein a power driven pump connected to the drum outlet for pumping effluent therethrough. A polyurethane plastic bag (not shown) lined the drum and had a perforated bottom wall which rested on the top of the pump enclosure.
Disposed within the drum and liner were four vertically spaced beds of heulandite zeolite pebbles (not shown) which were similar to the beds 51, 56, 57, and 61 in FIG. 2, each of said beds being enclosed within a plastic mesh bag (not shown). A bed (not shown) of hydrophilic cellulose pellets, enclosed within a nylon mesh bag and disposed within the bottom of the drum liner bag, rested on the top of the pump enclosure and had the lowermost bed of zeolite pebbles superimposed thereon. The bed of hydrophilic cellulose was similar to the beds 50, 54, 55 and 60 in FIG. 2, except for the hydrophilic, rather than hydrophobic, character of the cellulose therein.
Interposed between the lowermost zeolite bed and the zeolite bed next above it was a bed of hydrophobic cellulose pellets similar to the beds 50, 54, 55 and 60 in FIG. 2. Interposed between the last mentioned zeolite bed and the third zeolite bed from the bottom was another bed of hydrophobic cellulose pellets like the first mentioned bed of hydrophobic pellets. Interposed between the third zeolite bed from the bottom and the topmost zeolite bed was another bed of hydrophilic cellulose pellets similar to the first mentioned bed of hydrophilic cellulose.
Between each of the adjacent beds of zeolite pebbles and cellulose pellets was interposed a circular multilayer laminated pad of hydrophobic cellulose fibers similar to the pads 49, 52, 53 and 58 in FIG. 2. The same type of pad overlaid the topmost bed of zeolite pebbles and also underlaid the bottommost bed of hydrophilic cellulose pellets. Each of the beds of zeolite pebbles and cellulose pellets was enclosed within a plastic mesh bag of the type enclosing the beds in FIG. 2 and each of said beds extended radially into snug contact with the drum liner around its periphery. The cellulose pads similarly extended into snug contact with the drum liner around their peripheries. The zeolite beds contained about 2 pounds of zeolite each, and the cellulose beds contained about 10 pounds of cellulose each.
The principal constituents of the feed stream passed through the drum just described were those which would be expected to be present in the waste water resulting from washing of truck bodies, engines and chassis, i.e., oil and grease and diesel fuel. This waste water also contained some of the surfactant used in the car or truck washing solution to effect removal of the aforementioned constituents.
Table 1 indicates that the influent feed stream passed through the described drum and into contact with the zeolite in the presence of the surfactant therein had a Total Oil and Grease content of 3,920 milligrams per liter (mg/1), which was reduced to 7 mg/l in the effluent, said reduction being equal to 99.8 percent, i.e., substantially 100 percent, of the oil and grease in the feed stream. Concomitantly the Total Petroleum Hydrocarbons-Diesel which was present in the influent feed stream in the amount of 56.6 mg/l was reduced to less than 0.5 mg/l in the effluent, said reduction being equal to more than 99.1 percent, i.e., substantially 100 percent, of the total petroleum hydrocarbons-diesel in the feed stream. Anything approaching these results is unheard of in the art of waste water treatment, particularly with respect to the diesel fuel removal.
TABLE 1______________________________________ Analysis Analysis of WW of After Before TreatmentConstituent Treatment Effluent Units Method______________________________________Oil & Grease, 3920 7. mg/l EPA 413.1TotalTotal Petroleum 56.6 <0.5 mg/l EPA 8015MHydrocarbons-Diesel______________________________________
Table 2 illustrates the results produced by passing a waste water feed stream from a car wash serially through three connected drums of the type used in the treatment of the feed stream which was productive of the Table 1 data. It will be observed that the feed and effluent streams in Table 2 were analyzed for total chromium, as well as for total oil and grease and total petroleum hydrocarbons-diesel.
The feed stream in Table 2 was more dilute than that in Table 1, and passage thereof through the three drums, into contact with the zeolite in the presence of the surfactant in the feed stream, was productive of an effluent content of 9 mg/l of total oil and grease, compared to a feed stream content of 71 mg/1, representing a reduction equal to 87.3 percent of the total oil and grease in the feed stream. The total petroleum hydrocarbons-diesel was present at the level of 94.5 mg/l in the feed stream but was present in the effluent at less than 1 mg/1, representing a reduction equal to more than 98.9 percent, i.e., substantially 100 percent, of the total hydrocarbons-diesel in the feed stream. The total chromium in the feed stream was 553 mg/1, whereas the total chromium content in the effluent was only 0.97 mg/1, representing a reduction equal to 99.8 percent, i.e., substantially 100 percent, of the chromium in the feed stream.
The results in Table 2 conform generally to those in Table 1, as far as oil and grease and total hydrocarbon-diesel are concerned, but the total chromium results show the completely unexpected effectiveness of the invention with respect to removal of substantially all of the chromium from waste water simultaneously with removal therefrom of the oil and grease and diesel fuel. Such removal of a heavy metal from waste water is unheard of in the waste water treatment art.
As an interesting sidelight to the testing reported in Table 2, effluent water produced in this run was transferred to a fish tank as the only liquid therein, and four goldfish were placed in that water. The goldfish lived between eight and fifteen weeks.
TABLE 2______________________________________ Analysis Analysis of WW of After Before TreatmentConstituent Treatment Effluent Units Method______________________________________Oil & Grease, 71 9 mg/l EPA 413.1TotalTotal Petroleum 94.5 <1 mg/l EPA 8015MHydrocarbons-DieselChromium, Total 553 0.97 mg/l EPA 218.1______________________________________
Utilizing the same type of set up as that which was productive of the data in Table 2, a feed stream was prepared by mixing with about 30 gallons of waste water containing oil and grease, about 8 ounces of dry surfactant composition of the type used in car washing solutions, a portion of strontium as strontium chloride, a portion of lead as lead nitrate, a portion of chromium as chromic acid and a portion of ethylene glycol. This feed stream was tested for the amounts of oil and grease, the added metals and ethylene glycol and was passed serially through the drums of the type which were productive of the data in Table 2.
The effluent produced was tested for the presence of the same constituents as the feed stream was, and as shown in Table 3, the oil and grease content of the waste water feed stream was 555 mg/1, whereas the content thereof in the effluent was 7 mg/1, representing a reduction equal to 98.7 percent, i.e., substantially 100 percent, of the total oil and grease in the feed stream. The strontium content of the feed stream was 311 mg/1, whereas the content thereof in the effluent was 0.85 mg/1, representing a reduction equal to 99.7 percent, i.e., substantially 100 percent, of the strontium in the feed stream. The lead content of the feed stream was 26.4 mg/1, whereas the lead content of the effluent was 0.95 mg/1, representing a reduction equal to 96.4 percent of the lead in the feed stream. The chromium content of the feed stream was 67.3 mg/1, whereas the content thereof in the effluent was 0.63 mg/1, representing a reduction equal to 99 percent, i.e., substantially 100 percent, of the chromium in the feed stream. The ethylene glycol in the feed stream was present at less than the minimum detectable limit (MDL) of the test used (i.e., less than 2.5 mg/1).
TABLE 3______________________________________ Analysis of Analysis of Waste Water After Before TreatmentConstituent Treatment Effluent Units Method______________________________________Oil & Grease, 555 7. mg/l EPA 413.1TotalStrontium 311 0.85 mg/l EPA 200.7Calculatedas SrCl.sub.2Lead calculated 26.4 .95 mg/l EPA 239.1as PbNO.sub.3Chromium 67.3 .63 mg/l EPA 218.1TotalEthylene <2.5 <2.5 mg/l EPA 8240Glycol______________________________________
In view of the fact that in the nuclear energy field isotopes of strontium are made dangerously radioactive, the ability of the invention to remove substantially all of the strontium from waste water may contribute to the development of safe disposal procedures for radioactive waste.
Utilizing the same type of set up as was productive of the data in Tables 2 and 3, except that the zeolite used was changed to a clinoptilolite, and about 4 ounces of surfactant of the type generally used in car washing solutions was added to each drum, a feed stream of ocean water was passed serially through the drums. The feed stream, as well as the effluent, was tested for sodium, chloride, pH, and hardness (as CaCo 3 ).
As shown in Table 4, the feed stream sodium content was 8,950 mg/1, whereas the effluent content thereof was 130 mg/1, representing a reduction equal to 98.5 percent, i.e., substantially 100 percent, of the sodium in the feed stream. The feed stream chloride content as 20,100 mg/1, whereas the effluent content thereof was 3,100 mg/1, representing a reduction equal to 84.6 percent of the chloride in the feed stream. The pH of the feed stream was 8.1, whereas the pH of the effluent was 8.0. The feed stream hardness was 6,040 mg/l of CaCO 3 , whereas the effluent hardenss was 312 mg/l of CaCo 3 , representing a reduction equal to 94.8 percent of the CaCo 3 in the feed stream.
This data clearly shows the remarkable effectiveness of the invention for the desalinization of sea water. As noted above, the disparity between the sodium content of the feed stream and that of the effluent represents a reduction equal to 98.5 percent of the sodium in the feed stream. This is also unheard of in the water treatment art, and it is accomplished in inexpensive apparatus, in contrast to the expensive desalination process equipment currently in use.
TABLE 4______________________________________ Analysis of Ocean Water Analysis of Before After TreatmentConstituent Treatment Effluent Units Method______________________________________Sodium 8,950. 130. mg/l EPA 273.1Chloride 20,100. 3,100. mg/l EPA 300.pH 8.1 8. mg/l EPA 150.1Hardness 6,040. 312. mg/l SM2340 Cas CaCO.sub.3______________________________________
For use in the same type of set up as in the previous run, a feed stream of sludge was taken from a settling tank of a truck service station. This sludge was diluted with an equal amount of fresh tap water and the diluted feed stream was analyzed to the extent possible. However, because of the nature of the feed stream, testing for certain constituents was not possible. The before treatment sample was a two phase liquid containing a large percentage of oil., and the analysis was performed on a representative portion of each phase to determine the concentration of the entire sample to the extent possible.
The diluted feed stream was passed serially through the drums, and the effluent was tested for the same constituents as the feed stream, as well as for others for which testing of the feed stream was impossible. The results of this testing are set forth on Table 5 and are particularly notable because of the showing that the invention can simultaneously remove additional metals from waste water, and the consistency in the disparity between the values of the constituents in the feed stream and those of the same constituents in the effluent shown in parentheses below. This disparity is particularly pronounced with respect to the light weight metal barium (8.34/0.04), representing a reduction equal to 99.5 percent, i.e., substantially all, of the barium in the feed stream and the light weight metal boron (1.46/<0.05) representing a reduction equal to more than 65.75% of the boron in feed stream. With respect to the heavy metals (defined as those having a specific gravity of 5.0 or above) the feed stream and effluent values in parentheses, together with the percentage reduction produced, in terms of a percentage of the amount of the respective metal in the feed stream, are as follows: cadium (0.02/0.0011) a reduction of 94.5 percent, chromium (0.51/<0.05) a reduction of more than 90.2 percent copper (19.1/0.08) a reduction of 99.6 percent, i.e., a reduction of substantially 100 percent, iron (184/0.42) a reduction of 99.8 percent, i.e., a reduction of substantially 100 percent manganese (5.02/0.2) a reduction of 96 percent zinc (16.7/0.76) a reduction of 95.4 percent. Table 5 also evidences the fact that with respect to hazardous solvents such as phenolics (0.349/<0.05) the disparity between feed stream and effluent content produced by the invention represents a reduction equal to more than 85.7 percent of the phenolic content of the feed stream. Also notable is the disparity evident with respect to influent and effluent biochemical oxygen demand (41,200/162) a reduction of 99.6 percent, i.e., a reduction of substantially 100 percent and total petroleum hydrocarbon-diesel (147,000/<0.5), a reduction of 99.999 percent, i.e., a reduction of substantially 100 percent, all of which finds no precedent in the prior art.
TABLE 5______________________________________ Analysis of Waste Analysis of Water After Before TreatmentConstituent Treatment Effluent Units Method______________________________________pH 6.9 7.60 Units EPA 9045Arsenic <0.02 <0.02 mg/l EPA 206.3Barium 8.34 0.04 mg/l EPA 200.7Cadmium 0.02 0.0011 mg/l EPA 200.7Chromium, 0.51 <0.05 mg/l EPA 200.7TotalCobalt <0.1 <0.1 mg/l EPA 200.7Copper 19.1 0.08 mg/l EPA 200.7Cyanide, Total <0.30 <0.05 mg/l EPA 9010Iron 184. 0.42 mg/l EPA 200.7Lead 1.72 0.1 mg/l EPA 239.1Manganese 5.02 0.2 mg/l EPA 200.7Mercury <0.001 <0.001 mg/l EPA 245.1Nickel 0.34 <0.01 mg/l EPA 200.7Selenium <0.01 <0.01 mg/l EPA 270.3Silver <0.05 <0.05 mg/l EPA 200.7Zinc 16.7 0.76 mg/l EPA 200.7Phenolics 0.349 <0.05 mg/kg EPA 420.1Biochemical 41,200. 162. mg/l EPA 405.1OxygenDemandSodium 142. 125. mg/l EPA 200.7Boron 1.46 <0.5 mg/l EPA 200.7Total 147,000. <0.5 mg/kg EPA 8015MPetroleumHydrocarbon-DieselTotal 27. mg/l EPA 160.2SuspendedSolidsSurfactant 38. mg/l EPA 425.1(MBAS)LAS Mol.Wt. 342Dissolved <0.10 mg/l SM4500S2-DSulfideOil & Grease 10. mg/l EPA 413.1TotalColor 20. Units EPA 110.2Chloride 74.6 mg/l EPA 300Sulfate 234. mg/l EPA 300Hardness 257. mg/l SM2340 Cas CaCO.sub.3Fluoride 0.13 mg/l EPA 340.2Total Dissolved 653. mg/l EPA 160.1Solids______________________________________
For the next run, the same type of set up as that which was productive of the data in Table 5 was used, except that all of the cellulose pads and beds used therein were of hydrophobic cellulose. No hydrophilic cellulose was used, because it was found that, due to its water absorptivity, it tended to disintegrate too rapidly. The waste water feed stream was taken from a settling tank at the same truck center as that from which the feed stream for Table 5 was taken. The waste water sample was not as thick as the previous one, and it was diluted with an equal amount of fresh water to facilitate analysis for all of the constituents noted in Table 6.
The waste water feed stream was then run serially through the drums and the effluent therefrom was analyzed for the same constituents as the feed stream. Table 6 provides comparative analyses of the feed stream and effluent. Notable disparities between the levels of constituents of the feed and effluent streams can be found in Table 6 with respect to the metals barium (6.34/0.05), a reduction of 99.2 percent, cadium (0.09/0.015) a reduction of 83.3 percent, iron (177/0.56) a reduction of 99.68 percent, i.e., a reduction of substantially 100 percent, lead (0.95/<0.1) a reduction of more than 89.5 percent, zinc (4.92/0.86) a reduction of 82.5 percent, maganese (7.24/0.1) a reduction of 98.6 percent, copper (1.83/<0.05) a reduction of more than 97.3 percent, chromium (0.45/<0.05) a reduction of more than 89.5 percent, and nickel (0.18/0.012) a reduction of 93.3 percent.
Also notable are biochemical oxygen demand (228/81) a reduction of 64.5 percent, total suspended solids (16,300/15.1) a reduction of 99.91 percent, i.e., a reduction of substantially 100 percent, oil and grease (98/17) a reduction of 82.7 percent, sodium (106/63.5) a reduction of 40.1 percent, total petroleum hydrocarbons-Diesel (292/1) a reduction of 99.66 percent, i.e., a reduction of substantially 100 percent, and disolved sulfide (6/<0.1) a reduction of more than 98.3 percent. Since certain sulfide compounds are known to be malodorous, a significant reduction in dissolved sulfides may remove a potential source of air polutions from waste water.
TABLE 6______________________________________ Analysis of Waste Analysis of Water After Before TreatmentConstituent Treatment Effluent Units Method______________________________________pH 8.3 7.2 Units EPA 150.1Arsenic 0.03 <0.01 mg/l EPA 206.3Barium 6.34 0.05 mg/l EPA 200.7Cadmium 0.09 0.015 mg/l EPA 213.2Chromium, 0.45 <0.05 mg/l EPA 200.7TotalCobalt <0.1 <0.1 mg/l EPA 200.7Copper 1.83 <0.05 mg/l EPA 200.7Cyanide, Total <0.05 <0.05 mg/l EPA 335.2Iron 177. 0.56 mg/l EPA 200.7Lead 0.95 <0.1 mg/l EPA 239.1Manganese 7.24 0.1 mg/l EPA 200.7Mercury <0.001 <0.001 mg/l EPA 245.1Nickel 0.18 0.012 mg/l EPA 249.2Selenium <0.01 <0.01 mg/l EPA 270.3Silver <0.03 <0.03 mg/l EPA 272.1Zinc 4.92 0.86 mg/l EPA 289.1Phenolics 0.11 <0.05 mg/l EPA 420.1Biochemical 228. 81. mg/l EPA 405.1OxygenDemandTotal 16,300. 15. mg/l EPA 160.2SuspendedSolidsSurfactant 26.5 17.5 mg/l EPA 425.1(MBAS)LAS Mol.Wt. 342Dissolved 6. <0.1 mg/l SM4-500S2-DSulfideOil & Grease 98. 17. mg/l EPA 413.1TotalColor dark black 50. Units Before visual exam After EPA 110.2Sodium 106. 63.5 mg/l EPA 200.7Chloride 33. 42. mg/l SM4500-C1-BSulfate 29.8 245. mg/l EPA 375.4Hardness 177. 257. mg/l SM2340 Cas CaCO.sub.3Fluoride 1.38 0.26 mg/l EPA 340.2Boron 1.91 1.84 mg/l EPA 200.7Total Dissolved 502. 431. mg/l EPA 160.7SolidsTotal 292. 1. mg/l EPA 8015MPetroleumHydrocarbons-Diesel______________________________________
FIG. 5 illustrates another embodiment of the apparatus of the present invention which, like the embodiments which were discussed earlier herein with respect to the runs productive of tables 1 to 6, does not involve a compartmented tank. FIG. 5 discloses a drum 74, which may be a 55 gallon drum having a cover 75. The cover 75 and drum 74 are adapted to sealingly interfit by virtue of a sealing gasket 116 and a tension band 117 whose function is similar to the tension band 41 in FIG. 3.
The cover 75 is fitted with an internal spray head 76 having an external connection fitting 77 provided with a manual shut off valve 78. The drum 74 is provided with a power driven pump 79 in the bottom thereof having an outlet pipe 80 which sealingly projects through the drum wall to an external connection which may take the form of a shut off valve 80.
Disposed in the bottom of drum 74 also is a table-like structure 81 which comprises a horizontally extending annular ring top portion 82 having four vertically depending legs, three of which appear in FIG. 5 and are numbered 83, 84 and 85. Supported on the annular ring 82 is a circular perforated plate 86 of any suitable material such as plastic or metal. Overlaying the plate 86 is a circular multilayer laminated pad 87 of hydrophobic cellulose fibers. A cylindrical bed 88 of activated carbon beads retained within a plastic mesh bag (not shown) is superimposed on the pad 87, and superimposed on the bed 88 is a cylindrical bed 89 of hydrophobic cellulose pellets also retained within a plastic mesh bag (not shown). A cylindrical bed 90 of zeolite pebbles retained within a plastic mesh bag (not shown) is superimposed on the bed 89.
Disposed within the drum 74 and resting on the zeolite bed 90 is a second table-like structure 91 of the same construction as the structure 81, except that the legs thereof, legs 92, 93 and 94 being shown, are shorter than the legs of structure 81. The annular ring top portion 95 of structure 91 supports a horizontal perforated plate 96 which may be the same as the plate 86. A circular cellulose pad 97, cylindrical bed 98 of cellulose pellets and cylindrical bed 99 of zeolite pebbles, which may be the same as pad 87, bed 89 and bed 90, respectively, are disposed on the plate 96 as shown.
Supported on the zeolite bed 99 is a table-like structure 100 which may be the same as the table-like structure 91, the legs 101, 102 and 103 being shown depending from an annular ring top portion 104. The annular ring 104 supports a circular perforated plate 105, and the latter is overlaid with a circular cellulose pad 106 which is like pads 87 and 97. Superimposed on pad 106 is a cellulose bed 107 which is like beds 89 and 98, and superimposed on bed 107 is a cylindrical bed of zeolite 108 which is like beds 90 and 99.
Supported on the zeolite bed 108 is a table-like structure which is the same as the structures 91 and 100, legs 110, 111 and 112 of which are shown depending from a horizontal annular ring top portion 113. A circular perforated plate 114, which is the same as plates 86, 96 and 105, is supported on the annular ring portion 113, and a circular filter 115 formed of glass fiber overlays the plate 114.
A second drum (not shown) and its contents were then assembled as duplicates of the drum assembly shown in FIG. 5. The inlet fitting 77 of drum 74 was connected to a source (not shown) of a feed stream of waste water, which in the instant case was a thirty five gallon mixing tank. The outlet fitting 80 of drum 74 was connected to the inlet fitting of the second drum.
A feed stream source was prepared in the mixing tank by placing therein 2.5 gallons of sea water, 8 ounces of diesel fuel, 8 ounces of ethylene glycol, 8 ounces of engine oil which had been used and was dirty, and 4 ounces of surfactant of the type used in car washing solutions. The 32 gallon mixing drum was then filled with fresh water up to the 30 gallon level. The drum 74 and its counterpart (not shown) connected in series therewith, were prefilled with fresh water and allowed to soak, after which the fresh water was pumped therefrom.
Prior to opening the valve 78 to permit the feed stream to flow into drum 74, the contents of the mixing tank were thoroughly stirred and a sample was taken for analysis. The valve 78 and the corresponding valve on the second drum were then opened, and the pump on drum 74 was activated to cause the feed stream to flow from the mixing tank into drum 74 and through all of the zeolite, cellulose and activated carbon beds therein, as well as through the cellulose pads therein. The pump in the second tank was activated to cause the effluent from drum 74 to flow through the second drum, as the feed stream fed to drum 74 flowed through the latter.
The effluent from the second drum was sampled and analyzed for the constituents used in the preparation of the feed stream in the mixing tank. The analytical results with respect to the feed stream and after treatment effluent are shown in Table 7.
The data in Table 7 shows that the form of the invention shown in FIG. 5 also performs in a manner unheard of in the prior art by reducing the total oil and grease from 17,800 mg/l down to 3 mg/l a reduction of 99.98 percent, i.e., a reduction of substantially 100 percent. It also reduces the total hydrocarbon-diesel from 58 mg/l to 0.53 mg/l a reduction of 99.09 percent, i.e., a reduction of substantially 100 percent. Significant reductions are also noted with respect to sodium (939/548) a reduction of 41.6 percent and chloride (1860/773) a reduction of 58.4 percent.
TABLE 7______________________________________ Analysis of Waste Analysis of Water After Before TreatmentConstituent Treatment Effluent 1 Units Method______________________________________Oil & Grease, 17,800 3 mg/l EPA 413.1TotalTotal 58 0.53 mg/l EPA 8015MPetroleumHydrocarbons-DieselEthylene glycol <5,000 <500 mg/l EPA 8015MNote:InterferencespresentChloride 1,860 773 mg/l SMA500-Cl BSodium 939 548 mg/l EPA 200.7pH 7.3 6.9 Units EPA 150.1Hardness as 756 429 mg/l SM2340 CCaCo.sub.3______________________________________
As has been demonstrated by the discussion of the data in tables 1 to 7 herein, the invention is capable of producing up to substantially 100 percent reductions in a wide variety of unwanted substances in waste water, sea water, or soil, such substances including petroleum hydrocarbons, such as oil and grease and diesel fuel, salt, barium, boron, calcium, sodium and strontium, heavy metals, hazardous solvents (phenolics), ethylene glycol and dissolved sulfides. In addition, substantial reductions in biochemical oxygen demand can be effected. Also in contrast to certain other water treatment methods, the invention acts simultaneously on all of the unwanted substances susceptible thereto, rather than on one at a time. Moreover, the invention does not require expensive apparatus to perform its function.
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An apparatus and method for removing unwanted substances from media such as water and soil. Various industrial waste water streams can be treated simply and effectively to remove therefrom such unwanted substances as petroleum hydrocarbons, heavy metals, phenolics, salt, ethylene glycol, and strontium, and sea water can be similarly treated to remove salt as well as petroleum hydrocarbons therefrom. Waste water or sea water is contacted with zeolite in the presence of a surfactant, and optionally hydrophobic cellulose, to effect removal of the unwanted substances therefrom; and soil contaminated with petroleum hydrocarbons, salt or agricultural chemicals can be rejuvenated by mixing the soil with zeolite and a surfactant followed by washing. The apparatus and method provides simultaneous removal of a wide variety of unwanted substances from a feed stream passed therethrough, in contrast to prior art procedures effective to remove only one such substance per treatment. The method is further effective to suppress the formation of foul smelling gas in standing water containing petroleum hydrocarbons and one or more substances tending to promote such gas formation.
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CROSS REFERENCES TO RELATED APPLICATIONS
This application is a division of Ser. No. 028,386, filed Apr. 4, 1979, which is a continuation of Ser. No. 649,995, filed Jan. 19, 1976, both now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to gas-liquid contacting devices and the use of such devices in liquid treatment systems. The invention additionally relates to oxygen-absorption processes requiring repeated and prolonged air-liquid contact in sequential stages. The invention especially relates to methods and apparatus for aeration pumping of sewage in aerobic purification systems such as oxidation ditches and aeration ponds. The invention further relates to processes for treating slurries, particularly water treatment processes employing granular carbon.
2. Review of the Prior Art
Many processes have been developed for absorbing a gas in a liquid in order to effect a chemical reaction that precipitates a solute, decomposes a dissolved compound, bleaches suspended fibers, or forms a desired solution, for example. Some liquid treatment processes require that a gas be absorbed in the liquid in order to support living organisms such as fish or bacteria. Among the liquid treatment processes that support bacteria with dissolved oxygen, commonly termed aerobic processes, a large proportion treat aqueous wastes such as municipal sewage, cannery wastes, dairy wastes, meat-processing wastes, and the like.
Such aerobic processes are commonly accelerated by concentrating and activating the bio-organisms, termed bio-mass or activated sludge, and returning this sludge to be mixed with incoming wastewater which supplies food for the organisms. Activated-sludge processes for aerobic treatment of wastewaters have followed two main lines of development: vertical-flow aeration basins and circuit-flow oxidation ditches.
In an early oxidation-ditch process, Dutch Pat. No. 87,500 discloses horizontally mounted rotors having brush surfaces for adding oxygen to sewage and causing the sewage to flow for a period of time in a closed-loop circuit within an ovally laid-out ditch, the liquid then being clarified by settling and excess sludge being removed. In subsequent developments directed to adding oxygen to sewage and inducing circuit-flow circulation in oxidation ditches, U.S. Pat. No. 3,336,016 discloses an S-shaped duct, U.S. Pat. No. 3,510,110 the combination of a longitudinal partition and a vertically disposed surface aerator which is adjacent thereto, and U.S. Pat. No. 3,846,292 a plurality of subsurface ejector aerators.
Finally, U.S. Pat. No. 3,900,394 discloses a sewage purification process, to be carried out in a circuit-flow oxidation ditch having an impeller-type aerator at one or both ends, which comprises sequential aeration of incoming sewage, aerobic decomposition and depletion of its oxygen content, introduction of additional sewage to the oxygen-starved bacteria, and, simultaneously, aerobic decomposition and denitrification of the additional sewage as the bacteria break down its nitrates.
Returning to the concept of vertical-flow aeration basins, U.S. Pat. No. 1,247,540 teaches a spaced array of subsurface air diffusers in a tank. U.S. Pat. No. 3,452,966 discloses an open-ended vertical tube, with a helical baffle therein for creating turbulence and mixing air and liquid, which is submerged in sewage liquid with its lower end above a gas bubble generator. U.S. Pat. No. 3,479,017 also describes one of several impeller aerators which are vertically disposed for beating the surface of a basin while causing vertical circulation of its contents. U.S. Pat. No. 3,664,638 discloses a static mixer which is presently used as the preferred subsurface aeration device in sewage aeration basins, particularly when mounted as in FIG. 2 of the drawings and spaced in close array on the of the basin bottom.
Vertical-flow aeration basins are typically aerated on a large scale with one or more impeller-type aerators which are vertically mounted and disposed at the surface of the liquid, as discussed in Water & Wastes Engineering, Sept. 1975, pages 76-79, using an aerator such as is described in U.S. Pat. No. 3,479,017 and producing a uniform dissolved-oxygen (D.O.) content of 2.0 mg/liter. Such impeller aerators are frequently mounted within and at the upper open end of a draft tube extending partially or entirely to the bottom of the basin so that the aerator can more efficiently pump liquid from the bottom of the basin, having a depth up to 40 feet, and disperse it over the surface of the basin, thereby improving vertical circulation over a wide area. When fitted with a gear reducer to spin a nine-foot diameter impeller at low speeds, oxygen transfer efficiencies of 3.5 pounds O 2 /hp/hour have been approached.
Returning to the circuit-flow oxidation ditch concept as presently put in practice, only horizontally mounted surface aerators, vertically mounted surface aerators without draft tube devices, and subsurface ejector aerators are used in oxidation ditches having closed-loop or circuit-flow circulation. No static mixers are employed in such oxidation ditches even though subsurface static aeration devices have oxygen transfer efficiencies, rated on a basis of pounds of oxygen transferred to or dissolved in liquid per brake horsepower per hour or per kilowatt-hour, that are equal to or better than the vertically mounted surface aerators and other aeration devices that are presently used in the sewage treatment field. A major advantage of aeration systems using the subsurface static aerator or mixer is that no moving mechanical parts or electrical motors are in contact with or near the liquid being treated because aeration is accomplished by concurrent passage of diffused air and liquid through and mixing within an open-ended vertical tube or conduit having a static internal mixing apparatus. Accordingly, a means for utilizing static mixers in oxidation ditches, while producing circuit-flow circulation therein, is greatly needed.
It is also unfortunate that both horizontally and vertically mounted surface aerators must be used at a relatively fixed level, although the impeller blades of a vertically mounted surface aerator can be slightly varied as to submergence in accordance with dissolved-oxygen content of the liquid being aerated. In contrast, static-mixer aerators can be used in aeration basins in which the surface is varied by two feet or more and also have no limitation as to depth of installation. Accordingly, a depth-variation means is needed for operating impeller aerators within operation ditches in which the depth is varied by several feet in order that these ditches can be available for additional use as storage facilities and for flow equalization of incoming wastewaters.
A basic consideration for this invention derives from the flow pattern, in both oxidation ditches and aeration basins, being principally vertical, with some accompanying horizontal flow in the former. Contact of liquid with air or oxygen is random. No method is available for controlling liquid circulation or frequency of liquid-gas contact. Although frequency of liquid-gas contact appears to be inconsequential because mixing of liquid having various contents of dissolved oxygen soon produces a uniform average content, it is quite important from an efficiency viewpoint. This is so because the necessary driving force increases non-linearly as the dissolved-oxygen content increases.
In consequence, if a portion of the liquid, initially having zero dissolved oxygen, contacts a gas such as air several times, it at first absorbs oxygen very readily but increasingly slowly thereafter. Vertical circulation causes some aerated water to be directly back-mixed into the intake of the aerator. Thus, energy is wasted by attempting to re-aerate water that has already been aerated. A need consequently exists for a flow control method and means for minimizing vertical circulation and turbulent mixing and for bringing liquid and gas into singly occurring contact.
Furthermore, accelerating a mass of liquid to a flow velocity of one foot per second (fps) and decelerating such flow to zero velocity, if in situ clarification in an oxidation ditch is desired, requires both energy and time. A need thus exists for a flow control means for rapidly accelerating and decelerating a mass of liquid, without the random mixing and vertical circulation that presently occurs, in order to combine clarification and aerobic digestion in a sequential procedure within the same oxidation ditch.
Static mixers are hereinafter termed static aerators, whether or not the gas being mixed is air. Impeller-type and submerged-turbine aerators are hereinafter termed surface aerators unless otherwise specifically defined. An aerator is in general a liquid-gas contact pump which is hereinafter to be understood to include a static aerator, a surface aerator, and a fountain discharging a liquid as a jet, spray, and the like into a gaseous atmosphere, such as air.
In prior art treatment of wastewaters, relatively dense foreign objects, which are commonly termed grit, are removed from raw sewage is separate treatment facilities before being sent to an oxidation ditch. A need thus exists, as a matter of simplicity and economy, for a grit-removal method and apparatus by means of which grit can be removed within an oxidation ditch without disturbing its normal aerobic digestive functions so that raw sewage influent can be sent directly from a collection facility to an oxidation ditch without an intermediate grit-removal step.
However, in prior art oxidation ditches, such as those sketched in FIGS. 1 and 4 of the drawings, translational movement of the liquid is created and roughly controlled merely by the momentum effect resulting from the motion of vertically disposed surface aerators, horizontally disposed surface aerators (brush type), or submerged ejector aerators. Turbulence, vertical currents, and non-uniform translational flows interfere with settling of grit in such an oxidation ditch. There is accordingly a concurrent need for a method and means for producing a highly uniform, accurately controlled, and plug-type flow of liquid within an oxidation ditch whereby grit settling and removal therewithin will be feasible.
Static aerators, as they are presently used in vertical-flow aeration basins, receive air from a dispersed grid of air-delivery lines, as indicated in FIG. 2 of the drawings, which are disposed along the bottom of a basin. If inspection, repair, or replacement of a portion of this grid must be performed, the entire basin may have to be partially or even entirely drained, and the static aerators may have to be disturbed. A need accordingly exists for an air delivery means which can be installed in an oxidation ditch and which can be separately removed, inspected, and repaired or replaced without disturbing the static aerators and without requiring drainage of the oxidation ditch.
Static aerators, as presently used for aerating wastewaters, are verticaly disposed and produce not only energy-wasteful mixing of non-aerated water with aeratored water but also vertical circulation of water without appreciable translational movement thereof. A need thus exists for an energy-conserving method and means for horizontally directing the flow of aerated water as it leaves the static aerator.
SUMMARY OF THE INVENTION
An object of this invention is to provide a liquid propulsion apparatus that comprises a barrier means in combination with a gas-contact pump means for producing translational movement of a liquid while absorbing a gas in the liquid.
An object is also to prevent vertical circulation of liquid from the discharge of a pumping device to its intake.
A further object is to provide a mounting means for enabling either a static aerator or an impeller aerator with draft tube to be used for aerating and circulating the liquid in an oxidation ditch without wasteful vertical circulation, random mixing, and repeated aeration of the same liquid.
A still further object is to provide a depth-variation means for enabling an impeller aerator or submerged turbine to be used in either an aeration basin or an oxidation ditch in which depth is selectively variable for storage purposes.
An additional object is to provide a flow-control means for accelerating and decelerating the translational flow of liquid in a channel for a liquid such as an oxidation ditch.
Another object is to provide a mounting means that enables an impeller aerator to be installed anywhere in an oxidation ditch and at any distance from a partition.
Another additional object is to provide a directional-flow intake for conserving and concentrating flow energy in liquid flowing toward the gas-contact pump means.
A further additional object is to provide a directional-flow discharge means for utilizing flow energy in the gas-liquid mixture discharged from the gas-liquid contact pump means to produce useful translational energy.
A still further additional object is to provide an overhead gas delivery apparatus for bringing compressed gas to each static aerator in an array thereof.
Still another object is to provide a means for converting an aeration basin to an oxidation ditch by installing static aerators as the aerating means.
A specific object is to provide an oxidation ditch comprising a grit removal means.
Accordingly, in satisfaction of these objects and in accordance with the spirit and scope of this invention, a barrier means in sealed combination with an aeration means is herein provided that: (1) controls the flow of liquid to the aeration means by allowing flow to occur only through such aeration means, (2) prevents vertical circulation from the exit to the entrance of the aeration means, (3) creates a differential head between an intake body of liquid and a discharge body of liquid on opposite sides of the barrier means having the aeration means as the sole flow-through connecting means, (4) uses the differential head as the energy source for translationally moving the discharge body of liquid, (5) uses the differential head as the energy source for continuously moving the liquid from the discharge body to the intake body in a circuit-flow oxidation ditch, (6) provides a mounting means for a plurality of static aerators, and (7) provides a mounting means anywhere within an oxidation ditch for an impeller aerator in combination with a draft tube, thus enabling an aeration basin having an existing aerator to be converted to an oxidation ditch without requiring a longitudinal partition to be adjacent to the aerator.
This barrier means is a liquid-tight barrier that is sealably attached to a liquid-gas contacting and pumping device between its intake and discharge ends, thereby dividing the liquid in which the pumping device operates into an intake body and a discharge body so that all of the liquid in the intake body must pass through the pumping device to reach the discharge body and none of the liquid in the intake body can pass therethrough more than once.
Operation of the liquid-gas contact pump through the liquid-tight barrier creates a positive differential head because energy has been imparted and transformed into a hydraulic head on the discharge side that is greater than the head on the intake side of the barrier. This differential head is used to provide flow energy for horizontally moving the discharge body of liquid, as in continuous-flow movement to a destination or in circuit-flow circulation within an oxidation ditch. Specifically, the differential-head device of this invention is useful as a flow-control device in both continuous-flow and circuit-flow circulation systems.
The barrier also facilitates controlled acceleration and deceleration of liquid in deep channels such as oxidation ditches. It additionally enables both the quantity flowing through an oxidation ditch and the dissolved-oxygen content therein to be accurately and independently controlled.
The barrier further provides a structure for mounting eithe submerged static mixers or draft tubes for surface-disposed impeller aerators or submerged turbines. The portion of the barrier to which the pumping device is attached may be horizontally, vertically, or obliquely disposed. In addition, a telescopic float mounting means for a surface aerator is provided that enables an oxidation ditch to be utilized for liquid storage and flow equalization of incoming wastewaters.
Translational movement of aerated liquid, as it is propelled by the hydraulic force created by gas-lift pumping through a liquid-tight barrier, is controlled so accurately and uniformly according to the process of this invention that a selected flow velocity can be maintained with negligible turbulence and vertical circulation. The flow is consequently plug-type and thus enables a suitable flow velocity to be selected and maintained so that biodegradable solids can be suspended and, at the same flow velocity and within the same oxidation ditch, grit can be selectively settled and removed. Such velocity-control capability enables this invention to be useful for both open-surface oxidation ditches and enclosed pipeline or continuous flow systems, either above or below grade.
Moreover, the gas-transfer characteristics can be controlled so accurately and independently that a selected dissolved-oxygen content can be maintained at such selected flow velocity without periodic interference therewith. Means are accordingly provided in the oxidation ditches and continuous flow systems of this invention for utilizing this uniform and laminar flow and this independently selectable gas transference so that grit is settled and removed within a circuit-flow oxidation ditch or a continuous-flow system without disturbing the aerobic activity therein.
A directional-flow intake means is also provided for static aerators so that the flow energy of the liquid which is approaching the barrier means is conserved, concentrated, and utilized within the static aerators to obtain more vigorous mixing of liquid and gas. Moreover, a directional-flow discharge means is additionally provided for static aerators so that the flow energy in the gas-liquid mixture being discharged from the static aerators is utilized to produce useful translational movement of the discharged liquid, thus augmenting the flow energy produced by the differential head.
If no directional outlets are attached to the static aerators, they are preferably arranged along a barrier in a regular array. With such directional outlets attached, they are preferably arranged in a staggered array in order to minimize interferences and consequent turbulence among the discharged streams.
A gas-delivery apparatus is further provided for use with either array of static aerators so that a gas, such as compressed air or oxygen, can be delivered from a single header which is controlled by a single valve. Operation of this valve not ony enables gas transference to be selectively maintained but also enables to very large mass of liquid within an oxidation ditch, for example, to be selectively put in motion or selectively stilled for clarifying, settling suspended solids, and removing sludge. This gas-delivery apparatus can be submerged within the intake body of liquid, as is generally known in the art, or it can be disposed overhead with downflow gas delivery lines, each equipped with a control valve, leading to the intakes of the static aerators. Each downflow gas delivery line is preferably coaxially disposed within each static aerator. However, it is also suitable to attach a downflow gas delivery line to the tubular shell, either inside or outside thereof, of a static aerator.
With such clarifying and sludge-removal capabilities, an oxidation ditch can function as the sole treatment facility for a wastewater system, except for storage requirements, particularly if two or more oxidation ditches are rotatively operable so that intermittent clarification and partial sludge removal occur in one of the oxidation ditches while grit settling and removal and aerobic digestion continue in the other oxidation ditches.
Moreover, the oxidation ditches of this invention can provide storage capacity and hence are additionally useful for flow equalization of incoming wastewaters. If the aeration means is a plurality of static aerators, the discharge body of the liquid above the barrier means is provided according to this invention with two or more feet of variable depth so that the surface of the entire oxidation ditch can be raised or lowered by this variable depth, whereby a large amount of liquid can be stored and highly variable flows can be equalized. If the aeration means is a surface aerator, this invention additionally provides a telescopic mounting means for attachment of a floatmounted surface aerator to the barrier means and, in combination therewith, sufficient depth in the discharge body for the surface of the entire oxidation ditch to be correspondingly raised or lowered for flow equalization and storage.
Thus this invention provides apparatuses and methods that are capable of handling all wastewater effluent from a major source by sequentially operating a plurality of oxidation ditches of this invention as follows: (A) intermittently clarifying within and partially removing sludge from one oxidation ditch; (B) simultaneously and continuously settling and removing grit from and aerobically digesting within the remaining oxidation ditches; and (V) simultaneously but intermittently varying the surface levels within the remaining oxidation ditches in response to variations in flows of raw wastewater influent to provide storage and equalization of the flows from the major source.
With a known volumetric flow rate of wastewater from a source of wastewater, such as a municipality, a poultry processing plant, a fruit cannery, a paper mill, or a slaughter-house, for example, an oxidation ditch is designed according to this invention according to the following steps:
A. determine the number of aerators required for oxygen transfer.
B. determine the circuit channel flow rate by multiplying the flow pumping rate of a selected aerator times the number of aerators determined in Step A.
C. multiply the number of aerators by the power requirements of each static aerator to obtain the total horsepower requirements for aeration.
D. dividing the volumetric flow rate by the desired linear flow rate (within the range of 0.75-1.25 ft/sec), that will provide both settling of grit and suspension of biogradable solids, to obtain the needed cross-sectional area of the flow channel, and
E. according to economic factors, determining the width and depth of the flow channel.
Unlike other closed-loop circuit systems, this invention provides the only closed-circuit liquid treatment system. in which a major portion of the reactor basin can be composed of full flowing or partially full flowing pipelines or conduits installed above or below grade and constructed of metal, concrete, fiberglass, or other material pipe or conduit sections that can be shop or field assembled and field connected in reduced time and at reduced cost when compared to field erected concrete or steel tankage presently used in the construction of waste treatment aeration basins. Furthermore, unlike existing closed-loop circuit treatment systems used solely for sewage purification by the activated sludge treatment method wherein air and oxygen is added to the sewage by means of impeller-type surface aerators, horizontal brush-shaped surface aerators, or submerged ejector-type aerators, installations designed according to this invention can be adapted for gas transfer and process mixing use in many water, waste and other liquid treatment processes such as chlorine contact disinfection-post aeration, chemical flocculation, aerated grit removal, aerated flow equalization, activated sludge aeration, extended aeration, flow equalization in combination with activated sludge or extended aeration, aerated grit removal in combination with activated sludge or extended aeration, flow equalization and aerated grit removal in combination with activated sludge or extended aeration, aerated granular or powdered activated carbon contact for soluble organic pollutant removal, and aerated lagoon aeration. In addition, the flow-control apparatuses and methods of this invention are useful for fish farming and shrimp farming, for leaching processes involving mineral ores in slurry form, and for chemical processes involving slurries (such as by absorption of gases to react with a solute and create a precipitated slurry). Installations according to this invention have a minimum capacity limitation of about 5,000 gallons per day and no maximum capacity limitation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an oxidation ditch of the prior art having a longitudinally disposed partition and a surface aerator, rotating about a vertical axis, which is arranged at one end of the partition for aerobic treatment of sewage, somewhat as disclosed in U.S. Pat. No. 3,510,110.
FIG. 2 shows a static aerator of the prior art, comprising a tube having curved sheet-like elements therewithin which are attached to a central mounting shaft, as disclosed in U.S. Pat. Nos. 3,664,638 and 3,794,300, the tube being attached to a concrete block for positioning in a body of liquid to be aerated.
FIG. 3 shows a sewage treatment system of the prior art employing horizontally disposed static aerators as an underground pipeline reactor for mixing oxygen with deaerated sewage and recycled activated sludge while these liquids are enroute to a clarifier, as taught in U.S. Pat. No. 3,607,735.
FIG. 4 shows an aerated oxidation ditch of the prior art in which a bank of ejectors is mounted at considerable depth to aerate a liquid and act as the sole propelling force for moving the liquid around the ditch in a closed-loop circuit, as taught in U.S. Pat. No. 3,846,292.
FIG. 5 is a view in elevation of a two-vessel treatment system constructed according to this invention and having a horizontally disposed barrier which is penetrated by a vertically disposed static aerator connecting an intake body of liquid to a discharge body of liquid for producing a differential head therebetween.
FIG. 6 represents a section in elevation of a flowing liquid system having a barrier between an intake portion and a discharge portion, at least part of the barrier being horizontally disposed and attached to and penetrated by a static aerator which extends thereabove almost to the surface of the discharge portion.
FIG. 7 is a view in elevation of a static aerator which is suspended from the horizontal portion of a barrier in a flowing liquid circuit, the aerator being equipped with an intake bell at its bottom, a directional outlet at its top, and a coaxial air delivery pipe to produce a differential head and flow energy.
FIG. 8 is a perspective view of the upper part of a static aerator which is equipped with a collar and flange for suspending the aerator from a horizontally disposed barrier.
FIG. 9 is a perspective view of a static aerator having an intake bell and a directional outlet as in FIG. 7, with a double collar for attaching the outlet to the aerator and a wide flange for suspending the aerator and sealably covering the large hole in the barrier which permits the aerator to be lifted through the barrier.
FIG. 10 is a sectional elevation through a flowing liquid system having a barrier which is partially inclined and partially horizontally disposed in combination with an aerator device using two static aerators, one being vertically disposed and one horizontally disposed, and further showing the negative psuedo head created by velocity energy.
FIG. 11 represents a section of a flowing liquid system having a vertically disposed barrier which is penetrated by a static aerator having both horizontal and vertical parts which are entirely in the intake portion of the liquid.
FIG. 12 represents a section of a flowing liquid system having a vertically disposed barrier which is penetrated by a static aerator having two vertical parts and an S-turn therebetween, half of the aerator being in the intake body and half in the discharge body of the liquid.
FIG. 13 shows a section of an oxidation ditch having an inclined barrier which is penetrated by five banks of static aerator tubes, all tubes being within the intake body of liquid and reaching to the bottom thereof.
FIG. 14 represents a section of an oxidation ditch having an inclined barrier which is penetrated by five banks of vertically disposed static aerators which are all in the intake body and extend to differing depths therein.
FIG. 15 shows an elevational cross section of a flowing liquid treatment system having three sequentially arranged barriers and gas absorption devices of differing tubular types which cumulatively produce a series of differential heads.
FIG. 16 shows an elevational cross section of a section of a flowing liquid treatment system in which the barrier, as a pair of opposed and spaced-apart sheets having a bubble-splitting means therebetween, forms a rearwardly inclined and sheet-like static aerator which is fed by an elevated gas-supply line.
FIG. 17 is a plan view of an oxidation ditch having a plurality of longitudinally disposed partitions therein and which includes a grit-trapping means, denitrification portion, and an adjacent head-producing aeration means.
FIG. 18 is a cross-section in elevation of the barrier-type head-producing means of FIG. 17, taken on the line 18--18 of FIG. 17.
FIG. 19 is a cross-section in elevation of the grit-trapping means of FIG. 17, taken on the line 19--19 thereof.
FIG. 20 is a perspective view of an exemplary grit-removing means for use with the grit-trapping means of FIG. 19.
FIG. 21 is a plan view of a staggered array of static aerators having directional outlets.
FIG. 22 is a perspective view of a gas-delivering header system for the staggered array of static aerators with directional outlets of FIG. 21.
FIG. 23 is a continuous-flow liquid-treatment system having means for repeated gas absorption treatment in a pair of rows of differential-head devices of submerged static aerators between which the liquid shuttles.
FIG. 24 is an elevation view along one side of the continuous-flow system of FIG. 23, taken on the line 24--24 of FIG. 23.
FIG. 25 is an elevation view along one end of the continuous-flow system of FIG. 23, taken along the line of 25--25 of FIG. 23.
FIG. 26 is a perspective sketch of a section of a continuous-flow pipeline system for treating wastewater along the median of an interstate highway.
FIG. 27 is a plan view of a closed-circuit oxidation ditch for treatment of wate liquors, having at one end a differential-head device which comprises a horizontally disposed barrier and several banks of vertically disposed static aerators suspended from the barrier, in a discharge body of liquid being above the barrier and flowing away therefrom and an intake body of liquid being below the barrier and flowing towards it, so that the ditch may be described as having an intake side and a discharge side.
FIG. 28 is a sectional elevation through the differential-head apparatus of FIG. 26 and taken along the line 28--28 of FIG. 27 through the discharge side.
FIG. 29 is a sectional elevation taken along the line 29--29 of FIG. 27 through the intake side.
FIG. 30 is a sectional elevation across both intake and discharge sides of the oxidation ditch of FIG. 27, taken along the line 30--30 therein, and looking toward the differential-head apparatus.
FIG. 31 is a plan view of an oxidation ditch having a differential-head apparatus, comprising a horizontally disposed barrier and banks of static aerators suspended therefrom, which is arranged in one side of the ditch.
FIG. 32 is a longitudinal sectional elevation, taken on line 32--32 of FIG. 31, which shows the barrier and suspended static aerators therein.
FIG. 33 is a sectional elevation taken across both sides of the oxidation ditch of FIG. 31, taken along line 33--33 thereof.
FIG. 34 is a plan view of an oxidation ditch formed of a U-shaped underground pipe with an exposed differential-head producing means, using a horizontally disposed barrier attached to a plurality of banks of static aerators at one end thereof to connect the pipe.
FIG. 35 is a sectional elevation through the differential-head producing means of FIG. 34, taken along the line 35--35 on the discharge side of the oxidation ditch.
FIG. 36 is a sectional elevation, taken along the line 36--36 of FIG. 34 on the supply side of the oxidation ditch.
FIG. 37 is an elevational cross-section across both portions of the U-shaped pipe of FIG. 34, taken on the line 37--37 thereof.
FIG. 38 is a sectional elevation through a liquid flow system having a barrier separating an intake body of liquid from a discharge body of liquid, with a horizontally disposed portion through which a vertically disposed pipe extends to the surface of the discharge body and is connected to a pump for creating a fountain and a differential head.
FIG. 39 is a sectional elevation across a differential-head apparatus of this invention comprising a draft tube which is slideably but sealably attached to a barrier with a floatation means at the upper end thereof and an impeller-type aerator operating within the draft tube at the surface of the discharge body of liquid.
FIG. 40 is a plan view of a closed-circuit oxidation ditch having a submerged-turbine aerator, creating a differential head through a horizontally disposed barrier at one end of the ditch.
FIG. 41 is a sectional elevation through the differential-head producing means of FIG. 40, taken along the line 41--41 on the intake side thereof.
FIG. 42 is a sectional elevation through the differential-head producing means of FIG. 40, taken along the line 42--42 thereof.
FIG. 43 is a sectional elevation which is exactly like FIG. 42 except that the impeller aerator is operating through a short draft tube extending from the horizontally disposed barrier to the surface only.
FIG. 44 is a plan view of an oxidation ditch having an impeller aerator in a draft tube attached to a differential-head producing barrier along one side of the oxidation ditch.
FIG. 45 is a plan view of an aerator pond of the prior art with partitions arranged to provide closed-circuit flow with repetitive aeration and clarification and, selectively, de-nitrification and including a differential-head producing impeller aerator.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1-4 show the existing state of the art for controlling the horizontal and vertical flows of liquid in aerobic wastewater treatment systems in which oxygen from a gas such as air or tonnage oxygen is dissolved in the wastewater by agitating its surface or by subsurface mixing of liquid with finely dispersed gas.
FIGS. 5-10, 15, 17, 18, and 26-35 relate to static aerators in combination with a barrier, having at least a portion that is horizontally disposed where attached to the static aerators, as a differential-head producing means.
FIGS. 11, 12, and 15 relate to static aerators in combination with a barrier that is vertically disposed, at least where attached to the static aerators, as a differential-head producing means.
FIGS. 13, 14, 15, and 16 relate to static aerators in combination with a barrier that is obliquely disposed, at least where attached to the static aerators, as a differential-head producing means.
FIGS. 17, 18, 21, 22, and 27-37 relate to closed-loop treatment systems using a differential-head producing means comprising banks of static aerators.
FIGS. 23-26 relate to continuous-flow systems using a differential-head producing means comprising banks of static aerators.
FIGS. 39-45 relate to closed-loop treatment systems using a differential-head producing means with impeller aerators.
A differential-head producing means 50 is shown in FIG. 5 in which a first vessel 51 is connected at its bottom to a second vessel 52. Feed liquid 56 continuously enters vessel 51 and passes into the lower part of vessel 52, where it forms an intake body 53. The second vessel 52 has a horizontally disposed barrier 59 therein whih separates intake body or pool 53 from discharge body or pool 54 of the liquid being treated. A static aerator 58 is sealably attached to barrier 59 and is suspended therefrom so that it protrudes into intake body 53 and extends almost to the bottom 55 thereof.
A gas 66 enters an inlet pripe 69 and is fed into the bottom of static aerator 68 through a bubble-producing means so that it entrains the liquid in intake body 53 and at least partially dissolves therein as both liquid and gas pass through static aerator 68 and continue upward as a bubbly stream which forms a boil 64 at the surface thereof. Intake body 53 has head 61, and discharge body 54 has head 62. The difference therebetween is differential head 63 which is produced by the static mixer-and-barrier combination of this invention. Static aerator 58 functions as an energy-imparting and gas-dissolving means through aerator distance 68, and gas 66 dissolves in the liquid above barrier 59 through distance 66 plus free-rise distance 65. The energy in the compressed air 66 is thus imparted to the liquid 56 to create the pressure energy in differential head 63 and to cause gas to be absorbed in the liquid.
The static aerator 58 is essentially a gas-liquid contacting means within a passageway connecting the intake and discharge bodies 53 and 54, respectively, and through which the liquid must pass. The preferred form of static aerator is a plurality of twisted ribbonlike strips, alternatively first disposed clockwise and then directed counterclockwise.
If the pumping action of gas 66 through static aerator 58 were not available, differential head 63 would be a negative head, i.e., head 62 would be less than head 61, representing an energy loss suffered by liquid 56 in passing through the connection between the vessels 51 and 52 and through the static aerator 58. The differential-head producing means 50 of this invention, therefore, overcomes the head-consuming friction represented by a normally encountered negative head and additionally produces differential head 63 which provides a hydraulic gradient that is useful for doing productive work, such as causing the liquid 56, now containing an absorbed portion of gas 66, to flow transversely from vessel 52 as liquid 57. The differential head may be scarcely perceptible in a large channel having relatively few aerators but nevertheless functions as herein described. Generally, the differential head in an oxidation ditch is one to a few inches high.
In FIG. 6, a section of flow system is shown. In this flow system is a differential-head producing means which comprises a barrier and a static aerator which is disposed entirely within the discharge body of the liquid. The barrier has a vertically disposed portion 77 and a horizontally disposed portion 74 which is penetrated by and sealably attached to the lower end of static aerator 75 which extends almost to the surface of the discharge body of the liquid.
Incoming liquid 71 forms the source or intake body of liquid, passes beneath horizontal portion 74 of the barrier, and is entrained by gas 72 diffusing from the inner tube at the bottom of static aerator 75. Gas absorption and channeling of the liquid-gas mixture occurs throughout the length of static aerator 75, and a pronounced boil 76 develops at the surface of the discharge body. Differential head 79 drives the outgoing liquid 73 transversely away from barrier 77.
FIG. 7 discloses a highly preferred embodiment of the invention in which the differential-head producing means 80 comprises a stepped barrier 87 and a static aerator 91 having an intake bell 92 at the lower end thereof and a directional outlet 93 at the upper end thereof to form a propulsion assembly, with a downflow gas delivery pipe 94 coaxially disposed and passing through the directional outlet 93 to the intake bell 92 and having diffusion holes 95 at its lower end for passage of incoming gas 84. The gas delivery pipe 94 can alternately be disposed along the wall of static aerator 91, either inside or outside thereof. Indeed, if the delivery pipe 94 is disposed outside of static aerator 91 and upstream of the upper vertical portion of stepped barrier 87 as downflow line 94a, so that it passes through surface 96 and, for example, terminates in a sparge ring disposed beneath intake bell 92, the entire gas delivery pipe 94 can be raised for inspection and repair without disturbing the stepped barrier 87 or the static aerator 91.
Intake bell 92 is close to the bottom 88 of the intake body of liquid 81, and the intake body 81 and the discharge body 82 are approximately equal in depth, having the same bottom 88. Incoming liquid 83 from the intake body 81 enters the intake bell 92, is entrained by gas passing through diffusion holes 95, moves up static aerator 91, and leaves directional outlet 93 to pass transversely and upwardly as stream 86 toward the surface 97. The differences between intake and discharge heads is differential head 98 and represents a driving force causing outgoing liquid 85 to move transversely away from the differential-head producing means 80.
The attachment means 100 that is shown in FIG. 8 comprises a band 103, which is attached to the tube of static aerator 101, and a flange 105, attached to the band 103, with which a static aerator 101 can be suspended from and sealably attached to a barrier, whether or not the barrier is horizontally disposed.
In FIG. 9, an attachment means 110 is shown which comprises a double collar 117, 118 and a broad flange 119 which is rigidly attached to the collars and is wide enough to fit over a hole 112 in a barrier 111. The collars 117, 118, which are rigidly attached to the flange 119, are also rigidly attached to the tube of the static aerator 113 and to the delivery elbow 115 thereabove, thus joining static aerator 113 and elbow 115. The hole 112 is necessarily large enough to permit intake bell 114 to pass therethrough, so that the aerators 113, with bell 114 and elbow 115, can be bodily lifted upwardly and through the barrier 111 for inspection and repairs.
FIG. 10 shows a section of a flowing liquid treatment system in which incoming liquid 131 being treated is guided downwardly by sloping portion 129 of a barrier of this invention into a depressed pool or body beneath horizontal portion 128 of this barrier. The liquid 131 then enters a static-aerator propulsion assembly 120, passes therethrough, and emerges as directed flow 132 to produce a depressed surface thereabove having velocity energy head 136 which is lower by negative pseudo head 130 than the intake head 135. Shortly thereafter, however, the velocity energy in the propelled and directed outgoing liquid stream 132 is dissipated into pressure energy, resulting in discharge head 137 which is greater than intake head 135 by positive differential head 139. This propulsion assembly 120, which may be arranged as a bank across the entire width of the channel, conserves existing flow energy and additionally directs at least a portion of its imparted energy as augmented flow energy for the liquid 132.
The static-aerator propulsion assembly 120 comprises an intake bell 122, elbow 123, a vertically disposed static aerator 121 which is suspended from and sealably attached to barrier 128, an elbow 124 through which passes a coaxial gas delivery pipe 125, and a horizontally disposed tube 126 which is selectively another aerator or an extension to increase liquidgas contact time and distance. The gas delivery pipe 125 is also suitably disposed, as in FIG. 7, along the periphery of static aerator 121, either inside or outside thereof, and is preferably attached to and disposed below sloping portion 129 of the barrier and then passes vertically downward to the mouth of intake bell 122 so that it can be raised for inspection and repair without interfering with the static aerator 121.
In FIG. 11 is illustrated a section of a flowing liquid system in which a liquid 143 enters a differential-head producing means of this invention and departs as a liquid 149. The differential-head producing means 140 comprises a vertically disposed barrier 144 and a static aerator comprising a vertical part 141 and a horizontal part 142 which is sealably attached to the barrier 144. A gas inlet pipe 145 delivers a finely dispersed gas to the static aerator from which it emerges to form a boil 148 on the surface of the intake body of liquid. One or both parts 141, 142 of the static aerator may be a static mixer device of the same or a different design or one part may be an empty tube. The differential-head producing means 140 creates differential head 147 which serves as a means of energy storage for transversely moving the liquid 149.
A differential-head producing means 150, shown in FIG. 12, comprises a vertical barrier 153 and an S-shaped static aerator 151 which is sealably attached to and on each side of the barrier 153. Finely divided gas from a gas inlet 154 enters the static aerator 151 and passed nearly vertically therethrough to produce a boil 155 on the surface of the discharge body of the liquid and a differential head 158 therein.
A differential-head producing means 160, illustrated in FIG. 13, comprises an inclined barrier 162, extending from the bottom 163 oppositely to the directional flow of the incoming liquid 165. A plurality of static aerators 161, perpendicularly disposed to the barrier 162 and sealably connected thereto, extend almost to the bottom 163 and are fed by dispersed gas from a gas inlet pipe 166. The liquid 165 is entrained by the gas entering the static aerators 161 and then rises through the discharge body of liquid on the far side of the barrier 162, producing differential head 168 which imparts flow energy to outgoing liquid 167.
In FIG. 14, another differential-head producing means 170 is shown which also comprises a rearwardly inclined barrier which is penetrated by a plurality of static aerators 171, 174, each aerator represented being typically a bank of aerators extending across the channel. These static aerators range from short tubes 171 to long tubes 172 but vary in proximity to the bottom 179 of the channel, the shorter aerators 171 approaching most closely and the longer aerators 172 being farthest above the bottom 179. Finely dispersed gas from gas inlets 174, each fed by gas delivery header 173, pass through the static aerators 171, 172 and through the discharge body of liquid 177, entraining liquid from the intake body of liquid 176 into the discharge body of liquid 177 to form differential head 178, thus furnishing flow energy to move the liquid transversely through the liquid treatment system.
FIG. 15 represents a liquid treatment system having three sequentially arranged means for producing a differential head, each being, for illustrative purposes, different in design but the differential heads produced by each being clearly cumulative. Beginning at the left side of FIG. 15, inclined barrier means 180 comprises a barrier having a vertically disposed portion 182 and an inclined portion 181 which is sealably connected to an inclined and perpendicularly disposed static mixer 183.
The middle part of the liquid treatment system shown in FIG. 15 comprises a differential-head producing means 190 having a barrier comprising a vertical portion 191 which is attached to the bottom 196 of the channel, an inclined portion 192, and the upper vertical portion 193 which is connected to a tubular static aerator 195 which is inclined in parallel to the inclined portion 192 and extends almost to the bottom 194, close to the bottom vertical portion 191. In this inclined static aerator 195, there is unusual opportunity for diffusion of gas into liquid through a lengthy contact tube while conserving length of channel.
A differential-head producing means 200 is shown on the right side of FIG. 15, comprising a barrier in three parts and a pair of static mixers. The barrier comprises a lower vertical portion 201, a horizontal portion 202, and an upper vertical portion 203. The static aerators 206 and 207 extend unequally to the bottom 194 and somewhat beyond the horizontal barrier 202 to which they are attached.
Into all of the static aerators, air inlets 184, 194, and 204 feed gas from a gas header 209. Entrained liquid in static aerators 183, 195, 206, 207 sequentially produce the cumulative differential heads 188, 198, and 208.
A sheet or plate-type aerator assembly forms the differential-head producing means 210 of this invention within the section of the liquid treatment system illustrated in FIG. 16. This aerator assembly comprises a pair of sheets 211, 212 having a bubble splitting means 213 therewithin. Although this plate-type aerator assembly can be vertically disposed or inclined forwardly, it is shown as inclined rearwardly, against the direction of liquid flow, in order to conserve space and allow additional time for absorption of the gas by the entrained liquid. The bubble splitting means 213 is suitably a stainless-steel wool or wire packing, closely spaced platelets, or any other bubble-splitting device known to the art. Additional sheets can be added in parallel to and suitably spaced from sheets 211, 212.
Liquid 215 enters a slot in the lower plate 211 close to the bottom of the intake body 216, passes through the packing between the pair of barrier plates 211, 212 and emerges through a slot at the top of barrier 212 and at the bottom of vertical barrier 214 to enter the discharge body of liquid 217. Gas passes through the overhead gas inlet pipe 219 and enters at a plurality of closely spaced points through the upper barrier plate 212, near the bottom thereof, to entrain the liquid 215 and produce differential head 218.
An aeration system 220 with flow-inducing partitions 221, 222, 223 is shown in FIG. 17. Central partition 221 extends from a differential-head producing means 240 at a first end of the basin and nearly to the other end thereof. A U-shaped partition 222 crosses central partition 221 and each of its arms also extends nearly to the other end. A pair of partial partitions 223 are spaced midway between central partition 221 and each arm of the U-shaped partition 222, being parallel to these partitions.
The differential-head producing means 240 is arranged so that its horizontally disposed barrier 243 supports an array of static aerators 244 and divides the contents of the rectangular chamber into a lower intake body and an upper discharge body. The intake body is connected to the contents of the basin 220 by a delivery inlet 245 on one side of partition 221, and the discharge body is connected to the contents of the aeration basin on the other side of partition 221 by the outlet 246, as shown in FIG. 18.
Incoming raw sewage 226 enters at one side of the seration system 220 into which an oxidation basin has been converted and soon passes over grit removal means 230. The sewage then makes five circular flows 224 around the ends of partitions 222, 223, 221, 223, 222. Grit outflow 231 is removed from grit. removal means 230. After the last circular flow 224, the sewage is substantially depleted of oxygen and incoming activated sludge 228 delivers large quantities of hungry bacteria which begin denitrification approximately at zone 229, ending at delivery inlet 245. The action of the static aerators 244, fed with air from air inlet lines which are not shown in the drawings, entrains sewage liquid therethrough and produces differential head 248 which furnishes the flow energy for moving the liquid around oxidation system 220 to inlet 245.
FIG. 19 shows in section an exemplary grit removal device 230 having a plurality of pockets 232 into which grit 233 falls by gravity as the incoming sewage flows thereover. A manually removable pipe 235 sucks grit 231a thereinto which becomes grit outflow 231, as indicated in FIG. 17.
Another suitable grit-removal device is illustrated in FIG. 20 in which a gravity flow line 236 receives grit from a grit pocket 232, leads to a grit valve 237 which is operated by a manual valve handle 239, and drains into a grit standpipe 238.
The static aerators 244 which are attached to the barrier 243 in FIG. 17 are arranged in regular rectangular array and are vertical tubes such as aerator 58 in FIG. 5, aerator 75 in FIG. 6, or aerators 204, 206 in FIG. 15. For static aerators with directional outlets 93 in FIG. 7, delivery elbows 115 in FIG. 9, or elbows 124 with horizontal static aerators 126 in FIG. 10, however, it is preferable to use the staggered array which is illustrated in FIG. 21 in such a differential-head apparatus 240 of FIG. 17 for static aerators 256 producing directed flows 255. Ther barrier 251 of FIG. 21 has holes 252 which are separated by spacings 253, 254, and the flows 255 are directed to provide minimum interference from nearby static aerators 256.
For either a regular or a staggered array of static aerators, a preferred apparatus 250 for delivering a gas, such as air, to the aerators is shown in FIG. 22 where a barrier 251 is equipped with directional-outlet aerators 256, each aerator 256, if constructed as in FIG. 2, being fed with compressed gas through a coaxially disposed downflow line 257 delivering compressed gas to the hollow shaft in its center. Air moves through main header 259 and valve 259v to the plurality of single-bank headers 258 with valves 258v to the downflow lines 257, each having a valve 257v. The valves 259v, 258v, 257v enable any static aerator 256 to be individually checked, removed, repaired, or replaced with negligible disturbance of the system. Moreover, the main valve 259v enables the mass of wastewater in the flow channel to be readily accelerated or decelerated because the restricted passageway represented by static reactors or draft tubes without aeration pumping soon slows the flow of wastewater therethrough when the air is shut off.
Continuous-flow pipeline systems for liquid treatment are illustrated in FIGS. 23-26. The zigzag or folded system 260 fo FIGS. 23-25 is adapted for use on a compact plot and permits light construction, such as warehouses, thereabove. The linear system 340 of FIG. 26 conveys treated liquid to a destination. Both folded and linear continuous-flow systems essentially comprise a plurality of reaction-pipe sections and a plurality of differential-head apparatuses which are each interconnected to and between two of the reaction-pipe sections. According to the hilliness of the terrain, each reaction pipe can be selectively inclined or can be connected to the discharge body and the intake body of the differential-head apparatuses at its intake and discharge ends, respectively, with inclines or declines of selected steepness.
The continuous-flow system 260 comprises criss-crossed pairs of slightly inclined reaction pipes 264, 265 and a pair of rows of side-delivery differential-head apparatuses 263, 266 at the ends of the pipes 264, 265 in addition to vertical-delivery differential-head apparatuses 262a, 262b at the inlet and outlet of the system 260, respectively.
Raw sewage flows through inlet pipe 261 into the intake body of pool 274 in the initial vertical-delivery differential-head apparatus 262a and flows upwardly through static aerators 268.
The discharge of each pipe 264 enters the intake body 274 of each apparatus 263, 266, 262b, and the aerated liquid in each discharge pool 275 enters the inlet of each pipe 264, 265 after having received dissolved gas, such as oxygen, from passage through the static aerators 268 in which a gas, such as air, flows from downflow lines 272 which are fed from gas headers 271, as most clearly shown in FIG. 25. The last pipe 265 enters the intake body in differential-head apparatus 262b so that liquid, which has been aerated in eight apparatuses 263, 266 and in two apparatuses 262a, 262b, leaves the discharge pool in final device 262b through outlet pipe 269 which can be oriented in any direction.
The system of FIGS. 23-25 is designed to handle a given flow of rae sewage per day at one foot per second when constructed of pipes 261, 264, 265, 269 having a 9-foot diameter, with pipes 264, 265 being 1,200 feet in length. The differential-head apparatuses 262a, 263, 266, 262b are conveniently open to the atmosphere. The differential head in each apparatus 262a, 263, 266, 262b, represented by liquid surfaces 277 in FIG. 25, furnishes the driving force for moving the sewage through the next pipe 264 or 265. The residence time is about four hours, and the flow-through time is approximately 22 minutes between aerations.
The continuous-flow system 340, a section of which is illustrated in FIG. 26, is conveniently embedded in the median 346 of an interstate highway having paved roads 347 and vehicular traffic 348. A horizontal pipe 341 is connected to a steeply inclined pipe 342 which is attached to the intake portion of a differential-head device 343. A slightly inclined pipe 344 is connected to the discharge portion of the apparatus 343 and is in turn connected to the intake portion of the differential-head apparatus 345. Another pipe 349 is connected to the discharge portion of apparatus 345. Continuing in this manner, the system 340 can pass through level and even slightly rolling country from a municipality to a disposal plant, such as a chlorination plant and an activated-carbon polishing plant employing static aerators in a differential-head apparatus of this invention. The highly purified effluent is then discharged into a natural body of water, such as a lake or river.
The closed-circuit oxidation ditch 280 which is shown in FIGS. 27-30 comprises a U-shaped flow channel, having sides 281, a bottom 283, a central partition 282, and a square aeration pumping apparatus 290 at one end opposite to the semicircular end. As clearly seen in FIG. 29. the bottom 283 begins at 284 to decline sharply to meet bottom 298 of the intake body beneath horizontal barrier 292 which is sealably attached to vertical barrier 291 which extends across the intake channel, from one side 281 to the end of the partition 282, and which continues across the discharge channel as submerged side 295 of the intake body.
An array of static aerators 293 is sealably attached to and suspended from the horizontal barrier 292 and extends nearly to the bottom 298. Some of the static aerators 293 are shown with bottom supports 294 as alternative but not preferred supports.
Raw sewage 301 enters the oxidation ditch 280, at a point subsequent to the aeration pumping apparatus 290 and subsequent to the outflow 306 of digested sewage, and joins the aerated sewage to form flow 302 which is joined by inflow 304 of activated sludge. The mixture of aerated sewage, raw sewage, and sludge moves past circular flow baffle 286 to become oxygen-depleted flow 303. Circular flow baffle 286, as is known in the art, promotes uniform, plug-type flow around the semicircular end.
The locations of the outflow 306, raw sewage influent 301, and sludge inflow 304 are not critical. The outflow 306 can indeed be located along any of the three outer sides of the discharge body above horizontal barrier 292, and the influent 301 can be located anywhere along the sides 291 and 281 that avoids backmixing with the outflow 306, but it is desirable to locate it reasonably close to or within the aeration pumping apparatus 290. The hydraulic gradient or differential head 309, shown by the drop from the liquid surface of the discharge body to the liquid surface of the approach to the intake body, represents hydraulic friction (energy loss) encountered during circuit flow around the oxidation ditch.
After mixing with sludge inflow 304, nitrates are broken down to supply oxygen, and nitrogen is liberated. This denitrification continues until the flow 303, having intake head 307, enters the static aerators 293 wherein an air delivery line (not shown in FIGS. 27-30) discharges finely dispersed air to pump the liquid upwardly as flow 305 and form discharge head 308 which is greater by differential head 309 than intake head 307. The potential energy in differential head 309 is gradually converted to flow energy which moves the liquid in the discharge body as flows 302, 303 within the channels of the oxidation ditch 280.
EXAMPLE
The following design calculations are for an oxidation ditch having a channel width of 10.5 feet and depth of 10 feet and a flow capacity of one million gallons per day of wastewater with 250 mg/l BOD(5), 250 mg/l suspended solids, and 30 mg/l NH 3 -Nitrogen, using static aerators for air-lift pumping.
(1) Oxygen requirements=1.5#O 2 /#BOD(5) applied +4.6 #O 2 /#NH 3 --N converted to nitrate nitrogen.
(2) Aeration basin design criteria:
(a) MLSS (Mixed liquor suspended solids)=4,000 mg/liter
(b) Food-to-microorganism ratio=0.05 # BOD/#MLSS (Mixed liquor suspended solids)
(c) Oxygen transfer efficiency correction factor at 21° C. to standard condition oxygen transfer requirements=1.40 for process condition oxygen transfer requirements.
(3) Typical system design
(a) Oxygen demand at process conditions=178.3 #O 2 /hour
(b) Oxygen demand at standard conditions=249.6 O 2 /hour
(c) Number of aerators for an aeration-pumping unit operating depth of 20.0 feet at 25 scfm (Standard Cubic Feet per Minute of air per aerator-from manufacturer)=60 units
(d) Total pumping rate at pumping rate per static aerator of about 800 gpm (from manufacturer)=48,000 gpm=107 cfs
(e) Barrier Dimensions, using aeration-pumping barrier as platform for 60 aerators in four rows of seven units and four rows of eight units, all four feet apart on center in regular array, is 32 feet square.
(f) Estimated Brake Horsepower for 60 aerators at 25 scfm per aerator in 20 feet water depth=73.2 HP.
(4) Design of aeration basin
(a) Volume=1.25 million gallons=167,089 ft 3
(b) Cross Sectional Area of closed circuit channel=107 ft 2
(c) Velocity in channel having depth of 10.0 feet and width of 10.5 feet=1.02 fps
(d) Channel Length=1,591 feet
(e) Time for Flow to pass around closed circuit=26 minutes.
The closed-circuit oxidation ditch 310 of FIGS. 31-33 is similar to the oxidation ditch 280 of FIGS. 27-30 except that the ovally laid-out flow channel has inclined sides with longitudinal bottom edges 316, earthern dividing strip 318, and a differential-head apparatus in one side channel. The slope for the sides, expressed as a horizontal:vertical-distance ratio, can be varied from 1:1 to 3:1. The flow of de-oxygenated wastewater moves down the decline having boundaries 317 as it meets vertical barrier 311 and forms the intake body beneath horizontal barrier 312, having intake bottom 314 and end 315. Static aerators 313 are sealably attached to and suspended from barrier 312. The liquid is air-lift pumped through the differential-head device to produce differential head 319 which provides the driving force for moving the liquid transversely around the ditch. A portion of the aerated liquid is promptly removed, the remainder mixing with raw wastewater for aerobic digestion and with return sludge for denitrification.
Alternative gas delivery systems 450 are also illustrated in FIGS. 30-33. A main header 451 delivers compressed gas to header valve 452 which admits gas to the overhead header 454 having selecter valve 454 or to the upstream header 457 having selecter valve 456. Downflow lines 457 lead from overhead header 453 to a submerged header 458 which is also connected to upstream header 457. Feeder-sparge lines 459 deliver gas from submerged header 458 to the intakes of each static aerator 313. An operator is consequently able to select overhead delivery by opening valves 452 and 454 and closing valve 456 or to select submerged delivery by closing valve 454 and opening valves 452 and 456. When the operator closes valve 452, the entire mass of liquid in the oxidation ditch 310 is quickly slowed, as when beginning a clarification procedure. When valve 452 and either valve 453 or valve 456 are opened at the end of a clarification procedure, the mass of liquid in the entire oxidation ditch is rapidly set in motion because backflow through the barrier means 311, 312 is impossible.
A closed-circuit pipeline reactor 330 of FIGS. 34-37 is underground except for approach zone 338 and differential-head apparatus 320 at one end of the U-shaped pipe which is oval in cross section and has sides 331. One half is aeration pipe or channel 332 and the other half is return pipe or channel 333. The differential-head apparatus 320 comprises a horizontal barrier 322 and a sealably attached vertical barrier 321 which is submerged across its discharge side to channel 332 as merely a side of the intake body 323 beneath horizontal barrier 322 but which extends above the liquid level on the intake side along the approach zone 338. A plurality of static aerators 325 are sealably attached to and suspended from horizontal barrier 322, extending downwardly close to bottom 328 of intake body 323. In the approach zone 338, having one side 338a, an inclined bottom 339 connects pipeline sides 331 of intake channel 333 to bottom 328.
The oval sides 331 of the U-shaped pipe in FIGS. 34-37 represent an arch pipe section, but circular, rectangular, square, and other cross-sectional conduits or pipe sections are useful and practicable. Preferably, the closed-circuit pipeline reactor 330 operates under submerged inlet and outlet conditions with the channels 332, 333 completely filled under a low hydraulic head. However, submerged operation is not critical to the performance of the closed-circuit pipeline reactor 330 which can be successfully operate with non-submerged inlets and outlets and with channels 332, 333 partially filled.
Raw wastewater, such as municipal sewage or the process discharge waters of a poultry processing plant, a meat processing plant, or the like, enters pipeline reactor 330 as inlet 334, subsequent to sludge return 329, and mixes with the returned sludge and the aerated liquid in aeration channel 332. The mixed liquid moves around the end of island 337 as flow 336 and then moves through return channel 333 into approach zone 338 and intake body 323, passes through static aerators 325 with the assistance of air from delivery pipes (not shown in the drawings) into discharge body 326, and then enters aeration channel 332. A portion continually leaves as outlet 335. Flow energy for this movement is visibly provided by differential head 327, as indicated in FIG. 36.
In FIG. 38, a fountain-aeration differential-head apparatus 350 is shown in sectional elevation as a section of an oxidation ditch. A vertical barrier 351 and a horizontal barrier 352 are sealably attached and extend across the entire channel of the oxidation ditch. A submerged pump 355 is disposed in intake body 353 at the intake end of fountain pipe 356 which passes through and is sealably attached to horizontal barrier 352. Fountain pipe 356 extends upwardly to and slightly beyond the surface of discharge body 354 so that spray 357 and differential head 358 are created by operation of pump 355.
This fountain-aeration apparatus 350 can be substituted for the static-aeration apparatus shown in FIGS. 27-37, but it is preferably used in situations where visual aesthetics have value, such as in apparatuses 343 and 345 of continuous-flow system 340 along an interstate highway.
In FIG. 39, a floating impeller aerator is shown in combination with a differential-head apparatus 360 having a horizontal barrier 361 which extends entirely across a channel, as in an oxidation ditch. A support tube 362 is sealably attached to barrier 361 and has a wear-resistant layer 363 of sealing material, such as a one-half inch thick layer of medium-density polyurethane foam, on its inner side. A float tube 364 slides telescopically within layer 363 and is rigidly attached to horizontal platform 365 which floats on the surface of discharge body 372 and is supported by a floatation means 366, such as rigid polystyrene foam.
A plurality of support struts 369a are attached to the upper surface of platform 365 and converge upwardly to a motor 369 which is centered above float tube 364. An impeller comprising scoop blades 367 is attached to impeller shaft 368, which is attached to and rotated by motor 369, and operates within float tube 364 at approximately the surface of discharge body 372. Thus this float-mounted impeller aerator moves freely upwardly and downwardly as the water level varies, and the impeller can additionallly be varied by a few inches in relation to platform 365, as is known in the art, in response to variations in dissolved-oxygen content of the discharge water.
Incoming liquid 374 in intake body 371 enters tube 362 or 364 (whichever is lower), continues upwardly as upflowing liquid 375 through float tube 364 into the impeller and is flung outwardly as spray 376 onto the surface of discharge body 372. The aerated liquid 377 moves horizontally onward through the channel.
The differential-head apparatus 360 is useful in flow-type systems such as oxidation ditches and continuous-flow pipeline systems if flow equalization thereto is needed and surface levels are selectively varied to provide liquid storage therewithin. However, if flow equalization is not needed, the tube 364 can be rigidly attached to the barrier 361 as a conventional draft tube, with the weight of motor 369 and the impeller being borne by the floatation means 365, 366, not by the barrier 361.
In FIGS. 40-42, a closed-circuit oxidation ditch 380 has a submerged turbine as a surface aerator 390. The ditch 380 comprises a pair of parallel straight sides 381, a pair of curved sides 382 at opposite ends thereof, a central straight partition 386, and a circular guide 383 which is spaced from one curved end 382 and from one end of partition 386. Its bottom 389 declines at 387 and becomes a narrow bottom having edges 388 beneath long draft tube 391.
With shaft 393, motor 394 drives submerged turbine 395 which is disposed at an intermediate depth above an air sparger ring 395a which is supplied with air from an air delivery line 395b and is inside draft tube 391. A vertically disposed barrier 397 blocks flow across the intake channel, being sealably attached to the opposite end of partition 386, to side 381, and to one straight side of a horizontally disposed barrier 396 having approximately a semi-circular shape. The curved side of barrier 396 is sealably attached to the adjacent curved side 382 and to bottom 389 at 392. Draft tube 391 is sealably attached to barrier 396 approximately midway of its length. The floating tube assembly shown in FIG. 39 is suitably substituted for the draft tube 391, however.
Raw sewage 384 enters the intake channel, for example, and mixes with deaerated liquid to form an intake body beneath barrier 396. The mixture then enters draft tube 391, mixes with air from sparge ring 395a, and is flung outwardly as spray envelope 399 onto the surface of the discharge body, producing differential head 398. Turbulent mixing of gas and liquid occurs throughout the spray envelope 399 while the spray passes through the gas atmosphere. A portion of the aerated liquid is withdrawn as outflow 385. The remainder mixes with incoming sludge 384a, moves within the bend formed by curved side 382 and circular guide 383 and is joined by influent 384.
In FIG. 43, a section of the same oxidation ditch 380 is shown in combination with an impeller aerator apparatus 400 which comprises a short draft tube 401, a horizontally disposed barrier 406 which is sealably attached to the intake end of draft tube 401, a vertically disposed barrier 407, an impeller aerator 405 operating within draft tube 401 at its upper end, a drive shaft 403, and a motor 404. Liquid in the intake body beneath barrier 406 enters the draft tube 401 and is flung outwardly as spray 409, creating differential head 408. The floating tube assembly shown in FIG. 39 is also suitably substituted for the fixed draft tube 401.
FIG. 44 shows a closed-circuit oxidation ditch having an impeller aerator apparatus 410 installed in one of its side channels. Similar to the construction of the oxidation ditch of FIGS. 40-43, its bottom begins to decline at 415 in an approach zone which extends beneath vertical barrier 416 to merge with a transversely disposed bottom beneath a horizontal barrier (not visible in the drawing) which extends from its sealed connection at 418 with the bottom of the channel to vertical barrier 416. A draft tube 411, having a motor 414 thereabove to operate an impeller aerator, extends at least to the horizontal barrier and may be a floating draft tube as shown in FIG. 39. Deaerated liquid 412 flows beneath vertical barrier 416 and becomes aerated liquid 413, its driving force being the differential head created by apparatus 410. A portion of the digested liquid is removed as effluent 442. The remainder mixes with influent 443. The mixture aerobically digests while moving in plug-type flow nearly completely around the ditch, being mixed with sludge return 444 shortly before encountering barrier 416.
FIG. 45 shows a typical vertical-flow aeration basins of the prior art which has been converted to an oxidation ditch 420 with an internal clarifier, without relocating or otherwise changing the impeller aerator 421, by adding vertically disposed partitions and a horizontally disposed barrier which is not visible in FIG. 45.
The partitions comprise clarifier partitions 423 having an intake opening for intake flow 437, a discharge opening for clarified discharge flow 439, and a sludge discharge opening for sludge flow 438. Partition 422 is the vertical barrier of the invention across the intake channel to the impeller aerator 421. The discharge body of liquid is bounded by the nearby partition 424, the vertical barrier 422, a transverse partition 424, and a submerged junction 429b of the bottom of the basin with the horizontal barrier. An approach zone to the intake body (which may or may not be excavated to a greater depth) exemplarily begins at 429a if the horizontal barrier is approximately at the depth of the bottom of the basin and the intake body is in an excavation therebeneath. Alternatively, if the horizontal barrier is substantially elevated above the bottom of the basin there is no need for a deepened approach zone so that junction 429a does not exist and junction 429b is a submerged vertical partition which defines the end of the intake body. A pair of outer longitudinal partitions 425, having a length nearly as great as the length of the basin, are parallel to and spaced from the longer sides 428 of the basin and form intake and discharge channels with the longer sides 423 of the clarifier and a pair of long outer channels with the sides 428 of the basin. A pair of end partitions 426, spaced inwardly from the outer partitions 425 and on either side of a central return partition 427, as is generally known in the art, are disposed at the end of the basin opposite to the clarifier. All partitions 423, 424, 425, 426, 427 are connected to each other and to sides 428 with curved baffles 429, as is known in the art.
Incoming wastewater 431, such as industrial food-process wastewater or municipal sewage, selectively enters the basin as influents 432, 433, and 434. The liquid in the channels makes seven circular flows 436 around the ends of the partitions 425, 426, 427 while passing through the basin and through the draft tube of the impeller aerator 421. The liquid can be aerated but once during each such pass and is selectively clarified and de-nitrified within the confines of the prior-art basin by suitable adjustment of flows 432, 433, 434, 438, 439.
In designing, constructing, and operating any system for aerobically treating wastewaters by means of a differential-head producing apparatus of this invention, any desired combination of barrier, draft tube, static aerator, impeller aerator, submerged turbine, float tube assembly, fountain assembly, oxidation ditch, and pipeline reactor may be made, depending upon BOD content, suspended-solids, content, corrosion potential, and flow rate of the wastewaters and upon available land, structural strength of the apparatus, horsepower availability, and the like. For systems for polishing treated wastewaters or potable water with activated carbon, similar latitude is available as to combining liquid-gas contactor devices and auxiliary equipment to manufacture any differential-head producing apparatus of this invention.
Because it will be readily apparent to those skilled in the art that innumerable variations, modifications, applications, and extensions of these embodiments and principles can be made without departing from the spirit and scope of the invention, what is herein defined as such scope and is desired to be protected should be measured, and the invention should be limited, only by the following claims.
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In aerobic wastewater treatment systems, such as sewage treatment, liquid in a channel spanned by a liquid-tight barrier is moved past the barrier by a liquid-gas contact pump, thus dissolving a gas in the liquid and creating a differential head that provides flow energy for moving the liquid in plug-type flow through the channel, which is preferably a continuous-flow pipeline or a circuit-flow oxidation ditch, without energy-wasteful vertical circulation. The barrier further provides a structure for mounting submerged static aerators or a draft tube, in combination with a surface aerator, such as a submerged turbine or surface-disposed impeller aerator, as the liquid-gas contact pump. The barrier is disposed at sufficient depth, when combined with static aerators or when telescopically attached to the draft tube of a floating surface aerator, to enable the liquid level to be selectively varied so that flow equalization to an oxidation ditch and wastewater storage therewithin are provided. Because of the plug-type flow and capability of maintaining it at 0.75-1.25 feet per second, a grit settling capability can be combined with aerobic digestive treatment within the oxidation ditch by placing a grit settling system slightly past the raw sewage inlet in a channel of the oxidation ditch. By employing a plurality of oxidation ditches, of which one is sequential used for clarification, and by incorporating a grit settling system within each of the oxidation ditches, the entire wastewater output from a large municipality, slaughterhouse, or poultry processing plant, for example, can be processed without preliminary or supplementary treatment in any other apparatus.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of my co-pending application Ser. No. 238,044, filed Feb. 25, 1981, and entitled "Traffic Light Control for Emergency Vehicles," which is a continuation-in-part of application Ser. No. 6,351, of the same title, filed Jan. 25, 1979 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention lies in the field of control devices for traffic lights, so as to modify or change the program of lighting, whenever an emergency vehicle is approaching the intersection at which they are positioned.
More particularly, this invention is related to an apparatus and method of control of the traffic lights at a street intersection, during the time interval that an emergency vehicle is approaching the intersection, and has turned on a unidirectional radio transmitter directed towards the receiver at the intersection.
2. Description of the Prior Art
There is considerable art in this area of emergency control of traffic lights. Some of the systems are operated by acoustical signals from an emergency vehicle, others by light signals, and still others by radio signals. Some of the control systems provide a green light for the traffic approaching the intersection in the direction from which the emergency vehicle is approaching and red in other directions. Others have different systems for lighting the traffic lights and so on. However, the system of this invention is designed to provide the greatest protection to individuals and normal vehicle traffic, and to provide as clear a path as possible for the emergency vehicles, than those shown in the prior art.
SUMMARY OF THE INVENTION
It is a primary object of this invention to provide an apparatus and method for emergency control of traffic lights at a street intersection in which lights are controlled by a customary type of traffic light control (TLC), that is adapted to control RED, AMBER, GREEN, WALK and DON'T WALK lights at an intersection.
It is a further object of this invention to provide an apparatus for emergency control of traffic lights by a control means that opens all circuits from the normal traffic light controller to all of the lights handled by that controller, and to substitute electrical power from a control means that applies the power selectively and alternatively to a first group of lights and then to a second group of lights but not to all of the lights.
It is a still further object of this invention to provide for control of the traffic lights under two different conditions--the first is when the vehicle is approaching the lights with emergency lights and siren on, in which case the radio transmitter is in automatic operation; and the other condition is when the emergency signals are not on, but it is still necessary to control the lights, and the manual switch is closed.
These and other objects realized and the limitations of the prior art are overcome in this invention by providing a radio transmitter in an emergency vehicle that has a directional antenna, which is positioned for radiation in the direction in which the vehicle is moving downline to a street intersection, where the signal lights are positioned. Normally a traffic light controller (TLC) is provided to sequentially light each of the traffic lights in a definite time program. In the vicinity of the traffic lights at the street intersection there is positioned an omni-directional radio antenna and a receiver, the output of which goes to a control circuit.
In the transmitter a plurality of oscillatory signals of selected different frequencies are mixed and used to modulate the radio carrier wave. This radiated signal is then detected at the receiver and is demodulated, and the detected frequencies are then sent to a frequency decoder, which, if the frequencies match, identifies the signal as a valid signal and coming from the emergency vehicle. The control then closes certain circuits to provide power to a first interrupter relay, which disconnects all traffic lights from the TLC. The control then selectively applies power on a pulsating basis to selected ones of the lights at the intersection.
The method of operation involves disconnecting all traffic lights, and then flashing in an on/off manner, sequentially, first the RED signal lights and then the AMBER signal lights and back again to RED lights, and then AMBER, and so on. This type of flashing signal in all directions at a single intersection is novel and is not customary in the normal operation of traffic and therefore can be identified as an emergency signal. This signal would instruct all drivers that an emergency vehicle is in their midst and they should move to the curb and stop as soon as possible. This flashing signal of RED/AMBER/RED, etc. can also include the flashing of the DON'T WALK signal light.
Since the GREEN light and WALK light are disconnected, these lights are permanently dark, and the only signals seen and shown in all directions are the sequentially flashing AMBER, RED, and DON'T WALK lights.
In the emergency vehicle, the radio transmitter is powered from a local power source and in the automatic operation is turned on whenever the emergency siren and flashing red lights are turned on. Thus, when the vehicle emergency signal is on, the frequencies F1 and F2 are transmitted sequentially by the radio transmitter. An additional manual switch is provided, so that a manual control can be placed on the transmission. When the manual control is applied, the frequencies F2 and F3 are transmitted simultaneously, and F1 is off.
In the receiver, alternating frequencies F1 and F2 are detected and identified and are used to control a timer which controls an electric switch, which powers the control mechanism. The timer, once tripped, counts to a selected number of clock periods, say thirty seconds, for example. If the F1, F2 transmission is still continuing at that time, the timer resets itself and goes through a new cycle of counts, and so on. If the transmission of frequencies F1 and F2 terminates, that when the counter reaches the limit of its current count cycle, it opens the electric switch.
The control mechanism also has a means to identify the frequencies F2 and F3. If these are received, they control the electric switch to operate the control mechanism without the timer. In other words, when the manual switch is turned off on the vehicle, the control of the electric switch by the frequencies 2 and 3 terminates.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and advantages of the invention and a better understanding of the principles and details of the invention will be evident from the following description taken in conjunction with the appended drawings in which:
FIG. 1 is a schematic diagram of the radio receiver and control circuitry.
FIG. 2 is a schematic diagram of the light control circuitry.
FIG. 3 is a schematic diagram of the radio transmitter system.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings and in particular to FIG. 1, there is shown a block diagram of the radio receiver and control circuitry, indicated generally by the numeral 10. The radio receiver and detector is indicated generally by the dashed box 12. Numeral 14 indicates generally the decoder and logic control circuitry contained within the second dashed outline.
An omni-directional antenna 16 is mounted in the street intersection in the vicinity of the traffic lights, and the radio transmission signal received by the antenna 16 is carried to the radio receiver 12 which is conventional in all respects. The receiver would normally comprise a radio frequency amplifier 18, oscillator 20, mixer 22, IF section 24, and detector 26, all of which are of customary design and well known in the art and need no further description. A power supply unit which provides selected power voltages for the elements of the receiver is indicated by the numeral 52 and is powered by a suitable power source on leads 49 and 50. This power is controlled by switch 51. Such a power supply unit as 52 is also well known in the art and needs no further description.
Referring briefly to FIG. 3, there is shown a block diagram of the electronic apparatus in the emergency vehicle. This comprises a conventional radio transmitter 82 connected to a directional antenna 80, which is mounted on the vehicle with its direction of propagation, or radiation, in the forward direction of the vehicle. A plurality of oscillators or tone encoders 84, 85, and 86 are shown, each one tuned to a different frequency such as F1, F2, and F3, which are selected for their uniqueness, in the sense that there is a minimum of general electrical noise in those frequency bands. The output signals or tones of these three oscillators or tone encoders are carried to a tone mixer 83 which combines the three frequencies and transmits them over line 81 to the transmitter, which modulates the radio carrier wave. The signal then goes to the antenna 80 and is received at the receiver antenna 16 of FIG. 1. The circuitry of the oscillators or tone controllers 84, 85, and 86 and the mixer 83 are conventional and well known in the art and need no further description.
A power supply 94 is provided with two output voltages identified as 2 and 1. The power voltage 2 powers the tone encoders 84 and 85, and the power voltage 1 controls the tone encoders 85 and 86. Furthermore, the power supply is designed to sequentially generate the tones 84 and 85 which are provided in a pulsating alternating fashion, whereas the tones provided by the tone encoders 85 and 86 would be on continuously. Since two pairs of different frequencies are needed, this can be provided by three different frequencies or, of course, by four different frequencies.
The power source 94 is supplied by power from two different sources. A vehicle source of power 88C, 88B supplies power through double pole single throw switch 23 to the power supply 94 through terminal 92. Power is alternatively supplied through switch 23, from a second source of power 88A, 88B to a timer or automatic pulsing device 90, which supplies power to 94 through lead 3-3.
Power on lead 88A comes from a source of power on the emergency vehicle, which also supplies power to the emergency signals on the vehicle, such as flashing lights, siren, etc. Therefore, when switch 23 is connected to 89, and the emergency lights are on, power is automatically supplied to the timer 90 and to lead 3-3. This provides the pulsating power for the two encoders 84 and 85. The continuous power control for the tone encoders 85 and 86 comes from the power supply 94 over lead 1 and is supplied from the source 88C, 88B through the switch 23 and lead 92. In other words, as the emergency vehicle approaches the intersection where the lights are to be controlled, if it has its emergency lights lighted, then the transmitter will be transmitting pulsating signals from 84 and 85 to the receiver. On the other hand, if the emergency light is not on, no transmission will be made unless the manual switch 23 is closed to 92. In that case, steady tone signals from 85 and 86 are then transmitted through the transmitter and antenna through the receiver 12 of FIG. 1. Tone encoder 85 is provided with diodes 85A and 85B so as to respond separately to the power supply voltages 2 and 1 from 94.
The detected signal from receiver 12 goes by lead 28 to each of the tone decoders 30, 32, and 34 in the decoder and logic control unit indicated by the dashed outline 14. Tone decoders 30 and 32 which represent the frequencies 1 and 2 of FIG. 3 control AND gate 36 through leads 37 and 38, and then to a timer unit 44, which closes a switch 48 for a selected period of time, such as 30 seconds, for example.
While the timer 44 is running, a voltage is applied through the diode 45 to the triac switch 48, which closes the circuit between leads 50 and 54. While a particular switch 48 is shown between leads 50 and 54, this is only by way of example, and any other type of controllable switch, such as relay, can, of course, be used. These are connected to output leads A and C which connect to corresponding leads A and C of FIG. 2. Lead B in FIG. 1 goes from the terminal 49 of the power source, whereas terminal C goes from terminal 50 of the power source. As seen from FIG. 1, there is a voltage between leads B and C equal to that across the power leads 49 and 50. Similarly, there is a voltage between leads A and B equal to the voltage between power leads 49 and 50 only when the switch 48 is closed by a voltage output of the timer through diode 45, or through the operation of the AND gate 42 through the diode 46.
The AND gate 42 is controlled by tone decoders 32 and 34 which operate on frequencies 2 and 3 which are effective whenever the manual switch 23 is closed to 92 of FIG. 3. Tone decoders 32 and 34 control the AND gate 42 over leads 39 and 40.
If the manual switch 23, 92 is not closed, the timer 44 is controlled only by the frequencies 1 and 2 which are transmitted whenever the vehicle emergency lights are on. On the other hand, when the manual switch 23, 92 is closed, frequencies 2 and 3 control the AND gate 42, and control the switch 48 directly. After the radio signal from the receiver terminates, such as when the vehicle moves past the intersection and the transmitting antenna no longer points in the direction of the receiving antenna, the signal disappears from lead 28, and therefore, the control on the AND gate 42 disappears and its output signal opens the switch 48, and conditions are then the same as before the vehicle had approached the intersection.
Referring now to FIG. 2, there is shown one embodiment of a control circuit. An interrupter relay, IR 62, is provided, the coil of which is controlled by the switch 48 through lead A, through the IR coil 62, and through lead 64 back to lead B. The interrupter relay 62 has a plurality of contacts 58 and 66, which are controlled in accordance with the dashed lines 74 and 74A.
The group of contacts 58 are placed one in each of the leads 60A, 60B, 60C, 60D . . . 60N, which are connected from the output terminals of the traffic light controller 56, and go to the traffic lights via leads 60. When the interrupted relay 62 is de-energized, all of the contacts 58 are closed, in which case the traffic lights are powered by leads 60 directly from the traffic light controller 56. When this interrupter relay 62 is de-energized, that is, when there is no received signal, the IR contact 66 which is normally operated through the means 74A is open.
The contact 66, which is a normally open contact on the IR relay, is connected from terminal B though lead 64 through a red relay coil 61, through lead 68, through an on/off flasher 70 of conventional design, through the contact 66, and through the line 65 back to terminal C. In other words, power is supplied from the terminals B and C to the red relay 61 through the contact 66 and the flasher 70.
A group of contacts 77 are mounted on the red relay, whose operating coil is 61, through mechanism indicated by the dashed line 76. One side of each of these contacts is powered by lead 64 from terminal B through lead 68, flasher 70, and lead 69 to a contact 77A, and then through each of their remaining contacts 72A, 72B, 72C which individually goes to one or another of the leads 60. Thus, relay contact 72A, which is normally open, goes to lead 60A to the red lights in one direction of travel. Contact 72B connects with lead 60D, which connects with the red lights in the cross-direction of travel. Contact 72C connects with the DON'T WALK lights in one direction. Thus, the red lights are on in all directions when the red relay 61 is energized through lead 68 and flasher 70.
The contact 77A is normally closed and provides power to the coil AR78 of the amber relay. Of course, this power is provided only when contact 66 is closed by operation of the IR relay 62. Closing contact 66 supplies power from B through coil 78 of the amber relay, contact 77A, contact 66, line 65 to C.
The amber relay AR78 controls contacts 73 through means 75. Contacts 73A, 73B, 73C respectively, which are all normally open, control on lead 60B AMBER lights in one direction, on lead 60E AMBER lights in the cross-direction, and on lead 60H the DON'T WALK lights in the cross-direction. Thus the red and amber relays, operating in an alternating manner, responsive to the timing of the flash 70, controlled by coil 71, control the RED and AMBER lights in an alternating manner.
It will, of course, be clear that other types of flashers, or timers can be used in place of 70,71. Also, other types of light sequences can be used, the RED lights in all directions, then on the next half-cycle, all of the AMBER lights, and so on, is the most effective.
Reviewing the circuitry of FIG. 2, when voltage is supplied to terminal A, it goes by lead 63 to the interrupter relay coils 62 which immediately opens the contacts 58 and closes the contact 66. Closing the contact 66 supplies power from lead 65 and terminal C through relay contact 66, through the flasher 70, and lead 68, to the red relay coil 61 and then back to the terminal B. The action of the flasher 70 is to interrupt the current flowing through the red relay coil 61 on an on/off sequential basis. Thus, the contacts 72 which are controlled by the red relay through means 76 sequentially open and close, open and close, selected ones of the contacts 72 which go to the ALL RED and DON'T WALK lights. Contact 77A, normally closed on the red relay, energizes amber relay 78 only when the red relay is de-energized by the pulsating of flasher 70. This produces the ALL RED, then ALL AMBER flashing program.
The overall action, therefore, is that when an approapriate radio signal is received, the switch 48 closes and immediately removes power from all of the lights at the intersection and immediately initiates a pulsating RED light on each of the RED lights and a pulsating AMBER on each of the AMBER lights which is out-of-phase with the RED lights, so it is RED, AMBER, RED, AMBER, and so on. The DON'T WALK lights are also intermittently powered and can be synchronous with either of the RED or the AMBER lights.
When the manual switch 23, 92 is open, the tone decoders 2 and 3 are turned off, and the AND gate 42 is disabled. If at that time the emergency lights on the vehicle are in operation and the tones 1 and 2 are being transmitted, the AND gate 36 keeps the timer 44 operating, and as long as it operates, it maintains the switch 48 in a closed position to keep the flashing lights going on as in FIG. 2. When the manual switch is opened, the automatic switch 23, 89 is closed and the timer 44 then continues its cycle until at the end of its selected interval it has no further radio signal applied to the AND gate 36. Then it opens the power through diode 45 to the switch 48, which disables the switch 48 and causes the interrupter relay to open, terminating the flashing light connections and closing all contacts 58 to the leads 60 from the traffic light controller 56, which is continuing in its normal cycling operation, and then continues to control traffic on that basis.
While the invention has been described with a certain degree of particularity, it is manifest that many changes may be made in the details of construction and the arrangement of components without departing from the spirit and scope of this disclosure. It is understood that the invention is not limited to the embodiments set forth herein for purposes of exemplification, but is to be limited only by the scope of the attached claim or claims, including the full range of equivalency to which each element thereof is entitled.
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A system for controlling traffic lights to clear intersections in advance of the approach of an emergency vehicle, in which a directional radio transmitter and antenna are provided on the vehicle, which transmits one or the other of two selected coded signals in the direction of movement of the vehicle. An omni-directional radio antenna and receiver are positioned at the intersection to receive the radiated signal from the vehicle approaching that intersection. The first coded signal includes a first pair of frequencies, and the second coded signal includes a different pair of frequencies, which are decoded by two similar pairs of filters. The signals cause a sequence of events including a closing of an interrupter relay which opens all circuits leading from the traffic light controller to all of the traffic lights, and controls the closing, alternately, of two sets of selected circuits, to apply power alternately to two selected sets of traffic lights.
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[0001] This application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 60/972,450, filed Sep. 14, 2007, and Application No. 60/972,522, filed Sep. 14, 2007, the disclosures of which are incorporated herein by reference in their entirety for all purposes.
BACKGROUND
[0002] 1. Field of the Invention
[0003] This invention relates generally to the field of clean coal energy production. More specifically, the invention relates to a method of combining two clean coal processes into a single facility.
[0004] 2. Background of the Invention
[0005] Natural gas, coal deposits, and biomass are abundant energy sources that often serve as fuel for power generation. The United States has significant known reserves of coal, and coal currently burned for power generation represents only a fraction of the total deposits that are available. This coal used for power satisfies approximately one-half of the electrical energy demand of the United States. Current and tightening emissions regulations limit the amount of sulfur, oxides of nitrogen, and greenhouse gas emissions, making coals high in these materials less favorable for electricity generation. Failure to comply with these regulations results in hefty penalties in the form of fines, shutdowns, and limited operations. Further, upgrading of current coal burning electric generation plants requires substantial investment. With increased awareness of environmental issues such as global warming, and greenhouse gases, this trend is predicted to continue, potentially making coal-burning plants unfavorable and expensive to operate.
[0006] Rising worldwide oil demand has increased the cost of oil distillates and encouraged development of alternative clean power facilities. One such power production facility is the Integrated Gasification Combined Cycle (IGCC) plant. Electricity is produced from the combustion of a synthesis gas (syngas) produced by the gasification of coal. Gasification is a method of reacting coal with limited oxygen at high temperatures for the production of synthesis gas. The process of gasification removes potential pollutants such as mercury, arsenic, nitrogen oxides, and sulfur oxides. Further benefits are realized when syngas is combusted, as the burning of syngas releases lower amounts of carbon dioxide. The lowered carbon dioxide emissions and technological advances make these facilities “capture ready,” since stored carbon dioxide from the coal is removed in the gasifier.
[0007] Conventional steam turbines require pressure, temperature, and corrosion resistant components to generate electricity. The limitations of these components dictate the upper range of the steam temperatures, and therefore limit efficiency of electric power production. In the case of an IGCC gas turbine, the same limitations do not apply. The gas turbine has a higher gas cycle firing temperature that feeds the compressor, burner, and turbine systems as a means of electricity production. The high-temperature exhaust-gas output of the turbine can be used to heat steam for a supplemental steam turbine, thereby increasing the overall efficiency of an electrical power plant.
[0008] Coal may also be converted to a synthetic liquid fuel by the conversion of syngas. Liquid fuels have an advantage over coal in that they are easily transported long distances without expensive processes or packaging. The process of converting coal to a liquid fuel typically involves a catalytic reaction of syngas to form liquid hydrocarbons. Fischer-Tropsch (FT) reactor facilities execute the vital step of catalyzed synthesis of petroleum substitute liquid fuels. The process occurs via a catalyzed chemical reaction in which the carbon monoxide and hydrogen in syngas are converted into liquid hydrocarbons. The production of liquid hydrocarbon fuels from solid material reduces dependence on oil distillates for fuels. The hydrocarbon production reaction is highly exothermic, and requires a cooled reactor to maintain conditions favorable for continued synthesis.
[0009] The IGCC and FT process represent two potential clean coal processes to reduce dependence on oil distillates. The former provides clean electrical power and the latter provides liquid hydrocarbons for further processing into products. Additionally, both processes require coal processing, air separation, and syngas production for operation. The current costs of material, process, capital, and infrastructure make individual investments in these processes expensive rendering them unfavorable for development. Previous discussions on the combination of facilities for these processes have centered on their shared starting material and parallel infrastructure requirements for the production of syngas. However, it is recognized that provided a singular source of syngas to operate a plurality of clean coal plants is disadvantageous for operational flexibility, the capacity to scale output to demand, and maintain production during maintenance, or in the case of a device failure.
[0010] Accordingly, there is a need in industry for a method of integrating IGCC and CTL facilities with operational flexibility, scalable output, and online maintenance.
BRIEF SUMMARY
[0011] These and other needs in the art are addressed in an embodiment of an integrated Coal to Liquid and Integrated Gasification Combined Cycle facility described herein. A novel method of combining a CTL fuel plant and an IGCC electrical plant by sharing the systems of coal intake, coal preparation, gas separation, and water units is described herein. This configuration allows the combined facility to offer advantages in efficiency of production, operational flexibility, scalability, and reliability by a multi-path integration of the processing units.
[0012] In embodiments, coal is received by the plant, and prepared for gasification in handling and preparation units. Additionally, air is separated into oxygen for gasification, and nitrogen for the IGCC gas turbine unit in a shared unit. The prepared coal and gas are routed to the CTL section or the IGCC section of the integrated facility. The direction of the processed materials transportation depends on factors involving the profitability of a given product, the quantity of processed material necessary to produce the product, and the maintenance status of the equipment. The production and purification of synthesis gas, or syngas occurs in the gasification and purification units, which both sections retain. An aspect of the disclosed process is that the produced syngas in one section may be provided to the adjacent section depending upon the profitability of a given product, the quantity of processed material necessary to produce the product, and the maintenance status of the equipment.
[0013] Byproduct, waste, or tail gases from the CTL section of the facility may be utilized in the IGCC section as a fuel for the gas turbines. In some cases the syngas feed stream to the CTL is not processed, thereby exiting the reactor for gaseous transportation to the IGCC section. These gases may also be recycled to increase the liquid product from the CTL Fischer-Tropsch reactor unit. Water and wastewater units may be shared between the sections of the facility.
[0014] The foregoing has outlined rather broadly the features and technical advantages of the invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] For a detailed description of the preferred embodiments of the, reference will now be made to the accompanying drawings in which:
[0016] FIG. 1 illustrates a schematic of non integrated operations of IGCC and CTL plants;
[0017] FIG. 2 illustrates a process flow diagram according to one embodiment of the method of integrating operations of IGCC and CTL plants;
[0018] FIG. 3 illustrates a detailed process flow diagram according to one embodiment of the method of integrating operations of IGCC and CTL plant;
[0019] FIG. 4 illustrates detailed process flow diagram according to one embodiment of the method of integrating operations of IGCC and CTL plant.
NOTATION AND NOMENCLATURE
[0020] Certain terms are used throughout the following descriptions and claims to refer to particular system components. This document does not intend to distinguish between components that differ in name but not function.
[0021] In the following discussion and in the claims the term “IGCC” is used to refer to an Integrated Gasification Combined Cycle electricity generation plant or facility. Similarly, the term “CTL” or “coal to liquid” is used to refer to a Fischer-Tropsch reactor based plant for the synthesis of liquid hydrocarbons from coal, or coal products without limitation by the individual processes involved. Additionally, the term syngas refers to a gaseous mixture comprised of varying amounts of the main components carbon monoxide and hydrogen with potentially other gaseous molecules.
[0022] In further discussion the term “facility”, “section” and “unit” are used in open ended fashion and thus should be interpreted to mean a premises for a system of components for the execution of a step, or series of steps and associated devices, or apparatuses within the described process.
[0023] In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to . . . .”
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Referring now to FIG. 1 , that illustrates the components of non-integrated facilities for coal to liquid (CTL) fuel production 10 and an integrated gasification combined cycle (IGCC) power plant 20 in a side-by-side manner. CTL facility 10 comprises a Fischer-Tropsch Reactor 47 for the production of liquid hydrocarbons. IGCC facility comprises IGCC gas turbine 53 for the combustion of syngas to produce electricity. Further, FIG. 1 illustrates the parallel or similar coal processing steps used in both the facilities. For example without limitation, these may include coal handling, 31 , 32 coal preparation 33 , 34 and gasifier (gasification unit) 35 , 37 , and syngas purifier 43 , 45 . Additionally, both facilities may comprise a process for gas treatment, water treatment, wastewater treatment, waste removal and/or similar processes understood by one skilled in the art.
[0025] In an embodiment, the disclosed process comprises a multi-path means to integrate the CTL 10 and IGCC 20 facilities. FIG. 2 illustrates a novel integrated facility 30 incorporating an integrated IGCC electrical plant section 20 and a CTL Fischer Tropsch liquid hydrocarbon production section 10 . In an embodiment, the coal handling 31 , and coal preparation 33 units from the CTL facility 10 are shared between both sections. Alternatively, it can be envisioned that the coal handling 31 and coal preparation 33 units are derived from the IGCC facility 20 coal handling 32 and coal preparation 34 units. Coal delivered to the facility arrives at the coal-handling unit 31 , before being moved to the coal preparation unit 33 . The coal is moved between units by conveyors, trucks, slides or other means as known to one skilled in the art.
[0026] Determination of which section requires coal for operations is made and the coal is distributed to the CTL gasification unit 35 , the IGCC gasification unit 37 , or both. The facility receiving the coal may be considered the receiving facility. Alternatively, the facility without active coal reception may be considered the opposite facility. Coal delivered to the CTL facility 10 is processed through gasification 35 , and syngas purification 45 to feed syngas stream 3 . Coal delivered to IGCC facility 20 is processed through gasification 37 and syngas purification 43 to feed syngas stream 3 .
[0027] The section of the integrated facility 30 receiving and processing coal from the coal preparation unit 33 determines the scale and operations of the opposing side. For instance, the IGCC facility 20 has a contract to produce a certain amount of electrical power from IGCC gas turbine 53 . In order to satisfy that contract, IGCC facility 20 uses at least a portion of the output from coal preparation unit 33 through IGCC gasifier 37 and syngas preparation 43 . CTL facility 10 and associated CTL gasifier 35 and syngas purification 45 only utilize remaining portion of coal. In further embodiments, the receiving facility uses all coal; alternatively a portion there of. Further, the opposing facility may supplement syngas stream 3 , which is routed to receiving facility in order to boost production.
[0028] In preferred embodiments, syngas stream 3 is a shared between the CTL facility 10 and the IGCC facility 20 . Syngas stream 3 is routed from either section of the integrated facility 30 to the other. For instance, syngas stream 3 is routed from the CTL facility 10 to the IGCC facility 20 , and vice versa, without limitation. In an exemplary situation, where maintenance requires the temporary shut down of the IGCC gasifier 37 , syngas stream 3 may be routed from the CTL syngas purifier 45 to the IGCC plant 20 . In certain embodiments, gasification units 35 , 37 and syngas purification 43 , 45 may contribute to syngas stream 3 between the facilities.
[0029] Referring now to FIG. 3 , gases required for the gasification of coal are processed and separated in the Air Separation Unit (hereinafter ASU) 39 of the integrated facility 30 . The CTL gasification 35 and IGCC gasification 37 units include their own air separation units. Preferably, the CTL gasification 35 and IGCC gasification 37 units share a single ASU 39 . The primary gas required is oxygen, which is distributed to the CTL gasifier 35 , the IGCC gasifier 37 , or both for the oxidation of coal and production of syngas. As previously discussed in regards to coal, the rate of delivery, and the facility, receiving the oxygen gas determines the scale and operational direction of the integrated facility 30 . The oxygen depleted air, is further separated so as to supply nitrogen to the IGCC gas turbine 53 . The ASU 39 produced gases, such as without limitation, oxygen and nitrogen, are transported inter-facility by enclosed conduits such as without limitation, pipes, tubes, pressurized lines, or tanks. The ASU 39 may utilize any suitable technologies to separate oxygen and nitrogen from air as understood by one skilled in the art. Examples include without limitation, compressors, columns, exchangers, pumps, or combinations thereof.
[0030] FIG. 4 illustrates further potential syngas 3 and off-gas sharing between the CTL section 10 and the IGCC section 20 of the integrated facility 30 . In embodiments, the off gases, produced by Fischer Tropsch reactors 47 and the off gases from the refining unit 51 , can be used to as a co-feed stream 5 with syngas to the IGCC gas turbine 53 . As necessary, the Fischer-Tropsch reactors 47 in the CTL section 10 may have the reaction temperature reversibly lowered. By lowering the temperature outside of the favorable reaction range, the result is the complete expulsion of syngas input as tail gas into co-feed stream 5 for feeding to the IGCC turbine 53 . Without lowering temperature, reactor 47 creates product stream 6 for product refining facility 51 . In certain embodiments, product refining comprises production of diesel, naptha, or other liquid hydrocarbons, without limitation. In further embodiments, the off or tail gases introduced to co-feed stream 5 may be used as a fuel feed to elevate steam temperature at an associated steam turbine generator 49 . In alternative embodiments, the off gases from co-feed stream 5 maybe returned to the reactor 47 through a tail gas recycling facility 59 .
[0031] Further, the IGCC section 20 of the integrated facility 30 may include Fischer Tropsch reactors 47 inline with the syngas supply stream from the purification unit 43 to the IGCC turbine 53 . In this manner, the IGCC section 20 may produce additional liquid fuels as market demands dictate. The tail gases produced in the reactors may be used to power the IGCC turbine 53 . In cases where electrical power is immediately required the temperature of the reactor is sufficiently lowered so that the syngas feed stream exits the reactor as unchanged tail gas. The salient details of this embodiment of the IGCC section 20 are disclosed in U.S. Pat. No. 6,976,362, incorporated herein by reference in its entirety for all purposes. In certain instances, this arrangement may comprise a bolt-on CTL facility 10 incorporated into IGCC facility to form an integrated facility 30 .
[0032] Water may be transported through a system of vessels, pipes, valves, and/or pumps, from the water unit to the entirety of the integrated facility 30 . The water may be supplied to the units of the CTL facility 10 including the reactor 47 , the product refining 51 , the syngas purification 43 and gasification 35 units. In further embodiments, water may be provided to a steam turbine 49 that utilizes heat and steam from the other units to produce quantities of electricity. The other units may comprise any portion of the integrated facility 30 , that generates suitable thermal waste, or heat for producing steam. Additionally, water may be routed from the gasification unit 35 to coal preparation unit 33 . The coal preparation facility 33 is shared by both CTL 10 and IGCC 20 plants. Water supplied to each unit of the CTL section 10 may be routed through other units in the integrated facility 30 , disconnected, or removed completely for treatment off premises, without limitations.
[0033] Water may also be transported to the IGCC syngas purification unit 43 , the gas turbine 53 and the heat recovery steam generator (hereinafter HRSG) 55 . Steam from HRSG is cycled to steam turbine 58 . Steam turbine 58 may produce additional electrical power. In further embodiments, water is provided to the IGCC gasification unit 37 . The IGCC gasification unit 37 may further provide water to the coal preparation unit 33 shared by the CTL 10 and IGCC 20 sections. Water supplied to each unit of the IGCC section 20 may be routed through other units, disconnected or removed completely, as known to one skilled in the art.
[0034] A wastewater treatment unit 57 may be included in the integrated facility 30 . The wastewater treatment unit 57 drains the syngas purification units 43 , 45 , the gasification units 35 , 37 , the CTL reactor 47 , the CTL product refining facilities 51 , the coal preparation unit 33 , and the IGCC gas turbine 53 of used water. Wastewater removal from individual units of the integrated facility 30 may be alternatively coupled, routed through other units, or omitted from the system. The wastewater may be recycled, reused, or treated and expelled from the integrated facility.
[0035] While embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described and the examples provided herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims.
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A novel method of combining the CTL fuel plant and IGCC electrical plant by sharing the systems of coal intake, coal preparation, gas separation, and water units is described herein. This configuration allows for the combined facility to offer advantages in efficiencies of production, operational flexibility, scalability, and reliability by a multi-path integration of the processing units.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a Section 371 filing of International Application No. PCT/DK2005/000285, filed 26 Apr. 2004, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a skin-protecting alkalinity-controlling composition as well as the use of a composition comprising at least one carboxylic acid polysaccharide for skin protection and/or alkalinity control.
[0003] Pectin is a complex polysaccharide associated with plant cell walls. It consists of an alpha 1-4 linked polygalacturonic acid backbone intervened by rhamnose residues and modified with neutral sugar side chains and non-sugar components such as acetyl, methyl, and ferulic acid groups.
[0004] The neutral sugar side chains, which include arabinan and arabinogalactans, are attached to the rhamnose residues in the backbone. The rhamnose residues tend to cluster together on the backbone. So, with the side chains attached, this region is referred to as the hairy region and the rest of the backbone is hence named the smooth region.
[0005] In U.S. Pat. No. 5,929,051, Ni, et al. pectin is described as a plant cell wall component. The cell wall is divided into three layers, middle lamella, primary, and secondary cell wall. The middle lamella is the richest in pectin. Pectins are produced and deposited during cell wall growth. Pectins are particularly abundant in soft plant tissues under conditions of fast growth and high moisture content. In cell walls, pectins are present in the form of a calcium complex. The involvement of calcium cross-linking is substantiated by the fact that chelating agents facilitate the release of pectin from cell walls as disclosed by Nanji (U.S. Pat. No. 1,634,879) and Maclay (U.S. Pat. No. 2,375,376).
[0006] According to Dumitriu, S.: Polysaccharides, Structural diversity and functional versatility, Marcel Dekker, Inc., New York, 1998, 416-419, pectin is used in a range of food products.
[0007] Historically, pectin has mainly been used as a gelling agent for jam or similar, fruit-containing, or fruit-flavoured, sugar-rich systems. Examples are traditional jams, jams with reduced sugar content, clear jellies, fruit-flavoured confectionery gels, non-fruit-favoured confectionery gels, heat-reversible glazing for the bakery industry, heat-resistant jams for the bakery industry, ripples for use in ice cream, and fruit preparations for yoghurt.
[0008] A substantial portion of pectin is used today for stabilization of low-pH milk drinks, including fermented drinks and mixtures of fruit juice and milk.
[0009] The galacturonic acid residues in pectin are partly esterified and present as the methyl ester. The degree of esterification is defined as the percentage of carboxyl groups esterified. Pectin with a degree of esterification (“DE”) above 50% is named high methyl ester (“HM”) pectin or high ester pectin and one with a DE lower than 50% is referred to as low methyl ester (“LM”) pectin or low ester pectin. Most pectins found in plant material such as fruits, vegetables and eelgrass are HM pectins.
[0010] Pectins are soluble in water and insoluble in most organic solvents. Pectins with a very low level of methyl-esterification and pectic acids are for practical purposes only soluble as the potassium or sodium salts.
[0011] Pectins are most stable at pH 3-4. Below pH 3, methoxyl and acetyl groups and neutral sugar side chains are removed. At elevated temperatures, these reactions are accelerated and cleavage of glycosidic bonds in the galacturonan backbone occurs. Under neutral and alkaline conditions, methyl ester groups are saponified and the polygalacturonan backbone breaks through beta-elimination-cleavage of glycosidic bonds at the non-reducing ends of methoxylated galacturonic acid residues. These reactions also proceed faster with increasing temperature. Pectic acids and LM pectins are resistant to neutral and alkaline conditions since there are no or only limited numbers of methyl ester groups.
[0012] Pectin is a weak acid, and is less soluble at low pH than at high pH. Thus, by changing the pH of the pectin during manufacture thereof, a pectin having lower or higher solubility is provided. The pH is typically increased through the use of bases such as alkali metal hydroxides or alkali metal carbonates, but other bases are equally useable. For instance, by using sodium carbonate, sodium pectinate is formed and the higher the dosage of sodium carbonate and, thus, the higher the pH, the more of the carboxylic acids are transformed to their sodium salts.
[0013] However, at higher pH the pectin starts to de-esterify during pH-adjustment, handling and storage. Thus the pH should be maintained at a level at or below pH 6.
[0014] In some cases, pectin as manufactured is esterified in a block-wise fashion. WO 2004020472 describes this phenomenon as the block-wise de-esterification takes place in the raw material used for making pectin, and the disclosure relates to a method for eliminating this block-wise de-esterification.
[0015] WO 8912648 discloses a method for transforming block-wise de-esterified pectin into pectin with a random distribution of ester groups. The method involves the use of polygalacturonase, which splits the pectin molecule in those areas of the pectin molecule that are non-esterified. Thus, this method provides a lower molecular weight pectin having a higher degree of esterification than the block-wise esterified starting pectin.
[0016] According to Kertesz, Z. I: The Pectic Substances, Interscience Publishers, Inc, New York, 1951, pectic materials occur in all plant tissues. However, apples, beets, flax, grapefruit, lemons, limes, oranges, potatoes, and sunflower are of particular industrial importance. Lately, also the pectin in Aloe Vera has shown industrial utility.
[0017] Pectin according to the present invention needs not be extracted from the pectin containing starting material. Such crude pectin preparations are disclosed in U.S. Pat. No. 2,132,065, U.S. Pat. No. 3,982,003, U.S. Pat. No. 4,831,127, WO 9115517, U.S. Pat. No. 5,354,851, U.S. Pat. No. 5,403,612, U.S. Pat. No. 5,567,462, U.S. Pat. No. 5,656,734, and WO 9749734.
[0018] Other esterified carboxy acid polymers include, but are not limited to:
Pectin ethyl ester, made using ethyl iodide and heating as disclosed by Kertesz, Z. I.: The Pectic Substances, Interscience Publishers, Inc., New York, 251, 1951. In addition, pectic acid and pectinic acid may be totally or partially esterified with aliphatic, arylaliphatic, cycloaliphatic or heterocyclic alcohols. When the acid is only partially esterified, the remaining free carboxyl groups may be salified with inorganic or organic bases. The esters may be used in the pharmaceutical, biomedical, alimentary and cosmetic fields. The esters may be prepared from a quaternary ammonium salt of pectic acid or pectinic acid and an esterifying agent such as a halogenide as disclosed in U.S. Pat. No. 5,384,400. Esterified polysaccharide manufactured with a ketene dimer using an enzyme as a catalyst under mild reaction conditions as disclosed in U.S. Pat. No. 6,624,298. The polysaccharide used is at least one selected from the group consisting of cellulose ethers, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethyl-cellulose, guar, cationic guar, and hydroxypropylguar. Starch esters. Methods for the preparation of starch esters are described in the article by Tessler, M. M. and Bilimers, R. L., Preparation of Starch Esters, in Journal of Environmental Polymer Degradation 4 (1996) 85-89 and further disclosed in U.S. Pat. No. 6,605,715. Polymerized sugar esters as described in U.S. Pat. No. 5,859,217. Esters of alginic acid. Examples include ethylene glycol and propylene glycol esters, methyl ester, homologues of methyl ester, and esters of aromatic, araliphatic, alicyclic and heterocyclic alcohols. Also included are esters deriving from substituted alcohols such as esters of bivalent aliphatic alcohols as disclosed in U.S. Pat. No. 5,416,205.
[0024] According to www.smartskincare.com, sweat is a salty, watery solution produced by sweat glands, numerous microscopic channels opening onto the skin surface. As sebum and sweat mix up on the skin surface, they form a protective layer often referred to as the acid mantle. The skin is mildly acidic. In addition to helping protect skin from “the elements” (such as wind or pollutants), the acid mantle also inhibits the growth of harmful bacteria and fungi. If the acid mantle is disrupted or loses its acidity, the skin becomes more prone to damage and infection. The loss of acid mantle is one of the side effects of washing the skin with soaps or detergents of moderate or high strength.
[0025] According to U.S. Pat. No. 5,837,254, fungal infections of the vagina or urinary tract are difficult to eradicate and frequently recur but are rarely life threatening. The normal pH of the genital tract is 4.5 to 5, which is maintained by lactobacillus. The absence of lactobacillus and a normal pH promotes candidiasis as well as the herpes virus, birth control pills, a weak immune system, genetic factors, stress and a host of other factors, which foster the growth of yeast and fungal infections of the genital tract. Candida albicans grows readily in a moist environment at a pH of more than 5.
[0026] In U.S. Pat. No. 5,972,321 it is stated that although body odor may be partially due to certain chemicals secreted by sebaceous glands and eccrine sweat glands, major axillary (underarm) foul odor is due to secretions of the apocrine glands, which contain special nutrient materials for microorganisms. The apocrine glands secrete a milky fluid that has a pH range of 5 to 6.5 and initially consists of lipids, proteins and carbohydrates. Although gram-positive bacteria, which thrive on substances found on the moist skin surface, appear to be responsible for the production of malodor, the precise mechanisms of odor production are still unclear.
[0027] According to U.S. Pat. No. 4,666,707, bath salt compositions are prepared by incorporating perfume, colorant, plant extract, organic acid and so on into an inorganic salt mixture comprising sodium sulfate, borax, sulfur, sodium chloride, carbonate salt, etc., and are used for the purpose of providing the bath with perfume and/or color, or adequately stimulating the skin to thereby promote the blood circulation, the recovery from fatigue and/or the metabolism. Among such bath salt compositions, there are foaming bath salt compositions comprising a combination of a carbonate salt and an acid, which produces, in the bath, carbon dioxide gas bubbles to thereby cause a relaxing or refreshing sensation and render bathing enjoyable.
[0028] According to U.S. Pat. No. 6,589,923 and U.S. Pat. No. 4,335,025, upon washing with soap, a pH of 8-10 is established in the wash liquor. This alkalinity neutralizes the natural acid mantle of the skin (pH 5-6). Although in normal skin this acid mantle is reformed relatively quickly, in sensitive or pre-damaged skin irritations may result. A further disadvantage of soaps is the formation of insoluble lime soaps in hard water. Being alkaline, soap emulsifies the oily layer covering the natural horny layer (stratum corneum) of a person's skin and neutralizes a likewise natural acid mantle of the epidermis, which has, normally, an acid pH of approximately 5.5-6.5. Failure to readily regenerate the acid and oily part of the epidermis—particularly among older people—often results in dermatological symptoms, such as itching, chapping and cracking of the epidermis, especially in cold weather. Of course, always to be considered is that significant segment of the population, which is allergic to or cannot tolerate conventional soaps in view of a number of reactions (sensitivities) resulting from the use thereof.
[0029] According to U.S. Pat. No. 6,551,987, U.S. Pat. No. 6,013,618 and U.S. Pat. No. 5,626,852, pro-fragrances are compounds, which under certain conditions break down to fragrances. For instance, tris(9-decenyl) when exposed to suitable conditions (e.g., exposure to the acid mantle of human skin) breaks down to release a mixture of 9-decenol and 9-decenyl formate, both of which are fragrance raw materials.
[0030] In U.S. Pat. No. 6,352,700 it is stated that while products exist that are said to address the problems of skin irritation and inflammation, they inevitably fail to address the short-term impact of various additives on the pH balance of the skin, i.e., the skin's acid mantle. To put this into perspective, one need only to consider conventional facial tissue, toilet tissue, napkin and paper towel products that are used for wiping dry or wet skin. Upon contact with skin, the tissue products transfer some of the chemicals present in the tissue to the skin surface.
[0031] According to U.S. Pat. No. 6,150,405 and U.S. Pat. No. 5,667,769, some hair care preparations particularly for treating hair loss, contain hydroxyl scavengers.
[0032] According to U.S. Pat. No. 4,761,279, the application of a conventional shaving preparation of high alkalinity is often irritating to the skin.
[0033] U.S. Pat. No. 2,253,389 discloses the use of alkali to make pectin, which does not require sugar and acid to form gels. A gel is formed by soluble pectin in a neutral or slightly alkaline aqueous medium in the presence of a metal compound, and it is stressed that the alkalinity must be insufficient to convert pectin to pectate. The resulting gelling agent is particularly useful for substituting gelatine in jellies of water and milk.
[0034] GB 541,528 discloses the importance of applying low temperature for demethoxylating pectin. By controlling alkali hydrolysis of pectin at temperatures between 10° C. and the freezing point of the pectin solution, low ester pectin of high setting power and with a low setting temperature can be made. Hydrolysis is performed in an aqueous medium and the hydrolysis is terminated by neutralization. It is disclosed that the hydrolysis is very rapid at pH 12 and very slow at pH 8.5.
[0035] U.S. Pat. No. 2,478,170 discloses pectin with 20-30% remaining acid groups, which gel by the addition of calcium ions, with or without sugar. Alkalis are alkali metal hydroxides, ammonium hydroxide, sodium carbonate, organic ammonium bases etc. and the process involves an aqueous solution or extract of pectin being adjusted to temperatures below 35° C. and pH 10-12. When the desired methoxyl content is reached, pH is reduced to 4, and the pectinic acid is isolated.
[0036] In “The Pectic Substances”, Interscience Publishers, Inc., New York, 1951, Kertesz describes the effect of bases on pectin. When alkali is added to a pectin solution to an extent, which is higher than the amount needed for neutralizing the pectin, demethoxylation commences. This process consumes the alkali and the pH of the solution soon drops. Kertesz also refers to other findings, which suggest that the consumption of alkali increases as a result of the alkali concentration, or the duration of treatment with alkali, or as the temperature of the reaction is raised. Thus, he suggests that this alkali consumption may be utilized for determining the ester content of pectinic acids.
[0037] JP 2001226220 discloses the use of alcohol extracted Citrus junos seed pectin to make a skin lotion composed of said pectin, deep sea layer water and sea water or water. The lotion is characterized by being non-sticky, non-irritant and by having a low pH. Conventionally, pectin is extracted in water, whereas alcohol is known to make pectin insoluble. In addition, the disclosure does not discuss the composition of the pectin.
[0038] WO 02/14374 discloses the use of hydrocolloids as thickening or emulsifying agents for a variety of products, such as foodstuffs, pharmaceutical compositions, personal care products and beverages.
[0039] WO 04/005352 discloses the use of amidated pectins, such as in cremes, lotions and household products.
[0040] U.S. Pat. No. 6,509,311 discloses a gel system comprising propylene glycol alginate as a gelling agent, as a water binder, as an emulsifier and as a stabiliser.
[0041] A need for a composition remains, which is capable of providing buffering, thus avoiding a major increase in the pH of an aqueous system and/or useable for reducing the pH of aqueous systems, in which alkalinity is formed as a result of chemical and/or biological reactions, or as a result of alkalinity being imposed on the aqueous system by the environment. In particular, there is a need for a composition, which will protect the acid mantle, and there is a need for incorporating such a composition in articles, which are in contact with the skin, either human skin or animal skin.
BRIEF SUMMARY OF THE INVENTION
[0042] The present invention thus relates to a skin-protecting alkalinity-controlling composition comprising one or more carboxylic acid polysaccharides wherein at least one of said carboxylic acid polysaccharide(s) is a high DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%.
[0043] The present invention furthermore relates to a skin-protecting alkalinity-controlling composition comprising a mixture of at least one high DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%, and at least one low DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70%, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%.
[0044] The present invention furthermore relates to the use of at least one carboxylic acid polysaccharide for skin protection and/or alkalinity control.
[0045] The invention is disclosed in more detail in the following by means of the accompanying drawings and exemplary embodiments of preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0046] The foregoing summary, as well as the following detailed description of preferred embodiments of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there is shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:
[0047] FIG. 1.1 shows the alkali consumption of pectins of different molecular weight,
[0048] FIG. 1.2 shows the pH-drop over time for the above pectins by dissolution at 70° C.,
[0049] FIG. 1.3 shows the pH-drop over time for the above pectins by dissolution at 20° C.,
[0050] FIG. 2.1 shows the alkali consumption of pectins of different degrees of esterification (DE),
[0051] FIG. 2.2 shows the pH-drop of the above pectins by dissolution at 70° C.,
[0052] FIG. 2.3 shows the pH-drop of the above pectins by dissolution at 20° C.,
[0053] FIG. 2.4 shows the initial about 130 minutes pH-drop of the above pectins dissolved either at 70° or at 20° C.,
[0054] FIG. 3.1 shows the alkali consumption of either a block-wise or randomly esterified pectin of similar DE,
[0055] FIG. 3.2 shows the pH-drop of the above pectins dissolved at either 70° or 20° C.,
[0056] FIG. 3.3 shows the initial about 100 minutes pH-drop of the above pectins,
[0057] FIG. 4.1 shows the pH-drop of a pectin held at various temperatures,
[0058] FIG. 5.1 shows the effect of multiple alkali dosages to a pectin,
[0059] FIG. 6.1 shows the effect of pectin concentration on pH-drop,
[0060] FIG. 7.1 shows the pH-drop of ion-exchanged water without addition of pectin or other additions,
[0061] FIG. 8.1 shows the alkali consumption of propylene glycol alginates (PGA) of different degrees of esterification,
[0062] FIG. 8.2 shows the pH-drop of the above PGAs by dissolution at 70° C.,
[0063] FIG. 8.3 shows the pH-drop of the above PGAs by dissolution at 20° C.,
[0064] FIG. 8.4 shows the initial about 70 minutes pH-drop of the above PGAs by dissolution at either 70° or 20° C.,
[0065] FIG. 9.1 shows the effect of multiple alkali dosages to propylene glycol alginate,
[0066] FIG. 10.1 shows the pH-drop of lotions containing pectin in either the water phase or the oil phase,
[0067] FIG. 11.1 shows the pH-drop of cloth soaked in a solution of 0.01% pectin of different molecular weights,
[0068] FIG. 11.2 shows the pH-drop of cloth soaked in a solution of 0.05% pectin of different molecular weights,
[0069] FIG. 11.3 shows the pH-drop of cloth soaked in a solution of 0.10% pectin of different molecular weights,
[0070] FIG. 11.4 shows the pH-drop of cloth soaked in a solution of 0.20% pectin of different molecular weights, and
[0071] FIG. 11.5 shows the pH-drop of cloth soaked in a solution of 0.50% pectin of different molecular weights.
[0072] FIG. 12.1 shows the alkali consumption of a mixture of 50% of a pectin having a DE of 93.4% and 50% of a pectin having a DE of 9.6% dissolved at 70° C. and compared with the alkali consumption of the individual components.
[0073] FIG. 12.2 shows the pH-drop over time of the above mixture dissolved at 70° C. and compared with the pH-drop of the individual components.
[0074] FIG. 13.1 shows the alkali consumption of a mixture of 50% of a pectin having a DE of 93.4% and 50% of a propylene glycol alginate (PGA) having a DE of 55% dissolved at 70° C. and compared with the alkali consumption of the individual components.
[0075] FIG. 13.2 shows the pH-drop over time of the above mixture dissolved at 70° C. and compared with the pH-drop of the individual components.
[0076] FIG. 14.1 shows the alkali consumption of a mixture of 50% of a propylene glycol alginate (PGA) having a DE of 85% and 50% of a pectin having a DE of 9.6% dissolved at 70° C. and compared with the alkali consumption of the individual components.
[0077] FIG. 14.2 shows the pH-drop over time of the above mixture dissolved at 70° C. and compared with the pH-drop of the individual components.
DETAILED DESCRIPTION OF THE INVENTION
[0078] The skin-protecting alkalinity-controlling composition according to the invention comprises one or more high DE carboxylic acid polysaccharides selected from the group comprising pectin esters, esterified cellulose ethers, esterified hydroxyethylcellulose, esterified carboxymethylcellulose, esterified guar gum, esterified cationic guar gum, esterified hydroxypropyl guar gum, starch esters, and polymerized sugar esters.
[0079] A high DE carboxylic acid polysaccharide provides for a rapid pH-drop due to the low amount of free carboxylic acid groups present. Thus, if a rapid pH-drop is needed, a high DE carboxylic acid polysaccharide should be used. This fact can be utilized in a range of products intended to be applied to the skin of humans or animals. Uses include but are not limited to lotions, creams, foundations, face masks, hair care products, genital lotions, deodorants, ostomy products, feminine hygiene products, laundry products, bath salt products, soap products, fragrance products, lotionized tissue products, and shaving products. Further, such pectin can be used in similar products to treat animals.
[0080] In a preferred embodiment according to the invention, said high DE carboxylic acid polysaccharide is a pectin ester, preferably a pectin ester of aliphatic, arylaliphatic, cycloaliphatic or heterocyclic alcohols, more preferably an ester of methanol, ethanol, propanol or isopropanol, and most preferably an ester of methanol.
[0081] The advantage of using methanol esters of pectin is the natural occurrence of such ester. However, without being bound by theory, methyl esters of pectin are more prone to liberate the alcohol part thereof during de-esterification. Esters of pectin with higher alcohols are not as prone to alkaline de-esterification.
[0082] In a still more preferred embodiment of the invention, said pectin is of a molecular weight in the range from about 5,000 to about 140,000, preferably in the range from about 10,000 to about 125,000, most preferably in the range from about 10,000 to about 40,000. As demonstrated in example 1 below, the molecular weight of pectin has no influence on the alkali consumption or on the pH drop encountered. However, by adjusting the molecular weight of the pectin it is possible to adjust the amount of pectin, which may be dissolved or suspended in a final product. Thus, as disclosed in more detail in example 11, a lower molecular weight pectin is easier to dissolve and the viscosity of the resulting pectin-containing solution is lower than in a corresponding higher molecular weight-containing pectin. This fact can be utilized to obtain a relatively highly concentrated pectin-solution having suitably low viscosity, e.g. for use in fabric-treating products. The pectin having a molecular weight below about 40,000 can be made at concentrations above about 10% without causing unacceptable high viscosity. Such pectin could be manufactured and marketed as a concentrated solution with a pectin concentration in excess of 10%. Alternatively, the possibility of making such pectin solution in concentrations above about 10% makes spray-drying of such solutions economically feasible.
[0083] The degree of esterification indicates the average DE of any given polysaccharide. By controlling the distribution of ester groups along the polysaccharide chain to obtain either a random or a block-wise distribution of ester groups, it is possible to obtain a locally higher or lower DE polysaccharide. As demonstrated in example 3, the alkali consumption of a pectin having a block-wise ester group distribution is the same as the alkali consumption of a corresponding pectin having a random ester group distribution. However, the pH-drop of the two pectins is considerably larger for the block-wise esterified pectin, presumably because such pectin will act as a pectin with a higher average DE. Thus, by treating a block-wise esterified pectin with a polygalacturarase, which splits the pectin at non-esterified sites, a lower molecular weight pectin may be obtained having an increased DE.
[0084] In an alternative embodiment of the composition according to the invention, the ester groups of the polysaccharide thereof are thus distributed in a block-wise fashion.
[0085] In another embodiment of the composition according to the invention, the ester groups of the polysaccharide are distributed in a random fashion.
[0086] In another preferred embodiment according to the invention, the skin-protecting alkalinity controlling composition comprises a mixture of at least one high DE-carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%, and at least one low DE-carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70%, more preferably from about 5 to about 40%, most preferably from 10 to about 35%.
[0087] A carboxylic acid polysaccharide having a relatively low DE provides for a large alkali consumption capacity or buffer capacity.
[0088] An advantage of a higher buffer capacity is the ability of the pectin to neutralize an initial high concentration of alkali. This is an advantage particularly when fabrics are insufficiently depleted for alkaline washing powder. Thus, by combining a low DE and a high DE carboxylic acid polysaccharide, an initial alkali consumption buffering can be obtained succeeded by a pH-reduction.
[0089] In a preferred embodiment according to the invention, any of said high DE carboxylic acid polysaccharides and said low DE carboxylic acid polysaccharides is selected from the group comprising pectin esters, alginic acid esters, esterified cellulose ethers, esterified hydroxyethylcellulose, esterified carboxymethylcellulose, esterified guar gum, esterified cationic guar gum, esterified hydrocypropyl guar gum, starch esters, and polymerized sugar esters.
[0090] In a particular embodiment according to the invention, any of said high DE carboxylic acid polysaccharides and said low DE carboxylic acid polysaccharides is a pectin ester, preferably a pectin ester of aliphatic, arylaliphatic, cycloaliphatic or heterocyclic alcohols, more preferably an ester of methanol, ethanol, propanol or isopropanol, and most preferably an ester of methanol.
[0091] In a more particular embodiment according to the invention, any of said high DE carboxylic acid polysaccharides and said low DE carboxylic acid polysaccharides is a pectin having a molecular weight in the range from about 5,000 to about 140,000, preferably in the range from about 10,000 to about 125,000, most preferably in the range from about 10,000 to about 40,000.
[0092] In an alternative embodiment according to the invention, any of said high DE carboxylic acid polysaccharides and said low DE carboxylic acid polysaccharides is an esterified alginic acid.
[0093] In a preferred embodiment of the invention, any of said esterified alginic acids is an alginic acid ester of aliphatic, aromatic, araliphatic, alicyclic and heterocyclic alcohols, including esters deriving from substituted alcohols such as esters of bivalent aliphatic alcohols, preferably ethylene glycol or propylene glycol alginate. U.S. Pat. No. 5,416,205 discloses suitable alginic acid derivatives, and the reference is enclosed herewith in its entirety.
[0094] In a further embodiment according to the invention, the ester groups of any of said high DE carboxylic acid polysaccharides and said low DE polysaccharides are distributed in a block-wise fashion.
[0095] In another embodiment according to the invention, the ester groups of any of said high DE carboxylic acid polysaccharides and said low DE polysaccharides are distributed in a random fashion.
[0096] In another embodiment of the invention, a composition comprising at least one carboxylic acid polysaccharide selected from the group comprising pectin esters, alginic acid esters, esterified cellulose ethers, esterified hydroxyethylcellulose, esterified carboxymethyl-cellulose, esterified guar gum, esterified cationic guar gum, esterified hydropropyl guar gum, starch esters, and polymerized sugar esters is used for skin protection and/or alkalinity control.
[0097] In a preferred embodiment according to the invention, said carboxylic acid polysaccharide is a pectin ester, preferably a pectin ester of aliphatic, arylaliphatic, cycloaliphatic or heterocyclic alcohols, more preferably an ester of methanol, ethanol, propanol or isopropanol, and most preferably an ester of methanol.
[0098] In another embodiment according to the invention, said carboxylic acid polysaccharide is a pectin having a molecular weight in the range from about 5,000 to about 140,000, preferably in the range from about 10,000 to about 125,000, most preferably in the range from about 10,000 to about 40,000.
[0099] In another embodiment according to the invention, said carboxylic acid polysaccharide is an esterified alginic acid.
[0100] In another embodiment according to the invention, said esterified alginic acid is selected from the group comprising alginic acid esters of aliphatic, aromatic, araliphatic, alicyclic and heterocyclic alcohols, including esters deriving from substituted alcohols such as esters of bivalent aliphatic alcohols, preferably ethylene glycol alginate or propylene glycol alginate.
[0101] In another embodiment according to the invention, the ester groups of said polysaccharide are distributed in a block-wise fashion.
[0102] In another embodiment according to the invention, the ester groups of said polysaccharide are distributed in a random fashion.
[0103] In another embodiment of the use according to the invention, at least one of said carboxylic acid polysaccharide(s) is a high DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%.
[0104] In another embodiment of the use according to the invention, at least one of said carboxylic acid polysaccharide(s) is a low DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70%, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%.
[0105] In another embodiment according to the invention of the use of a composition, said composition comprises a mixture of at least one of carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%; and at least one carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70%, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%.
[0106] The composition according to the invention is suitable for use in personal care products.
[0107] In a preferred embodiment, said products are for use on human skin.
[0108] In another embodiment, said products are for use on animal skin.
[0109] In a particular embodiment according to the invention, the skin protecting alkalinity-controlling composition is used in a product selected from the group consisting of skin creams, skin lotions, deodorant products, fragrance products, hair care products, shaving products, soap products, and bath salt products.
[0110] In another embodiment according to the invention, the skin protecting alkalinity-controlling composition is used in a product selected from the group consisting of female hygiene products and diapers.
[0111] A particular advantage of the present composition is the fact that they are capable of controlling the alkalinity of the surface, to which they are applied, for a prolonged time. As demonstrated in examples 5 and 8, the carboxylic acid polysaccharides are capable of controlling the alkalinity at multiple challenges of alkalinity. This fact can be utilized in e.g. deodorant products, diapers or female hygiene products, which are repeatedly exposed to sweat that is decomposed by micro-organisms to alkaline substances. Thus, a prolonged effective alkalinity control may be obtained by the products according to the present invention.
[0112] In another embodiment according to the invention, the skin-protecting alkalinity-controlling composition is used in a product selected from the group consisting of ostomy products and wound care products.
[0113] In ostomy products a low solubility polysaccharide, such as a low solubility pectin, should be used, since the ostomy product should remain insoluble for a longer period of time during flushing by body fluids. In this particular case a combination of a low DE and a low pH pectin would provide for a longer durability of the ostomy product during use.
[0114] In a particular embodiment such low solubility low DE pectin should be combined with a higher solubility pectin having a higher DE to maintain a skin pH closer to the optimum skin pH of 5.5.
[0115] In still another embodiment according to the invention, the skin-protecting alkalinity-controlling composition is used in a product selected from the group consisting of lotionized tissue products, fabric treating products, and laundry rinse products.
[0116] Extraction of Pectin
[0117] Pectin is extracted using the following steps. The degree of esterification was controlled in the range of about 76% to about 30% through shorter or longer extraction times. The process is as follows:
1. 15 litres of water was heated to 70° C. in a stainless steel, jacketed vessel having a volume of 18 litres and equipped with a stirrer. 2. 500 g dried citrus peel or dried beet cossets was added to the water, and the pH is adjusted to 1.7-1.8 by addition of 62% nitric acid. 3. Extraction was carried out at 70° C. for 2-24 hours depending on the desired degree of esterification while stirring. 4. After extraction, the content of the vessel was filtered on a Bücher funnel using diatomaceous earth as filter aid. 5. The filtered extract was ion exchanged while stirring by adding 50 ml resin (Amberlite SRI L, produced by Rohm&Haas) per litre of filtered extract. While stirring, the ion exchange was carried out during 20 minutes while stirring. 6. The ion exchanged filtrate was filtered on a Bücher funnel equipped with a cloth. 7. The filtered ion exchanged filtrate was precipitated by adding it to three parts of 80% isopropanol while stirring gently. 8. The precipitate was collected on nylon cloth and pressed by hand to remove as much isopropanol as possible. 9. The hand pressed precipitate was washed once in 60% isopropanol and then dried at 70° C. in a drying cabinet at atmospheric pressure. 10. After drying, the pectin was milled.
[0128] Preparation of Pectin with Degree of Esterification Below 30%
1. The pressed precipitate made according to the procedure under a) point 8 was suspended in 60% isopropyl alcohol at 5° C. 2. Concentrated NaOH solution was added and the slurry was stirred for about one hour. The amount of NaOH is calculated to produce the desired DE. 3. The pectin solid was separated on nylon cloth, and washed twice in 60% isopropyl alcohol at pH 4. 4. The pectin solid was separated on nylon cloth, dried at 70° C. and milled.
[0133] Preparation of Pectin Different Molecular Weight
1. Pectin extracted according to a) was dissolved in about 80° C. ion exchanged water to form a 5% solution. 2. After cooling the solution to about 25° C., pH was adjusted to 5.50 with NH 3 . 3. Samples of the cold solution were treated with pectin lyase in concentrations ranging from 0 to 1300 micro litres per 10 litres of pectin solution. 4. Each sample was treated with its enzyme preparation for 1 hour at 25° C. while stirring. 5. After treatment, the pH was adjusted to 2.50 and the samples were heated at 80° C. for 10 minutes to inactivate the enzyme. 6. The samples were lastly precipitated in isopropyl alcohol, washed in isopropyl alcohol, dried and milled.
[0140] Preparation of Pectin with Degree of Esterification Above 80%
1. 50 g. pectin as prepared under a) was added 2.5 g. dimethylaminopyridine, 100 ml. methanol and 100 ml. heptane in suitable flask and the mixture was cooled to minus 4° C. 2. 15 ml thionylchloride was over a period of 10 minutes added as drops to the mixture. 3. Over about 24 hours, the mixture was allowed to heat to about 21° C. 4. The solid was filtered, washed twice with first 60% isopropyl alcohol and secondly with 100% isopropyl alcohol. 5. The solid was dried at about 70° C.
[0146] Preparation of Pectin with Different Distribution of Ester Groups
1. Pectin extracted according to a) was dissolved in about 80° C. ion exchanged water to faun a 2% solution. 2. The solution was cooled to 45° C. and pH was adjusted to 4.5 with NH 3 . 3. Samples were added 2-4% of enzyme preparation while stirring: Plant esterase (Collopulin) for a block wise de-esterification and bacterial esterase (Rheozyme) for random de-esterification. 4. The degree of esterification was monitored through titration with 2% NH 3 at constant pH of 4.5. 5. After de-esterification, decreasing the pH to 2.5 with HNO 3 and subsequently heating the sample to 80° C. for 10 minutes inactivated the enzyme. 6. The sample was precipitated in isopropyl alcohol, washed in isopropyl alcohol, dried and milled.
[0153] Determination of Molecular Weight (Mw) and Intrinsic Viscosity (IV)
[0154] For this, High Performance Size Exclusion Chromatography (HPSEC) with triple detection is used.
[0155] Principle: A pectin sample is fractionated according to hydrodynamic volume, using size exclusion chromatography. After separation, the sample is analysed by a triple detector system, consisting of a refractive index (RI) detector, a Right Angle Laser Light Scattering (BALLS) detector and a differential viscometer. Information from these detectors leads to determination of molecular weight (Mw) and intrinsic viscosity (IV). The Mark-Houwink factor is calculated using the molecular weight and intrinsic viscosity as obtained using this method.
[0156] Materials:
1. Pump model 515, Waters, Hedehusene, Denmark. 2. Degasser, Gynkotek, Polygen Scandinavia, Århus, Denmark. 3. Column oven, Waters, Hedehusene, Denmark. 4. AS-3500 Auto sampler, with sample preparation module, Dionex Denmark, Rødovre, Denmark. 5. 3 linear mixed bed columns, TSK-GMPWXL, Supelco, Bellefonte Pa., USA. 6. Liquid phase: 0.3 M lithium acetate buffer pH 4.8, Fluka Chemie AG, Buchs, Switzerland. 7. Dual detector, RI, Viscometry, Model 250, Viscotek, Houston, Tex., USA. 8. RALLS Model 600, Viscotek, Houston, Tex., USA.
[0165] Method:
[0166] Approximately 2 mg of the sample is weighed into a 2000 μl vial. The sample is then dissolved in the auto sampler, by following schedule: 8 μl of ethanol is added, then 1300 μl of acetate buffer (0.3 M, pH 4.8), sample is heated to 75° C. and mixed for 9.9 minutes. 300 μl of the preparation is diluted with 900 μl of acetate buffer, then mixing for 9.9 minutes. Sample is left at ambient temperature for 20 minutes. 100 μl of the sample is injected with a 100 μl full loop and flow rate is 0.8 ml/min. Two detectors are present in line, a right angle laser light Scattering (RALLS) detector (Viscotek) and a dual detector consisting of a refractive index detector and a viscometer (Viscotek).
[0167] The specific refractive index increment (dn/de) value for pectin is set at 0.144. Data from detectors are processed by tri-SEC software (Viscotek).
[0168] Determination of Degree of Esterification (DE) and Galacturonic Acid (GA) in Non-Amide Pectin
[0169] Principle: This method pertains to the determination of % DE and % GA in pectin, which does not contain amide and acetate ester.
[0170] Apparatus:
1. Analytical balance 2. Glass beaker, 250 ml, 5 pieces 3. Measuring glass, 100 ml 4. Vacuum pump 5. Suction flask 6. Glass filter crucible no. 1 (Büchner funnel and filter paper) 7. Stop watch 8. Test tube 9. Drying cabinet at 105° C. 10. Dessicator 11. Magnetic stirrer and magnets 12. Burette (10 ml, accuracy±0.05 ml) 13. Pipettes (20 ml: 2 pieces, 10 ml: 1 piece) 14. pH-meter/autoburette or phenolphtalein
[0185] Chemicals:
1. Carbon dioxide-free water (deionized water) 2. Isopropanol (IPA), 60% and 100% 3. Hydrochloride (HCl), 0.5 N and fuming 37% 4. Sodium hydroxide NaOH),
0.1 N (corrected to four decimals, e.g. 0.1002), 0.5 N
5. Silver nitrate (AgNO 3 ), 0.1 N 6. Nitric acid (HNO 3 ), 3 N 7. Indicator, phenolphtalein, 0.1%
[0194] Procedure—Determination of % DE and % GA_(Acid alcohol: 100 ml 60% IPA+5 ml HCl fuming 37%):
1. Weigh 2,0000 g pectin in a 250 ml glass beaker. 2. Add 100 ml acid alcohol and stir on a magnetic stirrer for 10 min. 3. Filtrate through a dried, weighed glass filter crucible. 4. Rinse the beaker completely with 6×15 ml acid alcohol. 5. Wash with 60% IPA until the filtrate is chloride-free (approximately 500 ml). 6. Wash with 20 ml 100% IPA. 7. Dry the sample for 2 hours at 105° C. 8. Weigh the crucible after drying and cooling in desiccator. 9. Weigh accurately 0.4000 g of the sample in a 250 ml glass beaker. 10. Weigh two samples for double determination. Deviation between double determinations must max. be 1.5% absolute. If deviation exceeds 1.5% the test must be repeated. 11. Wet the pectin with approx. 2 ml 100% IPA and add approx. 100 ml carbon di-oxide-free, deionized water while stirring on a magnetic stirrer.
[0206] (Chloride test on ash-free and moisture-free basis: Transfer approximately 10 ml filtrate to a test tube, add approximately 3 ml 3 N HNO 3 , and add a few drops of AgNO 3 . The filtrate will be chloride-free if the solution is clear, otherwise there will be a precipitation of silver chloride.)
[0207] The sample is now ready for titration, either by means of an indicator or by using a pH-meter/autoburette.
[0208] Procedure—Determination of % DE only (Acid alcohol: 100 ml 60% IPA+5 ml HCl fuming 37%):
1. Weigh 2.00 g pectin in a 250 ml glass beaker. 2. Add 100 ml acid alcohol and stir on a magnetic stirrer for 10 minutes. 3. Filtrate through a Büchner funnel with filter paper. 4. Rinse the beaker with 90 ml acid alcohol. 5. Wash with 1000 ml 60% IPA. 6. Wash with approximately 30 ml 100% IPA. 7. Dry the sample for approximately 15 minutes on Büchner funnel with vacuum suction. 8. Weigh approximately 0.40 g of the sample in a 250 ml glass beaker. 9. Weigh two samples for double determination. Deviation between double determinations must max. be 1.5% absolute. If deviation exceeds 1.5% the test must be repeated. 10. Wet the pectin with approximately 2 ml 100% IPA and add approx. 100 ml de-ionized water while stirring on a magnetic stirrer.
[0219] The sample is now ready for titration, either by means of an indicator or by using a pH-meter/autoburette. Note: It is very important that samples with % DE<10% are titrated very slowly, as the sample will only dissolve slowly during titration.
[0220] Titration using indicator:
1. Add 5 drops of phenolphtalein indicator and titrate with 0.1 N NaOH until change of color (record it as V 1 titer). 2. Add 20.00 ml 0.5 N NaOH while stirring. Let stand for exactly 15 min.
[0223] When standing the sample must be covered with foil.
3. Add 20.00 ml 0.5 N HCl while stirring and stir until the color disappears. 4. Add 3 drops of phenolphtalein and titrate with 0.1 N NaOH until change of color (record it as V 2 titer).
[0226] Blind Test (Double Determination is Carried Out):
1. Add 5 drops phenolphtalein to 100 ml carbon dioxide-free or dionized water (same type as used for the sample), and titrate in a 250 ml glass beaker with 0.1 N NaOH until change of color (1-2 drops). 2. Add 20.00 ml 0.5 N NaOH and let the sample stand untouched for exactly 15 minutes. When standing the sample must be covered with foil. 3. Add 20.00 ml 0.5 N HCl and 3 drops phenolphtalein, and titrate until change of color with 0.1 N NaOH (record it as B 1 ). Maximum amount allowed for titration is 1 ml 0.1 N NaOH. If titrating with more than 1 ml, 0.5 N HCl must be diluted with a small amount of deionized water. If the sample has shown change of color on addition of 0.5 N HCl, 0.5 N NaOH must be diluted with a small amount of carbon dioxide-free water. Maximum allowed dilution with water is such that the solutions are between 0.52 and 0.48 N.
[0230] Titration Using pH-Meter/Autoburette:
[0231] Using Autoburette type ABU 80 the following settings may be applied:
[0000]
Sample with
% DE < 10
Blind test
Proportional band
0.5
5
Delay sec.
50
5
Speed - V1
10
5
Speed - V2
15
5
1. Titrate with 0.1 N NaOH to pH 8.5 (record the result as V 1 titer).
2. Add 20.00 ml 0.5 N NaOH while stirring, and let the sample stand without stir-ring for exactly 15 minutes. When standing the sample must be covered with foil.
3. Add 20.00 ml 0.5 N HCl while stirring and stir until pH is constant.
4. Subsequently, titrate with 0.1 N NaOH to pH 8.5 (record the result as V 2 titer).
[0236] Blind Test (Double Determination is Carried Out):
1. Titrate 100 ml carbon dioxide-free or deionized (same type as used for the sample) water to pH 8.5 with 0.1 N NaOH (1-2 drops). 2. Add 20.00 ml 10.5 N NaOH while stirring and let the blind test sample stand without stirring for exactly 15 min. When standing the sample must be covered with foil. 3. Add 20.00 ml 0.5 N HCl while stirring, and stir until pH is constant. 4. Titrate to pH 8.5 with 0.1 N NaOH (record it as B 1 ). Maximum amount allowed for titration is 1 ml 0.1 N NaOH. If titrating with more than 1 ml, 0.5 N HCl must be diluted with a small amount of deionized water. If pH does not fall to below 8.5 on addition of 0.5 N HCl, 0.5 N NaOH must be diluted with a small amount of carbon dioxide-free water. Maximum allowed dilution with water is such that the dilutions are between 0.52 and 0.48 N.
[0241] Calculation:
[0000] V t =V 1 +( V 2 −B 1 )
[0000] % DE(Degree of Esterification)={( V 2 −B 1 )×100 }/V t
[0000] % DFA(Degree of Free Acid)=100−% DE
[0000] % GA*(Degree of Galacturonic acid)=(194.1 ×V t ×N× 100)/400 (194.1: Molecular weight for GA N: Connected normality for 0.1 N NaOH used for titration (e.g. 0.1002 N) 400: weight in mg of washed and dried sample for titration)
[0000] % Pure pectin={(acid washed, dried amount of pectin)×100}/(weighed amount of pectin)
[0245] Determination of pH-Drop
1. 1 g. pectin was dissolved in 100 g. deionized water at 70° C. and at 20° C. 2. The solution was placed in a thermostatically controlled water bath and continuously stirred. 3. 0.1 M NaOH was added to a pH of between 9 and 10, 4. The pH was recorded as a function of time
[0250] Deter Determination of Titration Curves
1. 2 g. pectin was dissolved in 200 g. deionized water at 70° C. and at 20° C. 2. The solution was placed in a thermostatically controlled water bath at 25° C. and continuously stirred. 3. 0.1 M NaOH was added to the solution and pH recorded as a function of added 0.1 M NaOH.
[0254] Propylene glycol alginate—Quantitative determination of the ester groups is carried out by the saponification method described on pages 169-172 of “Quantitative organic analysis via functional groups”, 4th Edition, John Wiley and Sons Publication.
1. Kelcoloid O manufactured by ISP Technologies, Inc. Esterification: High—about 85%. 2. Manucol Ester ER/K manufactured by ISP Technologies, Inc, Esterification: High—about 80%. 3. Kelcoloid HVF manufactured by ISP Technologies, Inc. Esterification: Medium—about 55%
[0258] Preparation of Lotion and pH-Drop in Lotion
[0259] Lotions were prepared according to the composition:
[0000]
TABLE 2.1.1
Composition of Lotion
Ingredient
grams
%
Comment
Isopropyl
59
18.11
Waglinol 6016; manufactured by
Palmitate
Industrail Quimica Lasem SA; Spain
Emulsifier
20
6.14
Emulium Delta; manufactured by
Gattefossé, France
Sodium
0.22
0.07
Analytical grade; manufactured by
benzoate
Merck, Germany, 0.09% in water
Potassium
0.15
0.05
Analytical grade; manufactured by
sorbate
Fluka, Switzerland, 0.06% in water
Pectin
2.44
0.75
1.00% in water, DE = 81.7%
Distilled
244
74.89
water
Total
325.81
100
pH of lotion: 3-4
[0260] Since the pH is ow, the lotion can be preserved with conventional food-grade preservatives.
[0261] Method 1:
1. Palmitate and emulsifier were mixed and heated to 75° C. in order to melt the emulsifier. 2. Pectin and preservatives were dispersed in distilled water and heated to 75° C.
[0264] 3, The hot oil phase was added to the hot water phase while stirring on magnetic stirrer.
4. The mix was cooled to about 30° C. on cooling bath while stirring and fill into appropriate container.
[0266] Method 2:
1. Palmitate and emulsifier were mixed and heated to 75° C. in order to melt the emulsifier. 2. Pectin was dispersed into the hot melt. Pectin is insoluble in the oil phase and consequently easy to disperse therein without formation of lumps. 3. Preservatives were dissolved in distilled water and the solution was heated to 75° C. 4. The hot oil phase was added to the hot water phase while stirring on magnetic stirrer.
[0271] The mix was cooled to about 30° C. on cooling bath while stirring and fill into appropriate container.
1. A piece of cotton was cut to fit into a petri dish. 2. The cotton piece was soaked in a pectin solution in distilled water and stirred on magnetic stirrer for about 5 minutes. 3. The wet cloth was hand-pressed and placed in a petri dish. 4. The cloth was dried over night in an oven at 50° C. 5. The dried cloth was wetted with 2 ml 0.001 M NaOH. 6. A piece of indicator paper (pH in the range 1-11) was placed on the cloth. 7. The color change of the indicator paper over time was recorded.
[0279] (Note: This test is indicative, only. It is not possible to read the pH accurately.)
[0280] The invention will now be described in more detail with respect to the following, specific, non-limiting examples.
EXAMPLES
Example 1
Effect of Molecular Weight
[0281] Five samples of different molecular weight, but with similar DE made from dried lemon peel were titrated and the pH drop over time recorded for samples dissolved at 70° C. and 20° C., respectively. The pH drop was measured at 30-32° C. Titration was done using 0.1008 M NaOH. The comment “unstable” refers to the pH-meter, which at high pH values showed an unstable reading.
[0000]
TABLE 1.1
Titration and pH drop of pectin with
molecular weight 123,000, DE = 71.4%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.12
0
9.83
0
9.72
1
3.19
1
9.47
1
9.4
2
3.26
2
9.27
2
9.21
3
3.33
3
9.13
3
9.08
4
3.41
4
9.03
4
8.98
5
3.48
5
8.94
5
8.9
6
3.56
18
8.39
6
8.82
7
3.63
54
7.66
19
8.29
8
3.71
72
7.38
30
8.08
9
3.8
102
7.16
62
7.44
10
3.91
175
6.86
97
7.15
11
4.02
1149
6.15
157
6.92
12
4.15
1194
6.12
193
6.85
13
4.29
14
4.48
15
4.72
16
5.13
17
6.84
17.5
8.52
Unstable
18
8.95
Unstable
[0000]
TABLE 1.2
Titration and pH drop of pectin with
molecular weight 108,500, DE = 71.4%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.12
0
9.7
0
9.64
1
3.17
1
9.44
1
9.35
2
3.24
2
9.28
2
9.16
3
3.3
3
9.13
3
9.02
4
3.37
4
9.04
4
8.91
5
3.44
5
8.93
5
8.83
6
3.52
8
8.66
15
8.3
7
3.59
22
7.98
23
8.06
8
3.68
61
7.42
30
7.81
9
3.77
101
7.02
43
7.48
10
3.87
158
6.88
56
7.32
11
3.97
188
6.84
69
7.22
12
4.09
1171
6.09
103
6.99
13
4.22
1188
6.05
159
6.82
14
4.39
210
6.74
15
4.6
16
4.91
17
5.55
17.5
7.02
Unstable
18
8.71
Unstable
[0000]
TABLE 1.3
Titration and pH drop of pectin with
molecular weight 95,000, DE = 72.3%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.03
0
9.9
0
9.57
1
3.1
1
9.55
1
9.33
2
3.15
2
9.33
2
9.18
3
3.22
3
9.22
3
9.06
4
3.29
4
9.13
4
8.97
5
3.36
5
9.04
5
8.89
6
3.43
6
8.98
6
8.82
7
3.51
13
8.61
41
7.52
8
3.59
25
8.05
49
7.38
9
3.67
31
7.87
66
7.23
10
3.77
49
7.51
78
7.16
11
3.84
66
7.34
100
7.11
12
3.95
104
7.04
141
6.96
13
4.08
128
6.95
162
6.92
14
4.2
159
6.89
172
6.92
15
4.35
1488
6.2
16
4.56
17
4.84
18
5.37
18.5
6.12
19
8.32
Unstable
19.5
8.94
Unstable
[0000]
TABLE 1.4
Titration and pH drop of pectin with
molecular weight 71,500, DE = 71.6%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.06
0
9.83
0
9.59
1
3.12
1
9.38
1
9.3
2
3.18
2
9.13
2
9.1
3
3.25
3
8.95
3
8.98
4
3.32
4
8.84
4
5.88
5
3.38
5
8.73
5
8.79
6
3.45
24
8.18
11
8.44
7
3.53
30
7.95
20
8.09
8
3.61
56
7.37
37
7.56
9
3.69
87
7.07
55
7.29
10
3.78
115
6.93
84
7.06
11
3.87
163
6.82
164
6.86
12
3.98
225
6.74
176
6.84
13
4.1
310
6.65
14
4.24
1216
6.09
15
4.4
1252
6.04
16
4.61
17
4.91
17.5
5.14
18
5.52
18.5
6.77
Unstable
19
8.63
Unstable
[0000]
TABLE 1.5
Titration and pH drop ofpectin with
molecular weight 41,500, DE = 73%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.04
0
9.83
0
9.53
1
3.09
1
9.36
1
9.22
2
3.15
2
9.1
2
9.05
3
3.21
3
8.93
3
8.9
4
3.28
4
8.81
4
8.78
5
3.34
5
8.7
5
8.68
6
3.41
10
8.34
6
8.61
7
3.48
19
7.93
20
7.94
8
3.56
29
7.64
26
7.77
9
3.64
45
7.34
55
7.22
10
3.73
67
7.13
76
7.11
11
3.81
129
6.9
122
6.93
12
3.91
199
6.8
159
6.87
13
4.02
1173
5.88
261
6.73
14
4.15
1193
5.85
15
4.29
16
4.46
17
4.7
18
5.06
18.5
5.39
19
6.22
Unstable
19.5
8.47
Unstable
20
9.04
Unstabie
[0282] FIG. 1.1 shows that the molecular weight of pectin has no influence on the alkali consumption.
[0283] The data in FIG. 1.2 do not suggest a change in the pH-drop resulting from a change in molecular weight. In practice, this means that a pH controlling preparation made from pectin can be made thick (high molecular weight) or thin (low molecular weight) or basically with any viscosity between the two extremes. In addition, if the alkali consumption is to be increased, a low molecular weight pectin preparation makes it possible to increase the concentration of pectin without making the alkali consuming preparation too viscous.
[0284] FIG. 1.3 shows that dissolution temperature does not change the drop in pH. Thus, irrespective of the molecular weight, pectin preparation for controlling pH can be made either hot or cold.
Example 2
Effect of Degree of Esterification
[0285] Eight samples were prepared with different degree of esterification ranging from about 9 to 93%. The samples were made from dried lemon peel. All were titrated and the pH drop over time recorded for samples dissolved at 70° C. and 20° C., respectively. The pH drop was measured at 30-32° C. Titration was done using 0.1008 M NaOH. The comment “unstable” refers to the pH-meter, which at high pH values showed an unstable reading.
[0000]
TABLE 2.1
Titration and pH drop of pectin with DE = 9.6%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
4.07
0
9.76
0
9.62
1
4.12
1
9.69
1
9.57
2
4.16
2
9.64
2
9.54
3
4.2
3
9.59
3
9.5
4
4.24
4
9.57
4
9.48
5
4.28
12
9.31
5
9.45
6
4.33
32
9.06
7
9.41
7
4.37
74
8.56
12
9.05
8
4.42
112
8.15
22
8.92
9
4.47
1479
7.27
49
8.76
10
4.52
4093
6.26
62
8.56
11
4.57
122
7.98
12
4.64
182
7.6
13
4.7
242
7.47
14
4.77
302
7.37
15
4.86
449
7.32
16
4.96
1382
7.21
17
5.08
1412
7.18
18
5.23
19
5.45
20
5.85
21
8.17
Unstable
[0000]
TABLE 2.2
Titration and pH drop of pectin with DE = 34.4%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.22
0
9.97
0
9.7
1
3.27
1
9.74
1
9.54
2
3.3
2
9.59
2
9.43
3
3.33
3
9.48
3
9.33
4
3.36
4
9.37
4
9.25
5
3.39
5
9.28
5
9.18
6
3.42
35
8.01
12
8.78
7
3.45
67
7.59
26
8.15
8
3.48
110
7.33
58
7.65
9
3.51
151
7.19
88
7.41
10
3.55
1483
6.54
189
7.1
11
3.58
12
3.62
13
3.65
14
3.69
15
3.74
16
3.77
17
3.82
18
3.86
19
3.9
20
3.94
21
3.98
22
4.03
23
4.08
24
4.13
25
4.17
26
4.23
27
4.28
28
4.34
29
4.4
30
4.47
31
4.54
33
4.72
35
4.97
36
5.16
37
5.45
38
6.2
39
9.76
Unstable
[0000]
TABLE 2.3
Titration and pH drop of pectin with DE = 71%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.11
0
10.21
0
9.73
0.2
3.12
0.5
9.85
1
9.24
0.42
3.14
1
9.65
2
8.92
0.6
3.15
2
9.35
3
8.68
0.84
3.17
3
9.1
4
8.48
1.2
3.2
8
8.39
9
7.88
1.6
3.23
10
8.21
14
7.56
2.08
3.27
20
7.73
23
7.23
2.4
3.29
31
7.5
33
7.07
3
3.34
45
7.3
44
6.96
3.4
3.37
75
7.12
48
6.94
4
3.42
115
7
4.8
3.49
150
6.91
5.68
3.56
190
6.86
6.02
3.59
260
6.85
6.6
3.64
285
6.82
7.6
3.73
320
6.78
8
3.76
360
6.75
9
3.86
390
6.73
10
3.97
10.4
4
11
4.07
12
4.2
13
4.34
[0000]
TABLE 2.4
Titration and pH drop of pectin with DE = 93.4%
Time,
Time,
ml
minutes,
minutes,
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.26
0
9.5
0
9.29
1
3.43
1
8.89
1
8.14
2
3.65
2
8.14
2
7.7
3
3.98
3
7.77
3
7.49
4
4.54
4
7.58
4
7.33
5
8.74
Unstable
5
7.45
5
7.21
11
7.04
8
7
15
6.9
13
6.81
20
6.79
23
6.61
25
6.7
33
6.51
30
6.62
1004
5.37
38
6.52
1018
5.3
[0286] FIG. 2.1 shows that one pectin is characterized by a higher starting pH than the rest, Conventionally, pectin is neutralized with an alkali metal base to a pH in the range 3-4 or even higher. This is mainly in order to preserve the pectin, but it also has an impact on the solubility of the pectin. However, if one moves the curve for DE-9.6% upwards to connect with the other curves, the picture becomes clear: With increasing DE and consequently decreasing galacturonic acid, the pectin can consume less alkali. Thus, if pectin is used to neutralize alkali, the degree of esterification and the starting pH should be as low as possible.
[0287] To further elaborate on this point, I define buffer capacity as ml. 0.1 M NaOH required to increase the pH by 1 pH unit, calculated from the part of the titration curve, which is steepest.
[0288] Thus, the approximate buffer capacities as calculated from FIG. 2.1 are:
DE=9.6% and DE=34.4%: Buffer capacity about 26 DE=71%: Buffer capacity about 12 DE=93.4%: Buffer capacity less than 6
[0292] FIG. 2.2 show a dramatic increase in the pH-drop as the degree of esterification is increased.
[0293] FIG. 2.3 shows the same dramatic influence of DE even when the pectin is dissolved at 20° C. The figure shows that at the high DE, the pH is eventually decreased below 5.5.
[0294] These results are compiled in FIG. 2.4 , in which the pH drop has been followed for the first up to about 130 minutes. It is evident that the pH-drop occurs to the same extent whether the pectin solution is made hot or cold.
[0295] For DE=93.4%, time to reach pH=8 is 2 minutes, for DE=71% it takes 12 minutes, for DE=34.4% the time is 35 minutes and for DE=9.6% it takes 130 minutes. In order to reach pH-7, the difference is even bigger. Pectin with a DE=71 is about 9 times slower than pectin with DE=93.4, and pectin with DE lower than 71% are slower than a factor 10 compared to pectin with DE-93.4.
[0296] Thus, if one needs to obtain a rapid pH decrease as a result of alkali generation, pectin with as high a DE as possible is preferred. If, on the other hand, the need calls for slower reduction of pH, then a lower DE would be preferred. Selecting pectin of a specific DE makes it possible to reduce the pH at a specific rate.
[0297] Another aspect is to combine pectin preparations of different DE. For example, one might combine a low DE pectin and a high DE pectin to achieve initial alkali consumption or buffer capacity and to provide pH reduction, when the buffer capacity is used.
Example 3
Effect of Methyl Ester Distribution
[0298] Two samples were made from dried lemon peel. One was de-esterified with a bacterial pectin esterase, which results in a random distribution of the methyl ester groups. The other was de-esterified with a plant pectin esterase, which results in a block wise distribution of the methyl ester groups. The samples were made to similar DE. Both samples were titrated and the pH drop over time recorded for samples dissolved at 70° C. and 20° C., respectively. The pH drop was measured at 30-32° C. Titration was done using 0.1008 M NaOH. The comment “unstable” refers to the pH-meter, which at high pH values showed an unstable reading.
[0299] FIG. 3.1 shows that the distribution of methyl esters in pectin has no impact on the alkali consumption. The galacturonic acid drives the alkali consumption.
[0300] FIG. 3.2 indicates a difference in the rate of the pH-drop. It also shows, that identical pH-drop is achieved whether the pectin has been dissolved hot or cold.
[0301] FIG. 3.3 shows the pH-drop in the first 120-130 minutes, and a random ester group distribution needs about 4 times longer to reach pH-8 compared to a blocky ester group distribution. Since the two pectin preparations have almost identical average DE, the faster pH-drop of a blocky ester distribution is explained by local concentration of ester groups. Thus, pectin with a blocky ester distribution will act as pectin with a higher average DE. In practice, this is important because one might treat a blocky pectin with polygalacturonase to increase the DE, which would constitute an easier way to make a high ester pectin than by using the process of re-methylation.
Example 4
Effect of Temperature
[0302] The pH drop for one sample having DE=71% and made from dried lemon peel was recorded at four different temperatures. The sample was prepared by dissolving the pectin at 70° C. and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath.
[0000]
TABLE 4.1
pH drop of pectin with DE = 71% at various temperatures
25-27° C.
30-32° C.
35-37° C.
45-47° C.
Time,
Time,
Time,
Time,
minutes
pH
minutes
pH
minutes
pH
minutes
pH
0.2
10.4
0
10.21
0
10.08
0
10.01
0.5
10.21
0.5
9.85
1
9.41
1
9.15
1
9.85
1
9.65
2
9.01
2
8.59
2
9.52
2
9.35
3
8.73
3
8.26
3
9.26
3
9.1
10
7.81
4
8.04
5
8.89
8
8.39
23
7.4
9
7.49
10
8.33
10
8.21
35
7.23
16
7.15
20
7.75
20
7.73
143
6.75
21
7.02
30
7.47
31
7.5
203
6.64
44
6.78
45
7.24
45
7.3
263
6.57
61
6.68
60
7.11
75
7.12
326
6.5
76
6.62
122
6.91
115
7
378
6.45
121
6.5
181
6.85
150
6.91
154
6.43
240
6.79
190
6.86
202
6.34
291
6.77
260
6.85
250
6.27
347
6.74
285
6.82
325
6.17
1298
6.32
320
6.78
420
6.06
1428
6.31
360
6.75
1508
6.3
390
6.73
1553
6.28
[0303] FIG. 4.1 shows that the rate of the pH-drop increases with increasing temperature. The rate is particularly increased as the temperature increases above about 30° C.
Example 5
Effect of Multiple Additions of Alkali
[0304] The pH drop for one sample having DE-71% and made from dried lemon peel was recorded at a temperature of 25-27° C. First, the pH was raised to about 10 with 19 ml. 0.1 M NaOH. When the sample had reached a pH of 6-7, the pH was again raised to about 10. This required 1.1 ml. 0.1 M NaOH. When the pH had reached 6-7, the pH was raised a third time to about 10, which required 1.2 ml. 0.1 M NaOH. The sample was prepared by dissolving the pectin at 70° C. and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath.
[0000]
TABLE 5.1
Multiple pH drop of pectin with DE = 71%
First dosage: 19 ml
Second dosage: 1.1 ml
Third dosage: 1.2 ml
0.1M NaOH
0.1M NaOH
0.1M NaOH
Time,
Time,
Time,
minutes
pH
minutes
pH
minutes
pH
0.2
10.4
0
10.08
0
10.22
0.5
10.21
0.5
9.88
2
9.63
1
9.85
1
9.71
7
8.76
2
9.52
2
9.44
12
8.32
3
9.26
5
8.93
32
7.64
5
8.89
10
8.36
67
7.17
10
8.33
20
7.73
92
7.07
20
7.75
40
7.32
152
6.93
30
7.47
70
7.06
212
6.87
45
7.24
85
6.97
272
6.82
60
7.11
175
6.65
332
6.78
122
6.91
1140
6.38
402
6.74
181
6.85
1165
6.37
482
6.74
240
6.79
291
6.77
347
6.74
1298
6.32
1428
6.31
1508
6.3
1553
6.28
[0305] FIG. 5.1 shows that the rate of the pH-drop stays unchanged after at least three cycles, where the pH is first increased to about 10, then after the pH has dropped increased to about 10. After one cycle, the DE is decreased to about 66%, so the ability to continue reducing pH is caused by an incomplete de-esterification.
[0306] Thus, if alkalinity is appears in pulses, for at least three times pectin is able to reduce the alkali. In fact, in one experiment, which went on for seven days, a 200 ml. 1% pectin solution of DE=71% consumed 73 ml. of a 0.1 M NaOH solution. After this period, the DE has decreased to 9.1%.
[0307] Thus, 2 g. pectin consumes 7.3 mmol NaOH, which corresponds to about 0.3 g. NaOH. It also means that about 0.23 g. methanol is produced, which in combination with the acid effect of pectin may explain the anti-microbial effect of pectin.
Example 6
Effect of Pectin Concentration
[0308] The pH drop for one sample having DE-81.7% and made from dried lemon peel was recorded at a temperature of 30-32° C. The concentration of pectin was 0.05-2%. The sample was prepared by dissolving the pectin at 70° C. and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath.
[0000]
TABLE 6.1
pH drop at different concentration of pectin solution with DE = 81.7%
0.05%
0.1%
0.2%
0.5%
1.0%
2.0%
Start
Start
Start
Start
Start
Start
pH = 3.62
pH = 3.70
pH = 3.46
pH = 3.15
pH = 2.96
pH = 2.87
0.8 ml 0.1M
0.8 ml 0.1M
1.7 ml 0.1M
4.4 ml 0.1M
7.6 ml 0.1M
15.5 ml 0.1M
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
0
9.89
0
9.89
0
9.98
0
10.1
0
9.8
0
10.02
1
9.87
1
9.63
1
9.67
1
9.72
1
9.26
1
9.34
2
9.82
2
9.55
2
9.52
2
9.45
2
8.95
2
8.95
3
9.7
3
9.47
3
9.38
3
9.23
3
8.69
3
8.66
4
9.66
4
9.4
4
9.25
4
9.03
4
8.48
4
8.43
5
9.63
5
9.32
5
9.14
5
8.89
5
8.3
5
8.22
11
9.42
9
9.09
11
8.6
12
8.1
9
7.87
9
7.75
21
9.19
19
8.59
16
8.2
22
7.66
19
7.51
19
7.39
31
9
29
8.12
26
7.72
32
7.5
29
7.38
29
7.25
41
8.81
39
7.72
36
7.48
42
7.39
39
7.27
39
7.18
51
8.63
49
7.58
46
7.35
52
7.33
49
7.19
49
7.13
61
8.33
59
7.45
61
7.24
62
7.27
59
7.13
59
7.1
[0309] FIG. 6.1 shows that at pectin concentrations above 1%, the pH-drop appears to be independent of the pectin concentration. However, even at very low concentrations of pectin, a clear drop in pH occurs.
Example 7
pH Drop of Water
[0310] Carbon dioxide is soluble in water, and this experiment shows the pH drop of ion-exchanged water over time without the presence of pectin or other additions. The temperature of the water was kept at 25° C. using a thermostatically controlled water bath.
[0000]
TABLE 7.1
pH drop of ion exchanged water
Time,
minutes
pH
0
10.67
18
10.63
36
10.57
56
10.56
81
10.55
125
10.43
165
10.3
297
10.23
330
10.07
[0311] FIG. 7.1 shows that over a period of about 5 hours, the “natural” drop of pH in water is about 0.5 pH-units, so the error is tolerable.
Example 8
Propylene Glycol Alginate—Effect of Esterification
[0312] Three samples with degree of esterification ranging from about 55 to about 85% were tested. All were titrated and the pH drop over time recorded for samples dissolved at 70° C. and 20° C., respectively. The pH drop was measured at 30-32° C. Titration was done using 0.1008 M NaOH. The comment “unstable” refers to the pH-meter, which at high pH values showed an unstable reading.
[0000]
TABLE 8.1
Titration and pH drop of high DE PGA
(Kelcoloid O. Esterification: High - about 85%)
Time,
Time,
ml
minutes
minutes
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.89
0
10
0
10.19
0.5
3.99
1
7.77
1
7.74
1
4.1
2
7.34
2
7.33
1.5
4.22
3
7.14
3
7.13
2
4.38
4
7
4
6.99
2.5
4.57
5
6.89
5
6.86
3
4.89
10
6.48
8
6.57
3.5
5.7
15
6.2
38
5.41
4
8.82
Unstable
25
5.81
68
5.07
53
5.29
132
4.77
70
5.12
1102
4.4
90
4.99
1142
4.4
116
4.89
127
4.85
[0000]
TABLE 8.2
Titration and pH drop of high DE PGA
(Manucol Ester ER/K. Esterification: High - about 80%.)
Time,
Time,
ml
minutes
minutes
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.76
0
10
0
10.2
0.5
3.82
1
7.85
1
7.97
1
3.91
2
7.38
2
7.44
1.5
4.01
3
7.17
3
7.23
2
4.11
4
7
4
7.08
2.5
4.24
5
6.87
5
6.95
3
4.39
7
6.66
9
6.58
3.5
4.58
12
6.29
15
6.26
4
4.89
17
6.03
31
5.75
4.5
5.63
27
5.69
59
5.28
5
8.88
Unstable
42
5.4
90
5.06
57
5.24
142
4.87
1114
4.54
1163
4.53
[0000]
TABLE 8.3
Titration and pH drop of medium DE PGA
(Kelcoloid HVF. Esterification: Medium - about 55%)
Time,
Time,
ml
minutes
minutes
NaOH
pH
Comment
70° C.
pH
20° C.
pH
0
3.81
0
10.21
0
10.29
0.5
3.85
1
8.66
1
8.78
1
3.9
2
7.98
2
8.07
1.5
3.95
3
7.65
3
7.72
2
4
4
7.47
4
7.51
2.5
4.06
5
7.35
5
7.37
3
4.12
7
7.16
7
7.16
3.5
4.19
12
6.82
12
6.82
4
4.26
27
6.3
27
6.27
4.5
4.34
47
5.91
52
5.84
5
4.43
67
5.69
77
5.63
5.5
4.53
97
5.5
95
5.53
6
4.66
152
5.31
1106
5.02
6.5
4.82
222
5.19
1148
5.02
7
5.07
7.5
5.56
8
8.03
Unstable
[0313] The pH drop for one sample, Manucol Ester ER/K, was recorded at a temperature of 30-32° C. First, the pH was raised to about 10 with 4 ml. 0.1 M NaOH. When the sample had reached a pH of 5-6, the pH was again raised to about 10. This required 2.5 ml. 0.1 M NaOH. When the pH had reached 5-6, the pH was raised a third time to about 10, which required 2.0 ml. 0.1 M NaOH. When the pH had reached about 6, the pH was again increased to about 10, which required 1.5 ml. NaOH. The sample was prepared by dissolving the pectin at 70° C. and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath.
[0000]
TABLE 8.4
Multiple pH drop of high DE PGA
First dosage
Second dosage:
Third dosage:
Fourth dosage:
4 ml 0.1M
2.5 ml 0.1M
2.0 ml 0.1M
1.5 ml 0.1M
NaOH
NaOH
NaOH
NaOH
Time,
Time,
Time,
Time,
minutes
pH
minutes
pH
minutes
pH
minutes
pH
0
10
0
10.24
0
9.89
0
9.97
1
7.85
1
8.29
1
8.26
1
8.7
2
7.38
2
7.62
2
7.64
2
8.04
3
7.17
3
7.36
3
7.37
3
7.67
4
7
4
7.2
4
7.21
4
7.47
5
6.87
5
7.07
5
7.09
5
7.33
7
6.66
9
6.64
9
6.7
11
6.84
12
6.29
14
6.29
13
6.45
16
6.56
17
6.03
19
6.04
18
6.23
22
6.31
27
5.69
24
5.85
23
6.06
31
6.03
42
5.4
147
5.13
57
5.24
[0314] FIG. 8.1 shows that as the degree of esterification increases in PGA, the less alkali can be consumed.
[0315] Buffer capacities are calculated to
PGA with DE about 85%: About 4.1 PGA with DE about 80%: About 5.7 PGA with DE about 55%: About 8.1
[0319] Thus, PGA provides less buffering effect compared to pectin.
[0320] FIG. 8.2 shows that as for pectin, PGA provides a faster pH drop with increasing degree of esterification.
[0321] FIG. 8.3 shows the same dramatic influence of esterification even when the propylene glycol alginate is dissolved at 20° C. The figure shows that at the high DE, the pH is eventually decreased to below 5.
[0322] FIG. 8.4 shows that the pH-drop occurs to the same extent whether the propylene glycol alginate solution is made hot or cold.
Example 9
Effect of Multiple Additions of Alkali to Propylene Glycol Alginate
[0323] The pH drop for one sample, Manucol Ester ERIK, was recorded at a temperature of 30-32° C. First, the pH was raised to about 10 with 4 ml. 0.1 M NaOH. When the sample had reached a pH of 5-6, the pH was again raised to about 10. This required 2.5 ml. 0.1 M NaOH. When the pH had reached 5-6, the pH was raised a third time to about 10, which required 2.0 ml. 0.1 M NaOH. When the pH had reached about 6, the pH was again increased to about 10, which required 1.5 ml. NaOH. The sample was prepared by dissolving the pectin at 70° C. and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath.
[0000]
TABLE 9.1
Multiple pH drop of high DE PGA
First dosage
Second dosage:
Third dosage:
Fourth dosage:
4 ml 0.1M
2.5 ml 0.1M
2.0 ml 0.1M
1.5 ml 0.1M
NaOH
NaOH
NaOH
NaOH
Time,
Time,
Time,
Time,
minutes
pH
minutes
pH
minutes
pH
minutes
pH
0
10
0
10.24
0
9.89
0
9.97
1
7.85
1
8.29
1
8.26
1
8.7
2
7.38
2
7.62
2
7.64
2
8.04
3
7.17
3
7.36
3
7.37
3
7.67
4
7
4
7.2
4
7.21
4
7.47
5
6.87
5
7.07
5
7.09
5
7.33
7
6.66
9
6.64
9
6.7
11
6.84
12
6.29
14
6.29
13
6.45
16
6.56
17
6.03
19
6.04
18
6.23
22
6.31
27
5.69
24
5.85
23
6.06
31
6.03
42
5.4
147
5.13
57
5.24
[0324] FIG. 9.1 shows a tendency for the pH-drop to become slower after two cycles.
Example 10
pH-Drop in Lotion
[0325] The pH drop in lotions made according to the two methods described in “Materials and Methods” section 2.1 were measured using pectin of about DE=81.7%.
[0326] 10 grams lotion was slurried in 50 ml distilled water and pH was adjusted with 0.1 M NaOH to about 10. Pectin concentration in slurry: 0.125%. Temperature: 30° C.
[0000]
TABLE 10.1
pH-drop of lotions
Method 1
Method 2
Minutes
pH
Minutes
pH
0
9.98
0
10.24
1
9.84
1
10.07
2
9.78
2
9.97
3
9.68
3
9.89
4
9.63
4
9.83
5
9.58
5
9.78
17
9.28
10
9.59
32
9.15
25
9.38
50
9.04
40
9.24
62
9
55
9.15
[0327] It may seem that when pectin is dissolved in the water phase before mixing with the oil phase provides for a more rapid pH-drop. However, when taking into consideration, that the curve for pectin dissolved in the water phase starts at a slightly lower pH, the two curves are close to identical. Thus, there is nothing to suggest that one of the methods for making the lotion influences the effect of the pectin.
[0328] The lotions were tested by 12 persons—6 females and 6 males, with the following remarks from the test persons:
Easy to spread on the skin Non-sticky Non-greasy Softens skin within one minute after application Skin-softening remains for at least 24 hours Removes skin-itching within one minute after application Skin-itching does not reoccur within 24 hours Athlete's foot is effectively combated for at least 24 hours
[0337] The lotion was also tested on one dog, which had developed a rash on the nose. Treatment of the nose with the lotion twice for one day reduced the rash visibly. To similar treatments over the next two days reduced to rash to an extent, where the rash was difficult to see.
Example 11
pH-Drop of Cloth
[0338] Cloths were prepared according to the method in “Materials and Methods” section above.
[0000]
TABLE 11.1
pH-drop of cloth soaked in a 0.01% pectin solution
0.01% pectin
Mw = 123,000
Mw = 95,000
Mw = 41,500
Mw = 25,000
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
0
11
0
11
0
11
0
11
20
9
20
9
20
9
20
9
140
8.5
140
8.5
140
8.5
140
8.5
290
8
290
8
290
8
290
8
500
7.5
500
7.5
500
7.5
500
7.5
[0000]
TABLE 11.2
pH-drop of cloth soaked in a 0.05% pectin solution
0.05% pectin
Mw = 123,000
Mw = 95,000
Mw = 41,500
Mw = 25,000
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
0
11
0
11
0
11
0
11
20
9
20
9
20
9
20
9
140
8.5
140
8.5
140
8.5
140
8.5
290
8
290
8
290
8
290
8
500
7.5
500
7.5
500
7.5
500
7.5
[0000]
TABLE 11.3
pH-drop of cloth soaked in a 0.10% pectin solution
0.10% pectin
Mw = 123,000
Mw = 95,000
Mw = 41,500
Mw = 25,000
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
0
11
0
11
0
11
0
11
20
9
20
9
20
9
20
9
140
8.5
140
8.5
140
8.5
140
8.5
290
8
290
8
290
8
290
8
500
7.5
500
7.5
500
7.5
500
7.5
[0000]
TABLE 11.4
pH-drop of cloth soaked in a 0.20% pectin solution
0.20% pectin
Mw = 123,000
Mw = 95,000
Mw = 41,500
Mw = 25,000
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
0
11
0
10
0
11
0
11
20
9
20
8.5
20
8.5
20
9
140
8.5
140
8
140
8
140
8.5
290
8
290
7.5
290
8
290
8
500
7.5
500
7
500
7.5
500
7.5
[0000]
TABLE 11.5
pH-drop of cloth soaked in a 0.50% pectin solution
0.50% pectin
Mw = 123,000
Mw = 95,000
Mw = 41,500
Mw = 25,000
Minutes
pH
Minutes
pH
Minutes
pH
Minutes
pH
0
10
0
10
0
10
0
10
20
8.5
20
8.5
20
8.5
20
8.5
140
8
140
8
140
8
140
8
290
7.5
290
7.5
290
7.5
290
7.5
500
7
500
7
500
7
500
7
[0339] FIG. 11 . 1 - 11 . 5 show that irrespective of the concentration of pectin during soaking, and irrespective of the molecular weight of the pectin, the pH-drop is quite similar.
[0340] However, when the cloth is soaked in a pectin solution, the dried cloth becomes stiffer. Table 11.1 shows this effect:
[0000]
TABLE 11.1
Stiffness of cloth as a function of pectin concentration
in soak and molecular weight of pectin
Pectin
M w
% in soak
123,000
95,000
41,500
25,000
0.01
Soft
Soft
Soft
Soft
0.05
Slightly
Soft
Soft
Soft
soft
0.1
Acceptable
Soft
Soft
Soft
0.2
Stiff
Acceptable
Soft
Soft
0.5
Too stiff
Stiff
Acceptable
Acceptable
[0341] Table 11.1 shows that as the molecular weight decreases, the cloth can contain more p in without becoming unacceptably stiff.
Mw=123,000 becomes unacceptably stiff at concentrations in the soak above 0.10% Mw=95,000 becomes unacceptably stiff at concentrations in the soak above 0.20% Mw=41,500 and Mw=25,000 become unacceptably stiff at concentrations in the soak above 0.50%.
[0345] A rinse is normally performed using 16 liters of water. Assuming that the rinse dosage is 100 ml, then 0.01% pectin in the rinse corresponds to a pectin solution of 1.57%. 0.05% pectin in the rinse corresponds to a pectin solution of 7.4%. 0.10% pectin in the rinse corresponds to a pectin solution of 13.79%. 0.20% pectin in the rinse corresponds to a pectin solution of 26.47% and 0.05% pectin in the rinse corresponds to a pectin solution of 44.44%.
[0346] The effect on Brookfield viscosity of such pectin solutions are shown in table 11.2:
[0000]
TABLE 11.2
Viscosity of different molecular weights
of pectin at various concentrations
Sample
%
Viscosity, cP
Comment
Mw = 123,00
1.6
229
4
12880
Not fully dissolved
Mw = 95,000
1.6
99.5
4
2840
Not fully dissolved
Mw = 41,500
1.6
11.3
4
73.6
8
790
12
19200
Not fully dissolved
Mw = 25,000
1.6
7.8
4
29.2
8
270
12
3560
Thick but dissolved
16
26800
Not fully dissolved
[0347] It is clear that as the molecular weights drops, it becomes easier to dissolve the pectin, and in addition the viscosity becomes lower. This enables a rinse to contain more pectin in lower rinse dosage.
[0348] For pectin with a molecular weight of 123,000, the maximum concentration of pectin in the rinse is about 2%, for a pectin with a molecular weight of 95,000, the maximum concentration of pectin in the rinse is about 3%, for a pectin with molecular weight of 41,500, the maximum concentration of pectin in the rinse is about 10% and for a pectin with molecular weight of 25,000, the maximum concentration of pectin in the rinse is about 12%.
Example 12
Effect of Blending Pectin Products
[0349] Pectin products having a DE of 93.4% and 9.6%, respectively were blended 1:1 and 100 g. 1% solution was prepared of the blend through heating to 70° C. The consumption of alkali at 25° C. and the pH-drop over time at 30-32° C. was recorded. Titration was done using 0.1008 M NaOH. The comment “unstable” refers to the pH-meter, which at high pH values showed an unstable reading.
[0000]
TABLE 12
Titration and pH drop of pectin blends
Time,
ml. NaOH
pH
Comment
minutes
pH
0
4.26
0
10.00
1
4.27
1
9.31
2
4.33
2
8.98
3
4.40
3
8.76
4
4.48
4
8.58
5
4.56
5
8.44
6
4.64
16
7.66
7
4.74
40
7.33
8
4.85
49
7.22
9
4.97
69
7.04
10
5.12
11
5.33
12
5.66
13
6.82
Slightly
unstable
14
9.73
Unstable
[0350] FIG. 12.1 shows that blending high DE pectin and low DE pectin results in an alkali consumption in between the alkali consumption of the individual pectin products.
[0351] FIG. 12.2 shows that the pH drop over time falls between the pH drop over time of the individual components.
[0352] Compared to the individual components, the blend of high DE pectin and low DE pectin provides for an increase in alkali consumption compared to pure high DE pectin and an increase in pH-drop compared to low DE pectin.
Example 13
Effect of Blending High Ester Pectin and Low Ester Propylene Glycol Alginate
[0353] A blend of 50% of a pectin having a DE of 93.4% and 50% of a propylene glycol alginate (PGA) having a DE of 55% was dissolved at 70% in a similar manner as in example 1.2 and compared with the alkali consumption of the individual components.
[0000]
TABLE 13
Titration and pH drop of blend of high ester pectin
and low ester propylene glycol alginate.
Time,
ml. NaOH
pH
Remarks
minutes
pH
0
3.66
0
10.00
1
3.77
1
9.24
2
3.9
2
8.51
3
4.05
3
8.05
4
4.22
4
7.76
5
4.46
5
7.57
6
4.83
7
7.34
7
6.47
Slightly
18
6.79
unstable
8
9.89
Unstable
28
6.55
97
5.87
[0354] FIG. 13.1 shows that the alkali consumption falls between the alkali consumption of the individual components, but the use of a mixture of a high DE pectin and a medium DE PGA results in a smaller increase in alkali consumption than observed with the mixture of a high DE pectin and a low DE pectin of example 12.
[0355] FIG. 13.2 shows that the pH-drop of the blend falls between the pH-drop of the individual components. However, even a relatively low esterified PGA provides for a faster pH-drop than a much higher esterified pectin.
[0356] Compared with the individual components the blend provides an increase in alkali consumption compared to the pectin product alone.
Example 14
Effect of Blending High De Propylene Glycol Alginate and Low DE Pectin
[0357] A blend of 50% of a propylene glycol alginate (PGA) having a DE of 85% and 50% of a pectin having a DE of 9.6% was dissolved at 70% in a similar manner as in example 12 and compared with the alkali consumption of the individual components.
[0000]
TABLE 14
Titration and pH drop of blend of high ester propylene
glycol alginate and low ester pectin
Time,
ml. NaOH
pH
Remarks
minutes
pH
0
4.06
0
10
1
4.12
1
9.04
2
4.18
2
8.55
3
4.25
3
8.22
4
4.33
4
7.97
5
4.4
5
7.79
6
4.49
20
6.9
7
4.57
34
6.6
8
4.68
44
6.47
9
4.8
69
6.25
10
4.94
93
6.12
11
5.13
12
5.41
13
6.5
Unstable
14
9.29
Unstable
[0358] FIG. 14.1 shows that the alkali consumption of the blend falls in between the alkali consumption of the individual components.
[0359] FIG. 14.2 shows that the pH drop over time falls between the pH-drop of the individual components.
[0360] Compared to the individual components, the blend provides for an increase in alkali consumption compared to propylene glycol alginate alone, and an increase in pH drop compared to low DE pectin alone.
[0361] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
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A skin-protecting alkalinity-controlling composition comprises one or more carboxylic acid polysaccharides. Said compositions are capable of providing buffering, and thus avoiding a major increase in the pH of an aqueous system and/or are capable of reducing the pH of aqueous systems, in which alkalinity is formed as a result of chemical and/or biological reactions. The compositions may be used in personal care products, such as skin creams and lotions, hygiene products, wound care products, fabric treating products etc.
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This is a continuation of application Ser. No. 673,024, filed Nov. 19, 1984, which was abandoned upon the filing hereof.
BACKGROUND OF THE INVENTION
This invention relates to a method of manufacturing a press lens which, after completion of the manufacturing steps, is so high both in configuration accuracy and in surface roughness that it is unnecessary to polish the lens.
Glass lenses are manufactured according to previously known methods in which glass is melted or softened, put into a metal mold, and the glass in the mold is pressed to have an external form which is generally similar to or approximating the desired final external form of the lens desired. The pressed lens is then subjected to cold grinding and polishing to make a finished lens.
The art has also described a procedure for pressing a lens having optical mirror surfaces which needs no grinding and polishing steps during the manufacturing in which a mirror-finished mold, is used to form the lens by pressing the lens-forming material in a non-oxidizing atmosphere. Glasslike carbon is disclosed as a suitable material for fabricating the mold in the specification of Japanese Patent Application Laid-Open No. 11277/1972, SiC or Si 3 N 4 are suggested as suitable mold materials in the specification of Japanese Patent Application Laid-Open No. 45613/1977, and a mixture of SiC and carbon are described as suitable mold materials in the specification of U.S. Pat. No. 4,168,961. It will be appreciated that if a lens can be manufactured in final form according to such a method, then the manufacturing cost can be greatly reduced and the processing time simplified because no grinding or polishing steps are required in the manufacturing process.
The following two methods of imparting an external form to a piece of glass which is substantially similar to the desired final external form are well known in the art. In the first method, molten glass having a viscosity of 10 to 10 3 poises is caused to drop in the form of a gob from the outlet, and the glass thus dropped, which is received by a mold at a temperature lower than the glass transition temperature, is pressed with a pressure of 2 to 10 kg/cm 2 . In this operation, the mold serves to shape the glass and to receive heat from the high temperature glass during pressing. The temperature of the mold is controlled and made lower than the glass transition temperature to prevent the mold from fusing with the glass. In this case, the pressing operation is stopped before the inside of the piece of glass thus formed is sufficiently solidified although the surface of the glass piece is cooled and solidified. Because of the difference in contraction between the cooled surface and the warmer inside of the glass piece, a so-called "shrink phenomenon" occurs with the piece of glass, and therefore the piece of glass thus formed is low in configuration accuracy. Indeed, if the pressing operation is carried out for a longer period of time at a low mold temperature, then the surface of the piece of glass is cooler than the inside thereof, and the piece of glass is easily cracked.
In the second method, a piece of glass stock such as a glass plate, a glass block or a glass bar, is cut to obtain a piece of glass having a predetermined volume dimensions, and the piece of glass thus obtained is coated with a release agent such as Al 2 O 3 or BN. The piece of glass thus treated is put in an oven where it is softened to about 10 5 poises and, thus softened, the piece of glass is quickly put in a mold and is pressed by a pressure of 5 to 50 kg/cm 2 . In this method, the related agent sticks to the surface of the product, and therefore it is necessary to grind and polish the product. On the other hand, in the press lens forming method disclosed by Japanese Patent Application Laid-Open No. 11277/1972 and U.S. Pat. No. 4,046,545, mentioned above, a piece of glass is put in a mold and it is pressed while it is being heated together with the mold. While the piece of glass together with and retained in the mold is being cooled, the pressing operation is continued until the temperature of the piece of glass becomes lower than the glass transition temperature. However, in this method, the cycle time to make a single pressed lens is considerably long, and the glass must be kept in contact with the mold for the long cycle time, as a result of which the surface of the mold is liable to be roughened unless special glass or a special mold material is used.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a mold which is used for the preform forming operation, an intermediate forming operation and the final forming operation.
FIGS. 2 and 3 are plan views outlining the arrangement of molds on turn tables. In FIGS. 2 and 3, N 2 gas is flowing out of the gaps in the molds, and all of the equipment is held in the atmosphere of N 2 gas.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors consider that factors essential for the successful manufacture of a press lens which, after completion of manufacturing operations is high both in configurational accuracy and in surface smoothness that it is unnecessary to grind and polish the pressed lens, are judicious selection of the mold and of the pressing conditions. A first condition essential for the mold is that the mold should be polished to a high surface smoothness, i.e., having any surface irregularities or pits of less than 100Å and finished with a high degree of configurational accuracy. In other words, the mold is carefully finished, dimensioned and polished so as to deliver a completed lens with the desired configuration and surface smoothness. For this purpose, the material of the mold must be of a fine composition or at least highly uniform. As the mold is used at high temperature, the material also must be sufficiently robust and exhibit the requisite high temperature strength and high temperature hardness. That is, the mold should not fuse with glass at high temperatures otherwise the surface of the mold will be roughened by glass. In addition, it is desirable to use for the substance forming the lens mold a material which is capable of preventing the surface of the mold from being roughened by oxidation due to air. It is, however, generally difficult to obtain a material which is completely free from oxidation. Therefore, it is necessary to use the mold in a non-oxidizing atmosphere, such as a N 2 , H 2 +N 2 , or CO+N 2 atmosphere. The mold which satisfies the above-described conditions is used in manufacturing the press lens in accordance with the method of the present invention.
This mold is much higher in accuracy and cost than a conventional mold used for forming a general external form by pressing. Accordingly, the pressing conditions should be selected so that the burden, i.e., the heat and pressure stress placed on the mold, is reduced. In order to form a pressed lens high in accuracy by the pressing procedure, the following two conditions are essential:
(1) the pressing operation is concluded with the temperature of the glass substantially equal to the temperature of the mold, so that any difference in temperature between the surface and the inside of the glass is eliminated or substantially completely eliminated. This prevents the occurrence of the shrink phenomenon.
(2) after the pressing operation is ended, i.e., when the glass is relieved from pressure, the glass has been sufficiently solidified such that it will not be deformed by gravity.
In order to meet these two conditions, a piece of glass having a high viscosity of about 10 9 to about 10 11 should be pressed by high pressure because with such a high viscosity it is necessary to use high pressure to deform the glass. However, in view of the effective maximum strength tolerance of the mold, it is desirable that the pressure applied is not higher than about 1000 kg/cm 2 . If the viscosity of glass exceeds 10 11 poises, it is substantially impossible to deform the glass by viscous flow; the operating viscosity is the range in which viscoelastic deformation occurs.
The fundamental conditions for forming a pressed lens having a high degree of dimensional accuracy are as described above. However, even if a high pressure press is employed, it is impossible to deform a piece glass having a high viscosity of 10 9 to 10 10 more than several microns to 100 microns in a limited period of time. For instance, in the case where a flat disk-shaped glass plate is formed into a spherical lens by pressing, the degree of deformation is much more than that described above. In a conventional press lens forming method, a piece of glass having a low viscosity at extremely high temperatures is pressed by a relatively low pressure, i.e., 2 to 10 kg/cm 2 , into a predetermined form. However, in this conventional method, the piece of glass thus treated shrinks after cooling, and as the piece of glass at high temperature is put in the mold, the surface of the mold is liable to be roughened.
The present inventors have found that if a piece of glass at a relatively low temperature, i.e., a piece of glass whose inside viscosity is 10 6 to 10 8 .5 poises, is put in a mold held at a temperature higher than the glass transition temperature and is pressed by a high pressure of 100 kg/cm 2 or higher, the piece of glass is sufficiently deformed to have a predetermined form and the pressing operation can be completed in a relatively short time.
Briefly stated, the present invention is characterized by a press lens forming method in which a piece of glass whose inside viscosity is 10 6 to 10 8 .5 poises is put in a mold at a temperature higher than the glass transition temperature and is pressed by a pressure of 100 kg/cm 2 or higher, the pressing operation being completed when the viscosity of the glass reaches 10 9 to 10 11 poises. When the pressing operation is completed, the temperature of the mold is substantially equal to that of the glass, and the temperature of the surface of the pressed glass product is substantially equal to that of the inside thereof.
The present invention also proposes a multi-step pressing method in order to improve productivity. As described above, generally stated the press for forming pressed lenses is used to perform two functions. In its first function, a piece of glass is relatively greatly deformed to give it a general external approximating that of the finished article form. In the second function, the configurational accuracy of the product is increased. Accordingly, the pressing operation can be performed in two or three steps, according to the functions of the process. In this case, for instance, two or three metal molds are set on a turntable, and a piece of glass supported by a ring-shaped mold is positioned into the molds and pressed successively. If this operation is carried out continuously, then the time required for pressing the piece of glass with each mold is reduced, thereby improving productivity.
In the case where a piece of glass a processed to have a general external form is used, i.e., a disk-shaped glass formed by punching a plate of glass or by cutting a round bar, or a piece of glass which is obtained by cooling a gob of glass formed according to a conventional method and by removing shearing marks therefrom is used, a preform forming operation is carried out in which, for instance, the piece of glass is supported by a ring-shaped mold, and heated and softened, e.g., by a laser beam, such that the viscosity of the inside of the glass becomes 10 6 to 10 7 .8 poises. Next the piece of glass, together with the ring-shaped mold, is put into a preform-forming mold where it is formed into a preform. In this operation, sand marks are removed from the piece of glass, and therefore the piece of glass may be one which is sand-ground. In succession, the piece of glass thus treated, together with the ring-shaped mold, is conveyed, so that in intermediate forming operation is carried out when the glass inside viscosity is 10 7 .5 to 10 9 poises, to a final forming operation which is carried out when the inside glass viscosity is 10 7 .5 or 10 8 .5 to 10 11 poises. This prevents occurrence of the shrink phenomenon, and the optical mirror surfaces of the mold are transferred to the piece of glass. It is preferable that prior to these steps the surface of the piece of glass is substantially heated to a temperature higher than that of the inside of the piece of glass. In each step, the temperature of the mold is set to a temperature higher than the glass transition temperature, but in the finial forming operation it is adjusted to a temperature substantially equal to or slightly lower than the temperature of the glass. Even if the intermediate forming operation or the final forming operation is eliminated, a press lens can be manufactured with high efficiency.
Use of the multi-step pressing method provides not only the desirable result that the productivity is improved, but also the advantage that an expensive mold which is high in surface accuracy and surface smoothness is used only in the final forming operation. In the final forming operation, the glass temperature is decreased, and the mold is in contact with the glass for only a short time. Accordingly, the service life of the mold is increased, and therefore the general manufacturing cost is greatly reduced.
Another embodiment of the process is a modification of the multi-step pressing method, in which a preform is used which is obtained by pressing a gob of glass in a conventional manner (with a glass viscosity of 10 to 10 3 and a pressing pressure of 2 to 10 kg/cm 2 ) to provide an external form generally similar to the desired final external form and similarly as in the abovedescribed case the intermediate forming operation and the final forming operation are carried out. In this case, the gob of glass thus formed should have no shearing marks. In general, in the conventional method of forming a lens by pressing, the temperature of the mold used is low, and therefore the product is liable to have a tree pattern. However, the tree pattern can be eliminated by the intermediate forming operation. Thus, the pressing operation can be carried out with high accuracy in succession with the glass melting operation.
The method of the present invention will now be further described with reference to the following working examples which are illustrative.
DETAILED DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a mold used for a preform forming operation, an intermediate forming operation, or a final forming operation. FIG. 2 is a plan view outlining the arrangement of molds, etc. on a turntable in Example 1 of this invention. FIG. 3 is a plan view outlining the arrangement of molds, etc. on a turntable in Example 2 of the invention. In FIG. 1, 1 is the upper mold, 2 is the ring-shaped mold, 2' is the holding part of the mold, 2, 3 are the lower molds, 4 is the sleeve, 5 is the inlet/outlet, 6 is the preform or gob. In FIGS. 2 and 3 the various positions represented are I is the glass supplying position, P P is the preform forming mold position, P I is the intermediate forming mold position, P F is the final forming mold position, T 1 , T 2 , T 3 and T 4 are the heating positions, O is the take-out position.
EXAMPLE 1
This example described a method of pressing. A dense flint glass group optical glass SF11 was used. A gob of optical glass SF11 was formed by the conventional molding method, as described above. After cooling, the gob thus formed was polished to remove shearing marks. The resulting gob was employed as a preform. The final configuration of the lens was in the form of a meniscus 12 mm in diameter and 5 mm in central thickness.
A metal mold made of tungsten carbide and coated with TiN was employed. The mold, as shown in FIG. 1, comprises the upper mold 1, a ring-shaped mold 2, the lower mold 3, a sleeve 4, and an inlet-outlet 5 for the glass and the ringshaped barrel. A preform 6, preheated to a temperature higher than the glass transition temperature, was placed on the ring-shaped mold 2 which was preheated in the same manner. Under these conditions a 850° C. heating unit arranged adjacent to the mold was used to heat the preform for about eighteen (18) seconds until the viscosity of the inside of the preform reached 10 6 .5 poises. The preform was inserted into the sleeve 4 of the mold through the inlet/outlet 5 while being supported by the ring-shaped mold. The preform was pressed by moving the upper and lower molds along the sleeve. In this operation, the temperature of the mold was 473° C., the pressing pressure was 200 kg/cm 2 , and the pressing time was 18 seconds. After annealing, the surface accuracy of the lens was within two Newton rings, and within a half line in astigmatic difference. Thus, the lens was accurate enough to be used as a photographic lens.
EXAMPLE 2
In this example a piece of glass obtained by cutting a plate of glass was used and a multistep pressing method was employed. The dense flint glass group optical glass SF11 was used. The final configuration of the lens formed was such that the diameter was 12 mm and the central thickness was 1 mm; both surfaces were concave. A preform-forming mold and a final forming mold made of tungsten carbide and coated with TiN were employed. Each of the molds, as shown in FIG. 1, comprises the upper mold 1, a ring-shaped mold 2, the lower mold 3, a sleeve 4, and an inlet/outlet 5 for the glass and the ring-shaped mold.
In FIG. 2, reference numeral 7 designates a table which is divided into eight equal sections which are radially arranged. The above-described mold assemblies are installed at the centers of the sections P P (press preforming) and P F (press final), respectively. Further in FIG. 2, reference numeral 8 designates a cylinder assembly in which eight piston cylinders 9 are radially arranged. The cylinder assembly 8 is turned in a stepping manner to stop at each section or position. Each cylinder 9 has a piston 10 with a ring-shaped mold holding member 11. At the position I, the piece of glass is placed on the holding part 2' of the ring-shaped mold 2. The piece of glass together with the ring-shaped mold 2 is moved to the heating positions T 1 and T 2 so that the glass is softened by heat. Then, at position P P , the glass and the ring-shaped mold 2 are moved into the sleeve 4 of the preform forming mold through the inlet/outlet 5. Under this condition, the upper and lower molds are moved along the sleeve, to press the glass on the ring-shaped mold 2. As the upper and lower molds are accurately guided by the sleeve, the mold can be centered with a high degree accuracy. The preform thus formed is moved to the third heating position T 3 together with the ring-shaped mold, where it is heated so that it is uniform in temperature. Thereafter, at the position P F , the preform is subjected to final forming in the mold in the same manner as that described above. The glass thus treated is cooled at the position T 4 . Then, at the position O, the pressed lens is removed from the ring-shaped mold, and is then sent to the following station where it is gradually cooled. The lens forming conditions by pressing in the example 2 are as listed in the following Table 1:
TABLE 1______________________________________Glass inside Viscosity Mold Press-temper- of the temper- Pressing ingature same ature pressure time______________________________________Preform 590° C. 10.sup.7 poises 478° C. 200 Kg/cm.sup.2 10 secformingFinal 469° C. 10.sup.7 poises 469° C. 380 Kg/cm.sup.2 10 secforming______________________________________
The surface accuracy of the lens thus formed was within two Newton rings and within a half line in astigmatic difference. Thus, the lens was sufficiently high in accuracy. In the example, the lens was thin, and therefore it was unnecessary to perform the intermediate forming operation. However, if a lens to be formed is relatively large in thickness, it is preferable that the intermediate forming operation is carried out between the preform forming operation and the final forming operation.
EXAMPLE 3
In the example, a coarse forming operation (a conventional operation of roughly forming an external form by pressing) was first carried out. Phosphate glass, having a glass transition temperature 420° C., n d 1,600 and ν d 63.5, was used. The final configuration of the lens was such that the diameter was 30 mm and the central thickness was 4 mm and that both surfaces were convex. In the coarse forming operation, a mold of cast iron was used. The coarse forming operation was carried with a lower mold movement type tunrtable in the conventional manner.
An intermediate and final forming turntable as shown in FIG. 3 was set next to the coarse forming turn table. In FIG. 3, at position I the coarse product is put in the ringshaped mold by a vacuum chuck so that it is supported by the holding part 2' of the ring-shaped mold 2. Under this condition, the coarse product is moved successively heating positions T 1 and T 2 , where it is heated. Thereafter, at the position P I the coarse product together with the ring-shaped mold is inserted into the sleeve 4 of the intermediate forming mold through the inlet/outlet 5, so that it is pressed. Then, at the position T 3 , the product is made uniform in temperature. At position P F , the final forming operation is carried out. The lens forming conditions by pressing in the example are listed below:
TABLE 2______________________________________Glass Viscosityinside Viscosity Moldtemper- of the temper- Pressing Pressingature same ature pressure time______________________________________Coarse 810° C. 20 370° C. 3 kg/cm.sup.2 5 secforming poisesInter- 490° C. 10.sup.7.5 448° C. 150 kg/cm.sup.2 15 secmediate poisesformingFinal 448° C. 10.sup.10.5 448° C. 380 kg/cm.sup.2 15 secforming poises______________________________________
The surface accuracy of the glass lens thus formed was within four Newton rings and within one line in astigmatic difference. Thus, the lens was sufficiently high in accuracy.
According to the present invention, a high precision press lens which needs no grinding and polishing after being formed by pressing can be manufactured in a relatively short period of time, and furthermore the glass temperature is relatively low and the pressing time short. Accordingly, the service lives of the expensive molds which have been polished with high accuracy can be increased. As a result, the manufacturing cost can be made much lower than that which is required when the conventional lens manufacturing method is employed.
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Optical lenses high in configurational accuracy with smooth surfaces are press molded in a carefully finished, polished and properly dimensioned mold preferably in a non-oxidizing atmosphere. The molding operation includes placing a quantity of glass having an internal viscosity of at least about 10 6 poises in such a mold while maintaining the mold at a temperature at least equal to the glass transition temperature and thereafter passing the glass into a lens of predetermined configuration at a pressure of at least 100 Kg/cm 2 . Performing procedures are also disclosed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/937,847 filed Jun. 29, 2007.
FIELD OF THE INVENTION
This relates to the field of medical devices and more particularly to catheters and catheter assemblies.
BACKGROUND OF THE INVENTION
Hemodialysis catheters are implanted into the vasculature of a patient, and have proximal ends that extend from the patient and are connectable to and disconnectable from tubing of a hemodialysis apparatus. Such catheters are provided with a first lumen and a second lumen coextending to respective distal tips that are carefully positioned at a selected site in a particular vessel of the patient, so that undialysed blood may be withdrawn from the patient's vessel while dialysed blood may be reintroduced into the patient's vessel simultaneously, at respective distal tip openings of the lumens. The catheter lumens may be coextending separate catheters or may be dual (or more than two) lumens of a single catheter separated by a septum wall. The distal tips of the two lumens are generally staggered along the vessel such that blood being withdrawn does not include any significant amount of dialyzed blood that has been reintroduced into the vessel at the more distal of the two distal tips.
When a particular dialysis procedure has been completed, the proximal ends of the catheter are disconnected from the tubes of the hemodialysis apparatus, and the lumens are generally inactive until the subsequent dialysis procedure, although fluid medication or saline may be infused into at least one of the lumens, if and when desired, or a blood sample withdrawn. However, blood is highly susceptible to coagulation and clot formation. The addition of a specific agent or locking solution to the catheter or any extracorporeal blood-contacting surface can reduce the incidence of coagulation by interfering and/or inhibiting the hematological chemistry of blood and its interaction with synthetic materials, such as those from which catheters are made.
It is conventional, then, to introduce anticoagulant locking solutions such as heparin into an implanted catheter between hemodialysis treatments, to prevent clotting of blood within the catheter, and which then is withdrawn for the subsequent dialysis procedure. Between hemodialysis treatments, the catheter is clamped off outside of the patient, creating a pressure gradient that holds the locking solution within the lumens. However, certain amounts of locking solution are known to enter the patient's blood stream through the open distal tips, especially in areas where side holes are present. The amounts introduced into the patient are generally not at a level to cause toxicity or disrupt a patient's hematology; however, the leaching of small amounts of locking solution from the distal lumen tips makes the catheter more prone to lumen clot-off.
One catheter assembly directed to minimizing amounts of locking solution entering the patient's blood stream is disclosed in U.S. Patent Publication No. US 2006/0253063 A1. In this application, the catheter includes a first lumen having a first distal tip, and a second lumen having a second distal tip, wherein the first and second distal tips having wall sections that are normally disposed in a closed position but are each openable under fluid pressure. While both lumens have openable distal tip wall sections, the first distal tip has a flap openable both inwardly and outwardly when the first lumen is subjected to negative pressure and positive pressure, respectively, relative to the blood pressure of the patient in whom the catheter has been implanted. The second lumen extends a selected distance distally of the first distal tip to a second distal tip that is a generally rounded tip when closed, and the second distal tip is defined by an openable section that is internally concave and may be formed by at least one slit cut into a closed rounded distal tip after extrusion of the lumen, defining at least two generally curved lip portions.
With respect to the above-discussed catheter system of Publication No. US 2006/0253063 A1, the several lip portions are openable outwardly under positive pressure applied to the distal end of the second lumen, and a closable together under negative pressure applied to the second lumen. Near the second distal tip, in the side wall of the second lumen are side port sections that are openable inwardly upon application of negative pressure to the proximal end of the second lumen. The closable and openable sections of the first and second distal tip sections of the first and second lumens operate thusly: during hemodialysis, negative pressure is applied to the first lumen and blood is drawn from a patient's vessel into the first distal tip and through the first lumen; positive pressure applied to the second lumen when blood enters the proximal end of the second lumen and separates the several lip portions at the second distal tip to re-enter the vessel. Were the reverse of the pressures to be caused by an incorrect hemodialysis connection, blood traveling into the first lumen would open the flap to enter the vessel, while negative pressure on the second lumen would close the several lip sections but open the side ports for blood to enter from the vessel. Between dialysis procedures, locking solution injected under low pressure into the catheter would fill both lumens since the distal tips would be in their closed, undeflected conditions, and when removed, blood from the vessel would enter both distal tips due to negative pressure on both lumens.
It is desired to provide a catheter that will minimize or eliminate the small amounts of locking solution entering a patient's blood stream from an implanted catheter between dialysis treatments.
BRIEF SUMMARY OF THE INVENTION
The present invention is a closable and openable catheter assembly of first and second catheters having respective first and second lumens, first and second distal portions, first and second proximal portions, first and second distal end portions, and first and second proximal end portions; first and second distal openings defined into the first and second distal end portions of the first and second catheters for fluid communication between the first and second lumens with vasculature of a patient when the distal portions of the first and second catheters are implanted in the vasculature; and an actuating assembly in operative association with respect to the first and second catheters, wherein actuation of the actuating assembly actuates at least one of the first and second distal end portions between opened and closed conditions wherein the first and second lumens are in fluid communication with the vasculature of the patient in the opened condition and the first and second lumens are not in fluid communication with the vasculature of the patient.
The present invention also includes an actuator assembly for a closable and openable catheter assembly where the catheter assembly includes a first and second catheter wherein one of the first and second catheters is axially movable with respect to the other to close and open distal openings of the first and second catheters, including a first actuator portion rotatably affixed about one of the first and second catheters, and a second actuator portion nonrotably affixed to the one of the first and second catheters, wherein relative rotation of the first actuator portion with respect to the second actuator portion and between first and second angular stops, permits and prevents respectively, axial movement between first and second axial positions of the second actuator portion with respect to the first actuator portion and also with respect to the other of the first and second catheters, wherein when the second actuator portion is in the first axial position, the distal openings of the first and second catheters are open and when the second actuator is in the second axial position, the distal openings are closed.
Also, the present invention includes a closable and openable catheter assembly, including a first catheter and a second catheter respectively having first and second distal end portions and having respective distal openings to vasculature of a patient when the catheter assembly is implanted within the patient; and each of the first and second distal end portions having respective closure structures to occlude the distal openings of the other when the catheter assembly is actuated to a closed condition, and which do not occlude the distal openings of the other when the catheter is actuated to an opened condition.
In a preferred embodiment, the catheter assembly comprises a dual lumen catheter wherein a first lumen is defined in a separate, generally coaxial inner catheter within an outer catheter and that is movable axially with respect to the second or outer lumen by manipulation remote from the distal end, of a proximal inner catheter end section extending proximally from a hub outside of the patient and separate from the proximal outer catheter end section, all while the assembly remains sealed. The first distal tip of the inner catheter extends at least to some extent distally of the second distal tip of the outer catheter and includes an enlargement, such as a closure cap assembly, sufficiently large in diameter to close off the distal opening of the outer catheter when positioned thereagainst in the closed catheter assembly position. While it is preferred that the enlargement include an aperture therethrough for guide wire placement, a valve traverses the aperture and allows for passage of the guide wire, where upon guide wire removal, the aperture seals closed.
The inner catheter includes at least one side port proximally of the enlargement for fluid communication between the first lumen and the vessel when the inner catheter is in the open position, and the inner catheter side ports are closed by the surrounding outer catheter when the inner catheter is in the closed position. Further, the inner catheter includes a barrier section that blocks and closes all outer catheter side ports preferably from within the outer catheter when the inner catheter is in the closed position, whereby no side ports in either the first lumen or the second lumen are open to the blood vessel when the catheter assembly is closed. Locking solution is successfully kept within the catheter assembly when in the closed position, and fluid flow successfully permitted when the catheter assembly is in the open position.
In a preferred embodiment of distal tip arrangement, the side ports of the outer catheter comprises a pair of elongate slots on opposite sides while the barrier section of the inner catheter comprises a pair of outwardly projecting ribs that are disposed in the respective slots and are movable therealong between forward or open, and rearward or closed, positions with respect thereto when the inner catheter is moved between open and closed positions.
The proximal end section of the inner catheter extends proximally through the hub of the assembly and is movable axially therewithin, and may have secured thereto an extension tube proximally of the hub by a connecting arrangement that is part of the present invention; the outer catheter proximal end may be joined to a respective extension tube within the hub, as is conventional.
Manipulation of the inner catheter between open and closed positions is preferably attained by controlled and limited axial movement of the inner catheter with respect to the assembly and the outer catheter. The proximally disposed actuator assembly for the inner catheter may comprise an adapter sleeve and a swivel sleeve, and the actuator assembly may also serve to connect the inner catheter to a respective extension tube. The swivel sleeve is located adjacent to the proximal hub exit for the inner catheter and provides an inner cylindrical wall surface having defined thereinto a pair of opposed first and second slots spaced axially therealong coextending circumferentially from respective opposed axial slots extending therebetween, defining first and second, or open and closed, positions, with the open position provided by the more distal first slot and the closed position provided by the more proximal second slot. The swivel sleeve is manually rotatable with respect to the assembly about the inner catheter proximally of the hub.
The adapter sleeve of the inner catheter is positioned proximally of the swivel sleeve but has a distal portion extending into the proximal end of the swivel sleeve, which distal portion includes a pair of detents on opposite sides of the distal portion and projecting radially outwardly. The adapter sleeve is movable axially with respect to the swivel sleeve and the hub only when the swivel sleeve has been rotated to an “open” position in which the axial slots are moved into alignment with the detents, which can then move axially along the axial slots and then circumferentially along either the first or second slot portion relative to the swivel sleeve. A pair of stabilizing posts may preferably extend distally from the distal end of the cylindrical body of the adapter sleeve and extend through the swivel sleeve adjacent to its inner surface to stabilize the coaxial orientation of the sleeves when in the closed position, when the adapter sleeve is relatively proximally spaced from the swivel sleeve. Visual indicators preferably are provided on both the adapter sleeve and the swivel sleeve, for the practitioner to determine the location of the slot followers with respect to the first and second slot portions to indicate the open or closed positions.
A method of the present invention comprises the steps of providing a catheter having an outer catheter and an inner catheter to which a hub is secured along the proximal portions thereof, the inner and outer catheter having respective distal portions extending to respective distal tip portions, and the inner catheter being movable axially within and along the outer catheter and the hub by an actuator assembly of the inner catheter to move a distal tip of the inner catheter relative to the distal tip portion of the outer catheter to open and close both catheters; and actuating the actuator assembly to move the inner catheter axially with respect to the outer catheter and the hub to move the inner catheter distal tip portion between open and closed positions relative to the outer catheter distal tip portion, to open and close the distal openings of both the inner and outer catheter lumens.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate the presently preferred embodiments of the invention, and, together with the general description given above and the detailed description given below, serve to explain the features of the invention. In the drawings:
FIGS. 1 and 2 are elevations view of the catheter assembly of the present invention in the closed and open positions, respectively;
FIGS. 3 and 4 are longitudinal cross-sectional views of the catheter assembly of FIGS. 1 and 2 , with the catheter assembly in the closed and opened positions, respectively;
FIGS. 5 and 6 are enlarged cross-sectional views of the distal end portion of the assembly of FIGS. 3 and 4 in the closed and opened positions, respectively, taken along lines 5 - 5 and 6 - 6 thereof, respectively;
FIGS. 7 and 8 are elevation and top views of the outer catheter's distal end portion, respectively, with an outer sleeve exploded therefrom in FIG. 7 ;
FIGS. 9 to 11 are top, elevation and cross-sectional views of the inner catheter's distal end portion, respectively, with the closure cap exploded therefrom in FIG. 9 and the cross-sectional view taken along lines 11 - 11 of FIG. 9 ;
FIG. 12 is an enlarged isometric view of the inner catheter's distal end portion;
FIGS. 13 and 14 are enlarged cross-sectional views of the inner catheter distal end with the closure cap components, in the exploded and assembled relationships, respectively;
FIGS. 15 and 16 are isometric views of the adapter sleeve and the swivel sleeve, respectively that comprise the actuator assembly for the inner catheter;
FIG. 17 is a diagrammatic view of the interior surface of the swivel sleeve of FIG. 16 ;
FIGS. 18 and 19 are enlargements of the hub of the assembly of FIGS. 3 and 4 , in cross-section, in the closed and opened positions, taken along lines 18 - 18 and 19 - 19 of FIGS. 3 and 4 , respectively; and
FIGS. 20 and 21 are exploded cross-sectional views of the proximal end of the hub showing the components that will be secured to the catheter assembly at the proximal end of the hub and with respect to the inner catheter, respectively, that will enable remote movement of the distal tip of the inner catheter, with FIG. 21 showing the adapter and swivel sleeves of FIGS. 15 and 16 .
DETAILED DESCRIPTION OF THE INVENTION
In the drawings, like numerals indicate like elements throughout. Certain terminology is used herein for convenience only and is not to be taken as a limitation on the present invention. The term “distal” is meant to describe the portion of a catheter according to the present invention that is inserted into a patient, and the term “proximal” is meant to describe the portion of a catheter according to the present invention that remains exterior of the patient. The terminology includes the words specifically mentioned, derivatives thereof and words of similar import. The embodiments illustrated below are not intended to be exhaustive or to limit the invention to the precise form disclosed. These embodiments are chosen and described to best explain the principle of the invention and its application and practical use and to enable others skilled in the art to best utilize the invention.
FIGS. 1 to 4 illustrate a catheter assembly 10 of the present invention in a closed condition and an open condition, respectively. The length of the catheter assembly has been shortened from its desired actual length. Catheter assembly 10 includes an outer catheter 12 , an inner catheter 14 ( FIGS. 3 and 4 ), a hub 16 , a first extension tube assembly 18 affixed to the proximal end 20 of the catheter assembly 10 in fluid communication with the inner catheter 14 , and a second extension tube assembly 22 affixed to the hub 16 to be in fluid communication with outer catheter 12 within hub 16 . The first and second extension tube assemblies are shown to include clamps therealong and luer fittings or connectors at proximal ends thereof, as is conventional. Preferably, the hub is insert-molded about the proximal end portion of the outer catheter. Through the use of mandrels and/or core pins (not shown), the hub 16 is molded to include an angled passageway 24 ( FIGS. 3 , 4 and 20 ) providing fluid communication between the lumens of the outer catheter and its extension tube assembly 22 ; the hub also is molded to include a linear passageway 26 therethrough into which a proximal end portion 128 (see FIG. 19 ) of the inner catheter 14 will extend as it exits from the proximal end 28 of the outer catheter to be joined to a steel cannula 29 such as by being expanded to extend over a distal end portion of the steel cannula forming a tight, sealed grip thereto, defining an inner catheter/steel cannula subassembly. Steel cannula 29 will continue through linear passageway 26 and protrude from hub 16 ; the inner catheter/steel cannula subassembly 14 , 29 is axially movable with respect to the outer catheter 12 and the hub 16 .
In accordance with the present invention and referring primarily to FIGS. 1 to 4 , a closure cap assembly 30 containing therewithin a valve is secured to the distal tip section 32 of inner catheter 14 and closes off the distal end opening 34 (see FIG. 12 ) of the lumen of the inner catheter. Closure cap assembly 30 is also sufficiently large in diameter to close off the distal tip opening 36 ( FIGS. 7 and 8 ) of the lumen of outer catheter 12 when the catheter assembly is in the closed position. Preferably, a containment sleeve 38 is affixed about, and is conterminous with, a distal end portion 40 of outer catheter 12 and having a distal sleeve end 42 that abuts a proximal surface 44 of closure cap assembly 30 when the catheter assembly is in the closed condition.
Seen in FIGS. 1 to 4 , outer catheter 12 of the present invention preferably includes a pair of elongate side slots 46 along the distal end portion 40 , permitting fluid communication of the lumen with the vasculature of the patient (when the catheter assembly is in the open condition). Side slots 46 are shown to extend to the distal tip of outer catheter 12 , at distal tip opening 36 (see FIG. 8 ); this is not required for operation of the invention, but is practical from a manufacturing and assembly standpoint. Inner catheter 14 also includes side slots 48 along its distal end portion 50 , extending proximally from proximal surface 44 of closure cap assembly 30 , establishing fluid communication with the vasculature of the patient when the catheter assembly is in the open condition.
Portions 52 of the inner catheter side wall appear in FIGS. 2 and 4 to 6 between the side slots 48 , joining the closure cap assembly 30 to the main portion of the inner catheter 14 . Inner catheter 14 further includes a pair of elongate ribs 54 along opposite sides of distal end portion 50 , best seen in FIGS. 9 to 12 , extending proximally from side wall portions 52 ; elongate ribs 54 are associated with elongate slots 46 of outer catheter 12 and are disposed therein and therealong upon assembly of the catheter assembly. Elongate ribs 54 are movable axially within elongate slots 46 during axial movement of the inner catheter with respect to the outer catheter 12 during actuation of the assembly between its opened and closed conditions, to open the outer catheter for fluid transmission therethrough. Distal tip section 32 of inner catheter 14 is defined distally of side slots 48 and side wall portions 52 , and becomes part of the closure cap assembly 30 . It is preferable for the distal end portion 50 of inner catheter 14 to undergo an insert molding manufacturing procedure for defining the elongate ribs 54 and the distal tip section 32 , which preferably includes formation of a surrounding sleeve 56 that serves to block communication between the inner catheter 14 and the outer catheter 12 , which is best shown in FIG. 12 .
Now referring to FIGS. 7 and 8 , distal end portion 40 of outer catheter 12 is seen to have a pair of opposed elongate slots 46 extending to the distal end thereof, in communication with the lumen of outer catheter 12 for fluid transmission with the vasculature of the patient when the catheter assembly of the present invention is in the opened condition. Containment sleeve 38 is affixed to the distal end portion 40 after assembly of the inner catheter within the outer catheter, and may be prepositioned along the outer assembly proximally of the distal end portion during assembly and then slid into position, acting to seal the outer catheter by covering most of the length of the elongate slots 46 , and also the elongate ribs 54 of the inner catheter, except for preselected proximal slot portions as seen in FIGS. 1 and 2 which are open to the vasculature when the elongate ribs 54 therein are in their distalmost positions when the catheter assembly is in the opened condition.
In FIGS. 9 to 12 , the distal end portion 50 of inner catheter 14 is shown, having sleeve 56 molded thereonto and including elongate ribs 54 and distal end section 32 . Cap member 58 is shown in FIG. 9 positioned to be affixed onto distal end section 32 of inner catheter 14 . Sleeve 56 is best shown in FIGS. 11 and 12 .
The structure of closure cap assembly 30 will now be described in detail with respect to FIGS. 13 and 14 . Cap member 58 includes a domed distal face 60 and includes a small diameter hole therethrough and centered with respect to domed distal face 60 ; hole 62 permits insertion and implantation of the catheter assembly into the vasculature of a patient through the use of a small diameter guide wire (not shown), as is conventional, facilitating the various curves and bends in the vasculature in order to precisely position the distal tip of the catheter assembly in position. Hole 62 is aligned with a corresponding hole 64 into distal end section 32 of inner catheter 14 , which in turn is centered with respect to the lumen of the inner catheter when cap member 60 is assembled to distal end section 32 . Cap member 60 further includes a shaped proximal cavity 66 having a capture flange 68 complementary to a capture recess 70 of distal end section 32 to physically secure the cap member to the distal end section; an annular groove 72 is formed into capture flange 66 for placement of a bead of adhesive to bond cap member 58 to distal end section 32 . Cap member 58 further preferably includes a capture recess 74 distally of capture flange 68 , into which becomes seated a distalmost flange 76 of distal end section 32 .
A valve 78 is inserted into cap member 58 , being seated in valve seat 80 in the distal portion of proximal cavity 66 . Valve 78 is shown to include a slit 82 partially transversely thereacross, which slit is normally closed but which is openable to permit passage therethrough of a guide wire. Tapering or funneling surfaces are defined through distal end section 32 and the distal end of cap member 58 to act as lead-ins for facilitating the insertion through the small diameter holes 62 , 64 , of a guide wire in the event that the catheter assembly after initial implantation were to be removed and replaced. Valve 78 remains closed after the catheter assembly has been implanted in the vasculature and the guide wire removed, even when the catheter assembly is in the opened condition since hole 62 is not used for fluid transmission.
Turning now to FIGS. 15 to 17 , an adapter sleeve 90 and a swivel sleeve 92 will now be described, that comprise the actuator assembly for axial movement of the inner catheter 14 . Adapter sleeve 90 has a proximal end projection 94 over which will be fitted the distal end of the extension tube assembly 20 , as seen in FIGS. 1 to 4 ; thus, adapter sleeve 90 serves as the connector of the extension tube assembly 20 to the inner catheter 14 . An annular collar 96 is located proximal to cylindrical body section 98 , and a smaller diameter distal section 100 extends distally from body section 98 to end faces 102 . A pair of detent projections or detents 104 are positioned on opposite sides of distal section 100 adjacent end faces 102 . A pair of stabilizing struts 106 extend distally forwardly from distal section 100 .
Swivel sleeve 92 is cylindrical, having a proximal end 108 and a distal end 110 . An array of grooves 112 preferably is formed on the exterior side surface thereof to facilitate manual gripping of the swivel sleeve during rotation thereof by the practitioner, during opening and closing the catheter assembly. Referring particularly to the diagram of FIG. 17 , into and along the interior surface 114 of swivel sleeve 92 is a slot arrangement 116 with which the pair of detents 104 of the adapter sleeve 90 cooperate to move the inner catheter/steel cannula subassembly 14 , 29 to defined fully opened and fully closed positions of the inner catheter 14 . Slot arrangement 116 comprises a pair of opposed axially extending slot portions 118 , circumferentially extending distal slot portions 120 and circumferentially extending proximal slot portions 122 communicating with axially extending slot portions 118 . At the proximal ends of the axially extending slots are seen short slot portions 126 extending to the proximal end 108 that permit positioning of the detents 104 of adapter sleeve 90 into the slot arrangement 116 during assembly of the adapter sleeve and the swivel sleeve to the steel cannula 29 as it projects proximally from the hub 16 (see FIGS. 3 , 4 , 18 and 19 ).
With respect to FIGS. 18 to 21 , the structure and operation of the actuation assembly 130 of the catheter assembly of the present invention will now be described. Actuator assembly 130 is affixed to the inner catheter proximal portion 128 in such a manner that adapter sleeve 90 and inner catheter 14 together are able to move axially with respect to swivel sleeve 92 ; detents 104 are able to be moved axially along axial slot portions 118 between the slot portions 120 , 122 . Swivel sleeve 92 is rotatably movable with respect to the adapter sleeve 90 and the inner catheter 14 , with detents 104 able to follow circumferential slot portions 122 at the proximal end of swivel sleeve 92 in an angular direction, or to follow circumferential slot portions 120 at the distal end 110 of the swivel sleeve in an angular direction opposite from that related to slot portions 122 , corresponding to the closed condition and the opened condition, respectively, of the catheter assembly of the present invention.
Actuator assembly 130 is affixed to the hub 16 in the following manner. Two additional components are utilized, preferably along with an o-ring, that are disposed primarily within the hub proximal end portion 132 associated with the inner catheter 14 and steel cannula 29 to which it is joined, in order to permit rotation of swivel sleeve 92 as well as sealing with respect to the inner catheter but which permits axial movement of the inner catheter 14 with respect to the hub. Linear passageway 28 of hub 16 receives thereinto a generally tubular outer sleeve component 134 that is bonded therewithin; outer sleeve 134 includes an external antirotation rib 136 preventing its rotation with respect to hub 16 and also serving as an antirotation strain relief in cooperation with a corresponding slot of the hub thereover ( FIGS. 18 to 21 ). A generally tubular inner sleeve component 138 is disposed within outer sleeve component 134 and around steel cannula 29 , and an o-ring seal 140 is disposed in the distal end 142 of outer sleeve 134 and is abutted by the distal end 144 of the inner sleeve upon assembly; o-ring 140 sealingly engages the outer surface of steel cannula 29 in a manner which permits the inner catheter/steel cannula subassembly 14 , 29 to move axially between opened and closed positions (see FIG. 21 ) and also defines a seal between the interior passageways of the hub and the proximal exit for steel cannula 29 . Preferably, inner sleeve 138 is bonded to outer sleeve 134 .
Inner sleeve 138 includes a flange/recess capture section 146 at its proximal end 148 , complementary to a corresponding flange/recess capture section 150 at the distal end 110 of swivel sleeve 92 . The flange/recess capture sections permit relative rotational movement of the swivel sleeve with respect to the hub 16 and, actually, the entire catheter assembly. Also, as seen in FIG. 20 , inner sleeve 138 includes a pair of strut-receiving slots 152 extending distally from the proximal end 148 , whereinto extend the stabilizing struts 106 of adapter sleeve 90 of the actuator assembly as the struts extend distally beyond the distal end 110 of the swivel sleeve when the catheter assembly 10 is in its opened condition and the inner catheter has been translated to its distalmost position.
Visual indicators are preferably provided with the catheter assembly 10 of the present invention to provide a clear indication to the practitioner whether the inner catheter is in its closed condition or its opened condition, since the distal portion of the catheter assembly is within the vasculature of the patient while the proximal portion including the hub 16 is external to the patient. A pair of axially extending marker stripes 160 are provided on the external surface of the swivel sleeve 92 at preselected angular locations on opposite sides of the sleeve. The adapter sleeve 90 is provided with two pairs of axially extending marker stripes 162 , 164 : one pair of marker stripes 162 is provided on the external surface of the section 98 and are associated with the opened condition of the catheter assembly, and become aligned with and adjacent to respective ones of the marker stripes 160 of the swivel sleeve when the adapter sleeve is in its distalmost position adjacent the swivel sleeve and fully rotated so that the detents are located at the termini of the distal slot portions 120 in the swivel sleeve; another pair of marker stripes 164 is provided on the external surface of the distal section 100 of the adapter sleeve, angularly offset from marker stripes 162 so that stripes 164 become revealed when the adapter sleeve 90 has been axially translated proximally from swivel sleeve 92 , and become aligned with marker stripes 160 of the swivel sleeve 92 when the swivel sleeve 92 has been rotated so that detents 104 are located at the termini of the proximal slot portions 122 in the swivel sleeve.
The various components of the present invention may be made from the following materials: inner and outer catheters 14 , 12 may be made for example of silicone, or may be of polyurethane; distal sleeve 56 defining the structure at the distal end of inner catheter 14 is preferably molded of material identical to that of the inner catheter; containment sleeve 38 for outer catheter 12 may be of material identical to that of the outer catheter; cap component 58 may be made of polyurethane; valve 78 may be made of silicone; hub 16 may be made of polyurethane; adapter sleeve 90 , swivel sleeve 92 , outer sleeve 134 and inner sleeve 138 may be made of polyvinyl chloride; o-ring 140 may be made of silicone; and the extension tubes 20 , 22 may be made of polyurethane as is conventional.
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
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A catheter assembly ( 10 ) having an outer catheter ( 12 ) and an inner catheter ( 14 ) extending coaxially through the outer catheter, and a hub ( 16 ). The inner catheter ( 14 ) is axially movable within and with respect to the outer catheter ( 14 ) by use of an actuator assembly ( 130 ) such that the catheter assembly has an opened condition permitting fluid communication with vasculature of a patient, and a closed condition preventing fluid communication with the vasculature of the patient. The opened condition permits the intended use of the catheter assembly such as for hemodialysis of the patient. In the closed condition, locking solution may be maintained in the catheter assembly and later removed therefrom, with essentially no locking solution leaving the catheter assembly or entering the patient. The actuator assembly ( 130 ) is secured to a proximal end portion ( 128 ) of the inner catheter ( 14 ) as it protrudes proximally from the hub ( 16 ), where it is accessible to the practitioner. The actuator assembly ( 130 ) may comprise an adapter sleeve ( 90 ) fixed to the inner catheter ( 14 ), and a swivel sleeve ( 92 ) which is rotatable with respect to both the adapter sleeve ( 90 ) and the hub ( 16 ).
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CROSS-REFERENCE TO RELATED APPLICATION
The present application claims the benefit under 35 U.S.C. §119(e) of provisional patent application Ser. No. 61/202,239, filed Feb. 9, 2009, the contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an expandable stent.
2. Description of the Prior Art
Stents are generally known. Indeed, the term “stent” has been used interchangeably with terms such as “intraluminal vascular graft” and “expansible prosthesis”. As used throughout this specification the term “stent” is intended to have a broad meaning and encompasses any expandable prosthetic device for implantation in a body passageway (e.g., a lumen or artery).
In the late 1980's, the use of stents attracted an increasing amount of attention due the potential of these devices to be used, in certain cases, as an alternative to surgery. Generally, a stent is used to obtain and maintain the patency of the body passageway while maintaining the integrity of the passageway. As used in this specification, the term “body passageway” is intended to have a broad meaning and encompasses any duct (e.g. natural or iatrogenic) within the human body and can include a member selected from the group comprising: blood vessels, respiratory ducts, gastrointestinal ducts and the like.
First generation stents were self-expanding, spring-like devices which were inserted in the body passageway in a contracted state. When released, the stent would automatically expand and increase to a final diameter dependent on the size of the stent and the elasticity of the body passageway. An example of such a stent is known in the art as the Wallstent™.
The self-expanding stents were found by some investigators to be deficient since, when deployed, they could place undue, permanent stress on the walls of the body passageway. Further, upon expansion, the stent would shorten in length in an unpredictable fashion thereby reducing the reliability of the stent. This led to the development of various stents which were controllably expandable at the target body passageway so that only sufficient force to maintain the patency of the body passageway was applied in expanding the stent—i.e., the so-called “balloon expandable stents”.
Generally, in these second generation systems, a stent, in association with a balloon, is delivered to the target area of the body passageway by a catheter system. Once the stent has been properly located (for example, for intravascular implantation the target area of the vessel can be filled with a contrast medium to facilitate visualization during fluoroscopy), the balloon is expanded, thereby expanding the stent by plastic deformation so that the latter is urged in place against the body passageway. As indicated above, the amount of force applied is at least that necessary to maintain the patency of the body passageway. At this point, the balloon is deflated and withdrawn within the catheter, and subsequently removed. Ideally, the stent will remain in place and maintain the target area of the body passageway substantially free of blockage (or narrowing).
A balloon-expandable stent which gained some notoriety in the art in the 1990's was known as the Palmaz-Schatz™ stent. This stent is discussed in a number of patents including U.S. Pat. Nos. 4,733,665, 4,739,762, 5,102,417 and 5,316,023.
Another stent which has gained some notoriety in the art in the 1990's was known as the Gianturco-Roubin Flex-Stent. This stent is discussed in a number of patents, including U.S. Pat. Nos. 4,800,882, 4,907,336 and 5,041,126.
Other types of stents are disclosed in the following patents:
U.S. Pat. No. 5,035,706 (Gianturco et al.),
U.S. Pat. No. 5,037,392 (Hillstead),
U.S. Pat. No. 5,147,385 (Beck et al.),
U.S. Pat. No. 5,282,824 (Gianturco),
Canadian patent 1,239,755 (Wallsten), and
Canadian patent 1,245,527 (Gianturco et al.).
While these prior art stents have achieved a varying degree of success, the art is constantly in need of new stents having improved flexibility and stability while being able to be readily implanted with little or no trauma to the target lumen. It would be highly desirably if such new stents additionally were relatively resistant to kinking during bending while maintaining wall apposition and side branch access (particularly important when deploying the stent in the aorta).
SUMMARY OF THE INVENTION
It is an object of the present invention to obviate or mitigate at least one of the above-mentioned disadvantages of the prior art.
It is another object of the present invention to provide a novel stent comprising, in two dimensions:
a plurality of undulating circumferential portions, each circumferential portion comprising alternating peaks and valleys; and a plurality of longitudinally extending portions connecting the plurality of undulating circumferential portions; wherein: (i) each of the plurality of longitudinally extending portions comprising a first longitudinally extending strut and a second longitudinally extending strut circumferentially offset with respect to the first longitudinally extending strut, the first longitudinally extending strut and the second longitudinally extending strut being interconnected by a connecting portion; and (ii) a pair of circumferentially adjacent first longitudinally extending struts in a pair of circumferentially adjacent longitudinally extending portions are circumferentially spaced at a first distance and circumferentially adjacent second longitudinally extending struts in the pair of circumferentially adjacent longitudinally extending portions are circumferentially spaced at a second distance, the first distance being greater than the second distance.
Thus, the present inventors have discovered a novel stent design which provides a very desirable balance between conformability while obviating or mitigating the disadvantages associated with crashing and out of tubular configuration that will be described below. Additionally, the present stent is relatively resistant to kinking during bending while maintaining good wall apposition and desirable side branch access. It is believed that these advantages accrue from the design of the longitudinal connector used to interconnect circumferential rings in the present stent, together with the orientation of circumferentially adjacent pairs of these longitudinal connectors. This will be described in more detail below.
While a specifically preferred embodiment of the present stent will be described below with reference to the drawings, the present stent may include one or more of the following features:
the connecting portion that connects two longitudinally extending struts may comprise at least one apex (i.e., one or more apices); a pair of the circumferentially adjacent longitudinally extending portions in two dimensions, may be configured to be substantially mirror images of one another along a longitudinal axis of the stent; a pair of the circumferentially adjacent longitudinally extending portions, in two dimensions, may be configured to be substantially non-superimposable mirror images of one another along a longitudinal axis of the stent; the section of first undulating circumferential portion between two ends of adjacent longitudinally extending portions connecting to a first undulating circumferential portion and the section of the second undulating circumferential portion between the other ends of the same two longitudinally extending portions to a second undulating circumferential portion adjacent to the first undulating circumferential portion, the first section and the second section having an equivalent number of peaks and valleys; the section of first undulating circumferential portion between two ends of adjacent longitudinally extending portions connecting to a first undulating circumferential portion and the section of the second undulating circumferential portion between the other ends of the same two longitudinally extending portions connecting to a second undulating circumferential portion adjacent to the first undulating circumferential portion, the first section and the second section having a different number of peaks and valleys; an adjacent pair of undulating circumferential portions may comprises an equivalent number of peaks and valleys; an adjacent pair of undulating circumferential portion may comprise a different number of peaks and valleys; the first longitudinally extending strut may comprise a straight portion; the second longitudinally extending strut may comprise a straight portion; each of the first longitudinally extending strut and the second longitudinally extending strut may comprise a straight portion; the first longitudinally extending strut may comprise a curvilinear portion; the second longitudinally extending strut may comprise a curvilinear portion; each of the first longitudinally extending strut and the second longitudinally extending strut may comprise a curvilinear portion; the first longitudinally extending strut may comprise a curved portion; the second longitudinally extending strut may comprise a curved portion; each of the first longitudinally extending strut and the second longitudinally extending strut may comprise a curved portion; the connecting portion may comprise a first strut segment connected to the first longitudinally extending strut and a second strut segment connected to the second longitudinally extending strut; the first strut segment and the second strut segment may be interconnected to define at least one apex; the first strut portion may comprise a straight portion; the second strut portion may comprise a straight portion; each of the first strut portion and the second strut portion may comprise a straight portion; the first strut portion may comprise a curved portion; the second strut portion may comprises a curved portion; each of the first strut portion and the second strut portion may comprise a curved portion; the first strut portion may comprise a curvilinear portion; the second strut portion may comprise a curvilinear portion; each of the first strut portion and the second strut portion may comprise a curvilinear portion; the at least one apex may comprise a curved portion; the at least one apex may comprise a straight portion; the at least one apex may comprise a pointed portion; the first strut portion and the second strut portion may be substantially mirror images of one another along a longitudinal axis of the stent; the first strut portion and the second strut portion may be non-mirror images of one another along a longitudinal axis of the stent; the first longitudinally extending strut may be connected to a valley of a first undulating circumferential portion and the second longitudinally extending strut may be connected to a peak of a second undulating circumferential portion adjacent to the first undulating circumferential portion; the first longitudinally extending strut may be connected to a peak of a first undulating circumferential portion and the second longitudinally extending strut may be connected to a peak of a second undulating circumferential portion adjacent to the first undulating circumferential portion; the first longitudinally extending strut may be connected to a valley of a first undulating circumferential portion and the second longitudinally extending strut may be connected to a valley of a second undulating circumferential portion adjacent to the first undulating circumferential portion; the first longitudinally extending strut may be connected to a first connection point intermediate a peak and a valley of a first undulating circumferential portion and the second longitudinally extending strut may be connected to a second connection point intermediate to a peak and a valley of a second undulating circumferential portion adjacent to the first undulating circumferential portion; the first longitudinally extending strut may be connected to a first connection point that is substantially midway between a peak and a valley of a first undulating circumferential portion and the second longitudinally extending strut may be connected to a second connection point that is substantially midway between a peak and a valley of a second undulating circumferential portion adjacent to the first undulating circumferential portion; the stent may comprise an even number of longitudinally extending portions interconnecting adjacent circumferential portions; ratio of the number peaks in each of an adjacent pair of circumferential portions to the number of longitudinally extending portions connecting the pair is 2:1; the stent may contain 4 longitudinally extending portions interconnecting an adjacent pair of circumferential portions; each of the pair of circumferential portions have 8 peaks; the stent may have a diameter of less than or equal to about 30 mm; the stent may contain 6 longitudinally extending portions interconnecting an adjacent pair of circumferential portions; each of the pair of circumferential portions may have 12 peaks; the stent may have a diameter of greater than about 30 mm. the stent may contain 8 longitudinally extending portions interconnecting an adjacent pair of circumferential portions; the stent may contain 12 longitudinally extending portions interconnecting an adjacent pair of circumferential portions; the stent may be a balloon expandable material; the stent may be constructed from a shape memory alloy; the stent may be configured to be self-expanding; the stent may be constructed from nitinol; the stent may be constructed from a material selected from the group consisting of stainless steel, titanium, tantalum, nitinol, Elgiloy, NP35N and cobalt-chromium alloy; the stent may be constructed from a non-metallic material; the stent may be constructed from a biodegradable material; and/or the stent may be constructed from a bio-absorbable material.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will be described with reference to the accompanying drawings, wherein like reference numerals denote like parts, and in which:
FIG. 1 illustrates a stent design, in two dimensions, that is outside the scope of the present invention;
FIGS. 2 and 3 , illustrate a stent shown in FIG. 1 in a bent configuration;
FIG. 4 illustrates a further stent design that is outside the scope of the present invention;
FIG. 5 illustrates the stent shown in FIG. 4 in a bent configuration;
FIG. 6 illustrates a stent product commercially available from OptiMed under the tradename “Sinus-XL stent” in a bent configuration;
FIG. 7 illustrates a perspective view of a preferred embodiment of a stent in accordance with the present invention;
FIG. 8 illustrates the stent shown in FIG. 7 in a two dimensional representation;
FIG. 9 illustrates the stent design shown in FIGS. 7 and 8 in a bent configuration;
FIGS. 10-12 illustrate the stent design shown in FIGS. 7-9 under various stresses;
FIGS. 13-15 illustrate various alternate embodiments of the longitudinally extending portion used in the stent design shown in FIGS. 7-9 ; and
FIG. 16 illustrates a portion of the two dimensional representation of the stent of the present invention in an expanded (a) and a crimped (b) state.
With respect to FIGS. 2 , 3 , 5 - 7 and 9 , it is noted that these drawings illustrate actual products. Of these, FIGS. 2 , 3 , 5 , 6 and 9 illustrate a stent product in a bent configuration. In order to facilitate understanding what is illustrated, it should be noted that half of the product along its longitudinal axis (i.e., 180°) is actually immersed in an opaque liquid (e.g., paint) so that what is actually shown is the product spanning approximately 180°. This protocol avoids complicating the illustrated view with the struts from the rear portion of the product (see, for example, FIG. 7 in which the entire product is illustrated).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Prior to discussing the preferred embodiments of the present stent, a discussion of the problems with prior art stents will be discussed with reference to FIGS. 1-6 .
With reference to FIG. 1 , there is illustrated a two dimensional representation of a stent 100 . By two dimensional representation, is meant a view of the stent as obtained by taking a tubular form of the stent, cutting it in a longitudinal direction and laying open/flattening the stent.
Stent 100 consists of a series of circumferential rings 110 . In the illustrated embodiment, there are six circumferential rings 110 .
Circumferential rings 110 are interconnected by longitudinal connectors 120 . In the illustrated embodiment, there are two longitudinal connectors that interconnect each pair of circumferential rings 120 .
Each longitudinal connector 120 consists of a flex member 125 that is disposed between a pair of straight sections 130 , 135 . Such longitudinal connectors are conventional in the art.
The stent design shown in FIG. 1 may be regarded as a so-called “peak-to-valley” design. By this it is meant that longitudinal connector 120 connects a peak of circumferential ring 110 with a valley of an adjacent circumferential ring 110 . In general, peak-to-valley designs are known in the art.
When stent 100 is bent, a number of problems are encountered.
With reference to FIG. 2 , stent 100 is shown in a bent state—this bent stent configuration is consistent with the type of bending often encountered during clinical use of stent 100 . As illustrated, a problem results in that various of circumferential rings 110 contact or “crash” on the adjacent circumferential ring 110 . For clarity, this is illustrated by circles A. As illustrated, during “crashing”, the crowns (peaks) of adjacent circumferential rings contact each other and overlap and/or kink. This can create significant problems for the physician trying to implant stent 100 . If the stent is to be implanted in a curved lumen, “crashing” results in interruption of blood flow and increased risk of thrombosis. Even if the stent is to be implanted elsewhere in the body (e.g., a relatively straight body lumen), if adjacent circumferential rings kink and become entangled, there is a risk that they will not untangle thereby compromising the ability of the stent to return to a proper straight configuration.
Further, while the bent configuration shown in FIG. 2 allows stent 100 generally to maintain its tubular configuration, the crashing of adjacent pairs of circumferential rings 110 adversely affects the flexibility of the stent and, can cause tangling of the crowns that in some cases, can result in damage to the stent. Tangling (resulting from “crashing”) of adjacent pairs of circumferential rings in the stent can also lead to the circumferential rings being out of axial alignment. If this is not noticed by the physician, it can lead to potentially disastrous results for the patient as a result of fracture, strut protrusion through artery wall, increased risk of embolism/thrombosis.
A more significant clinical problem with stent 100 can be seen with reference to FIG. 3 . Here, stent 100 is shown in a bent state in an artery 10 . As was seen in FIG. 2 , in this configuration, there is crashing of adjacent circumferential rings 110 (see circles A). In addition, a further problem can be seen. Specifically, circumferential ring 110 * actually rotates out of the tubular configuration to be in alignment with the longitudinal axis of the stent. This is clearly not an acceptable configuration of the stent and it cannot be correctly implanted in a safe manner when such a problem occurs. This problem is even more likely to occur clinically than “crashing” discussed above. When the problem does occur, it will not necessarily self-correct and, in most cases, would require some sort of intervention (possibility surgery) to remove an incorrectly implanted stent. In many cases, this exposes the patient to the very risk that was intended to be avoided by attempting an endovascular intervention.
Thus, while stent 100 illustrated in FIGS. 1-3 is very flexible, this high degree of flexibility appears to give rise to the crashing problem ( FIGS. 2 and 3 ) and the “out of tubular configuration” problem ( FIG. 3 ).
To overcome this problem, one could attempt to increase the number of longitudinal connectors used to connect each adjacent pair of circumferential rings—such a design is illustrated in FIG. 4 .
Thus, in FIG. 4 , there is illustrated a stent 200 having six circumferential rings 210 . Circumferential rings 210 are similar to circumferential rings 110 in FIGS. 1-3 . A series of longitudinal connectors 220 interconnect adjacent pairs of circumferential rings 210 .
The difference between the stent designs in FIGS. 1-3 and that in FIG. 4 is that there are two longitudinal connectors 120 connecting each pair of circumferential rings 110 in stent 100 shown in FIGS. 1-3 . In contrast, there are three longitudinal connectors 220 interconnecting each pair of circumferential rings 210 in stent 200 shown in FIG. 4 .
The result of adding an additional longitudinal connector 220 is significant. As shown in FIG. 5 , when stent 200 is bent, the “crashing” problem and the “out of tubular configuration” problem seen with stent 100 in FIGS. 1-3 is overcome. However, this comes at a cost of flexibility of stent 200 . As can be seen in FIG. 5 , when stent 200 is bent, the portion of the stent which forms the apex of the inner bend is susceptible to kinks—this is shown in circle B in FIG. 5 . This problem results due to the less flexible nature of stent 200 . For example, it can be seen in FIG. 5 that there is very little uniform bending of stent 200 . Rather, it appears that most of the bending forces are concentrated in the region of stent 200 shown in circle B. To achieve bending of stent 200 high force is typically needed. Thus, there can be too much stress applied to the artery leading to clinical complications such as dissection, rupture or other acute/chronic injury to the artery. Further, there is a risk of flexure fatigue failure associated with the region of stent 200 shown in circle B. Still further, there is excessive protrusion of elements of the region of stent 200 shown in circle B leading to an increased risk of thrombosis and/or limitation/denial of access to the distal portion of the lumen in which stent 200 is implanted.
This results in a compromise in the conformability of the stent. As is known in the art, “conformability” refers to the ability of the stent to conform to the shape of the vessel as opposed to forcing the vessel to conform to the shape of the stent. In summary, there is a problem on the one hand of great flexibility but crashing/out of tubular configuration associated with the stent shown in FIGS. 1-3 while, on the other hand, there is the problem with kinking and lack of conformability associated with the stent shown in FIGS. 4-5 . At least with respect to the stents illustrated in FIGS. 1-5 , these problems depend on whether there are two or three longitudinal connectors interconnecting adjacent circumferential rings.
With reference to FIG. 6 , there is illustrated a stent 400 shown in a bent state—this bent state is similar to the described above with reference to FIGS. 2 , 3 and 5 described above. Stent 400 is a stent product commercially available from OptiMed under the tradename “Sinus-XL stent” and is often implanted by a physician in the aorta of a patient, typically in a straight portion of that lumen. This stent is not well suited for delivery and/or implantation through/in a curved lumen. Specifically, the “Instructions For Use” contained with the product include the following statements:
“The sinus-XL stent is marked by its inflexible sinus wave structure. Thus, it must not be implanted at a joint or nearby a joint or in case of severe vessel/lumen curvatures.”
The reason for this cautionary instruction is apparent with reference to FIG. 6 which illustrates the Sinus-XL stent in a bent configuration. As shown, there is significant kinking of stent 400 in the apex region of the bend and, after repeated bending, various struts in the device actually fractured. As is further apparent, the relatively tight porous pattern of the device when placed across a branch artery raises the risk of compromising the access to the side branch it is covering—this is particularly problematic if the stent is implanted in the aorta and crosses various of the arteries branching off the aorta. In such a case, the physician is likely blocked from access to the covered arteries (know in the art as being “jailed in” and the like), thus preventing the interventional treatment of that artery in the future.
Thus, there does remain a need in the art for a stent design which has an improved balance between flexibility and conformability without causing problems associated with crashing and out of tubular configuration described above. It would be particularly advantageous if these attributes of the stent did not compromise the crimpability of the stent. It would be further particularly advantageous if the stent was relatively resistant to kinking during bending while maintaining good wall apposition and desirable side branch access.
With reference to FIGS. 7-12 , there is illustrated a stent 300 which accords with the preferred embodiment of the present invention. In FIG. 7 stent 300 is shown in an expanded state.
As seen in FIG. 8 , in two dimensions, stent 300 consists of a series of circumferential rings 310 . Adjacent pairs of circumferential rings 310 are interconnected by a series of longitudinally extending portions 320 . In the illustrated embodiment, there are four longitudinally extending portions 320 that interconnect with each pair of circumferential rings 310 .
Each longitudinally extending portion 320 consists of a pair of longitudinally extending struts 325 , 330 . In each longitudinally extending portion 320 , longitudinally extending struts 325 , 330 are circumferentially offset with respect to each other and are interconnected by a connecting portion 335 . Connecting portion 335 contains at least one apex 340 .
Adjacent pairs of longitudinally extending portions 320 are arranged in a specific manner. More particularly, circumferentially spaced pairs of longitudinally extending portions 320 are arranged so that a pair of a longitudinally extending struts 330 are spaced at a first distance C and a pair of longitudinally extending struts 325 are spaced at a distance D. As shown, distance C is greater than distance D.
When stent 300 is bent ( FIG. 9 ), it generally maintains is tubular configuration—i.e., the conformability of stent 300 is quite good. The poor conformability and kinking problem described above with respect to stent 200 in FIGS. 4-5 and stent 400 in FIG. 6 is reduced or avoided. In addition, the crashing and out of tubular configuration problem described above with respect to stent 100 in FIGS. 1-3 is reduced or avoided. This is primarily due to the design of longitudinally extending portions 320 and the orientation of circumferentially adjacent pairs of longitudinally extending portions 320 (as discussed above), which allows for necessary expansion when stent 300 is placed under tension and contraction when stent 300 is placed under compression. These longitudinal tension and compression forces are experienced when the stent 200 is placed on a curve as show in FIG. 9 . FIGS. 10-12 show in detail how the longitudinally extending portions allow for this expansion and contraction.
Thus, stent 300 provides a combination of advantages that is not seen as such with stent 100 in FIGS. 1-3 or stent 200 in FIGS. 4-5 or stent 400 in FIG. 6 .
FIG. 11 illustrates stent 300 in a neutral configuration—i.e., there are no stresses placed on the stent. In this configuration, peaks 345 , 350 in an adjacent pair of longitudinally adjacent circumferential rings 310 are spaced at a first distance E. When stent 300 is placed under tension (which occurs along the larger radius of a bend) ( FIG. 10 ), longitudinally adjacent peaks 345 , 350 of a longitudinally adjacent pair of circumferential rings 310 are longitudinally spaced at a distance F that is greater than E in FIG. 11 . As is also apparent from FIG. 10 , the distance between circumferentially adjacent pairs of apices 340 in longitudinally extending portions 320 increases when stent 300 is placed under longitudinal tension.
With reference to FIG. 12 , it can be seen that when stent 300 is placed under compression (which occurs along the smaller radius of a bend), longitudinally adjacent peaks 345 , 350 in a longitudinally adjacent pair of circumferential rings 310 are spaced at a distance G which is less than distance E in the neutral configuration of stent 300 ( FIG. 11 ). In addition, it can be seen that the distance between circumferentially adjacent pairs of apices 340 in adjacent longitudinally extending portions 320 generally decreases when stent 300 is placed under longitudinal compression.
This dynamic behaviour of the longitudinal connectors 320 when the stent is placed under compression or tension can be regarded as a pivoting action which improves the flexibility and conformability of stent 300 while minimizing or reducing having struts in the stent to contact or crash on each other. This advantage is also illustrated in FIG. 8 which shows stent 300 on a curve.
With reference to FIGS. 13-15 , there is illustrated a series of alternatives to longitudinally extending portions 320 illustrated in FIGS. 7-12 .
Thus, in FIG. 13( a ), longitudinally extending portion 320 is illustrated as a starting point for modification. In FIG. 13( b ) through 13 ( d ), there is shown modifications to longitudinally extending struts 325 , 330 . In FIG. 13( b ), longitudinally extending strut 325 is modified to include a curved flex member 327 that is located between a pair of straight portions 328 and 329 . Summarily, longitudinally extending strut 330 has been modified to include a curved flex member 332 that is located between a pair of straight sections 333 and 334 .
While flex members 327 , 332 in FIG. 13( b ) are depicted as S-shaped portions, it will be appreciated by those of skill in the art that the specific nature of the curved flex member may be modified and includes the various shapes of “flexure means” described and illustrated in U.S. Pat. No. 6,858,037 [Penn et al. (Penn)].
In FIG. 13( c ), longitudinally extending struts 325 , 330 have been modified such that each are substantially completely curved. In the illustrated embodiment, the struts have been modified to have a general S-shape. Of course, other curved shapes can be used.
In FIG. 13( d ), only strut 330 has been modified and it has a general C-shape, wherein there is no distinguishable transition between struts 330 and connecting portion 335 .
In FIGS. 14( b ) and 14 ( c ), there are illustrated modifications to connecting portion 335 of longitudinally extending portion 320 to include curved portions that are shown in FIGS. 13( b ) and 13 ( c ), respectively. In FIG. 15( b ) through 15 ( e ), there are illustrated modifications to apex 340 of longitudinal extending portion 320 .
Thus, in FIG. 15( b ), the apex of connecting portion 335 has been modified to be pointed. In FIG. 15( c ), this apex is flat. In FIG. 15( d ), this apex has been modified to have a pair of curved portions with a dimple in between. Finally, in FIG. 15( e ), the apex has been modified to have a flat portion with a curved flex member disposed therein.
Those of skill in the art will recognize it is possible to modify longitudinally extending portion 320 to include one or more of the features described in FIGS. 13-15 . That is, it is possible to combine the various modifications shown in FIGS. 13-15 in a single longitudinally extending portion 320 . Further, it is possible to modify the connecting portion between circumferential ring 310 and longitudinally extending portion 320 to have an apex similar to apex 340 comprised in connecting portion 320 .
In addition to the above stated advantages associated with stent 300 , there is a further advantage. Specifically, stent 300 , having circumferential rings 310 of similar profile and amplitude, can be readily crimped while reducing or avoiding pre-deployment crashing of the various struts in the design. This can be seen with reference to FIG. 16 .
The stent of the present invention may further comprise a coating material thereon. The coating material can be disposed continuously or discontinuously on the surface of the stent. Further, the coating may be disposed on the interior and/or the exterior surface(s) of the stent. The coating material can be one or more of a biologically inert material (e.g., to reduce the thrombogenicity of the stent), a medicinal composition which leaches into the wall of the body passageway after implantation (e.g., to provide anticoagulant action, to deliver a pharmaceutical to the body passageway and the like) and the like.
The stent is preferably provided with a biocompatible coating, in order of minimize adverse interaction with the walls of the body vessel and/or with the liquid, usually blood, flowing through the vessel. A number of such coatings are known in the art. The coating is preferably a polymeric material, which is generally provided by applying to the stent a solution or dispersion of preformed polymer in a solvent and removing the solvent. Non-polymeric coating materials may alternatively be used. Suitable coating materials, for instance polymers, may be polytetraflouroethylene or silicone rubbers, or polyurethanes which are known to be biocompatible. Preferably, however, the polymer has zwitterionic pendant groups, generally ammonium phosphate ester groups, for instance phosphoryl choline groups or analogues thereof.
Examples of suitable polymers are described in International application number WO-A-93/16479 and WO-A-93/15775. Polymers described in those specifications are hemo-compatible as well as generally biocompatible and, in addition, are lubricious. It is important to ensure that the surfaces of the stent are completely coated in order to minimize unfavourable interactions, for instance with blood, which might lead to thrombosis. This good coating can be achieved by suitable selection of coating conditions, such as coating solution viscosity, coating technique and/or solvent removal step.
In another embodiment of the invention, the stent may be joined to a cover material to form a so-called stent graft. The cover may be a polymer or non-polymer material and it may be natural or synthetic. Non-limiting examples of suitable covering materials include bovine, basilic vein or other natural tissue, PTFE, e-PTFE, polyurethane, Gortex™, bioabsorbable materials and the like. The cover material may be secured to the inside or the outside of the stent. Of course, it is also possible to form a laminate construction wherein a pair of cover materials (similar or dissimilar) sandwich or otherwise surround at least a portion of the stent. The cover material may be secured to the stent by bonding, suturing, adhesion, mechanical fixation or any combination of these. Further, if the cover material is a polymer material, it may be extruded onto the stent in such a manner that it envelops at least a portion of the stent. This technique may be used to join two or more stents with a flexible polymeric tube. This technique may also be used to join a stent to another prosthetic device such as a tube, a graft and the like. Thus, in this embodiment of the invention, the stent is incorporated into an endoluminal prosthesis. The cover materials may fully or partially cover the stent in the radial and/or circumferential direction.
The manner by which the present stent is manufactured is not particularly restricted. Preferably, the stent is produced by laser cutting techniques applied to a tubular starting material. Thus, the starting material could be a thin tube of a metal or alloy (non-limiting examples include stainless steel, titanium, tantalum, nitinol, Elgiloy, NP35N, cobalt-chromium alloy and mixtures thereof) which would then have sections thereof cut out to provide a stent having a predetermined design.
Thus, the preferred design of the present stent is one of a tubular wall which is distinct from prior art wire mesh designs wherein wire is conformed to the desired shape and welded in place. The preferred tubular wall design of the present stent facilitates production and improves quality control by avoiding the use of welds and, instead, utilizing specific cutting techniques.
In one embodiment, the present stent is configured to be a balloon expandable stent. In this embodiment, the stent can be made from a balloon expandable material such as stainless steel, titanium, tantalum, nitinol (certain grades), Elgiloy, NP35N, cobalt-chromium alloy and the like. The present stent may be implanted using a conventional system wherein a guidewire, catheter and balloon can be used to position and expand the stent. Implantation of mono-tubular stents such as this stent is conventional and within the purview of a person skilled in the art. See, for example, any one of U.S. Pat. Nos. 4,733,665, 4,739,762, 5,035,706, 5,037,392, 5,102,417, 5,147,385, 5,282,824, 5,316,023 and any of the references cited therein or any of the references cited herein above. Alternatively, the present stent may be manufacture from non-metal (e.g., polymer) materials and/or materials that are bioabsorbable.
It will be apparent to those of skill in the art that implantation of stent of the present can be accomplished by various other means. For example, it is contemplated that the stent can be made of a suitable material which will expand when a certain temperature is reached. In this embodiment, the material may be a metal alloy (e.g., nitinol) capable of self-expansion at a temperature of at least about 20° C., preferably in the range of from about 20° C. to about 37° C. In this embodiment, the stent could be implanted using a conventional catheter and the radially outward force exerted on the stent would be generated within the stent itself. Further, the present stent can be designed to expand upon the application of mechanical forces other than those applied by a balloon/catheter. For example, it is possible to implant the present stent using a catheter equipped with a resisting sleeve or retaining membrane which may then be removed with the catheter once the stent is in position thereby allowing the stent to expand. Thus, in this example, the stent would be resiliently compressed and would self-expand once the compressive force (i.e., provided by the sleeve or membrane) is removed. This is known as a self-expanding stent. Additional details on this approach may be found in U.S. Pat. Nos. 5,067,957 and 6,306,141.
Finally, it is preferred to incorporate one or more radioopaque markers in the present stent to facilitate view thereof during angiography typically used to guide the device to its intended location in the patient. It is particularly preferred to have at least one radioopaque marker at or near each of the proximal and distal ends of the stent. The material used as the radioopaque marker is preferably selected from the group consisting of gold, platinum, iridium, tantalum and tungsten.
While this invention has been described with reference to illustrative embodiments and examples, the description is not intended to be construed in a limiting sense. Thus, various modifications of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments.
All publications, patents and patent applications referred to herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety.
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A stent comprises a plurality of undulating circumferential portions, each circumferential portion comprising alternating peaks and valleys; and a plurality of longitudinally extending portions connecting the plurality of undulating circumferential portions. Each of the plurality of longitudinally extending portions contains a first longitudinally extending strut and a second longitudinally extending strut circumferentially offset with respect to the first longitudinally extending strut. The first longitudinally extending strut and the second longitudinally extending strut are interconnected by a connecting portion. Circumferentially adjacent first longitudinally extending struts in a pair of circumferentially adjacent longitudinally extending portions are circumferentially spaced at a first distance and circumferentially adjacent second longitudinally extending struts in the pair of circumferentially adjacent longitudinally extending portions are circumferentially spaced at a second distance. The first distance is greater than the second distance. The present stent has a very desirable balance of conformability and flexibility while obviating or mitigating crashing, out of tubular configuration and other problems (as discussed herein).
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BACKGROUND OF THE INVENTION
The present invention relates to a process for simultaneously passivating organochlorosilane reactor fines and generating values therefrom.
As shown in U.S. Pat. No. 4,500,724, methylchlorosilane reactor fines (hereinafter sometimes "silicon-containing fines") may be generated during the synthesis of methylchlorosilanes by the reaction of powdered silicon with methyl chloride, usually in the presence of a copper catalyst. Some of the generated fines are recycled, while others are discarded. As discussed in U.S. Pat. No. 5,274,158, a serious discarded fines management problem can occur with respect to build-up and disposition, as these materials are often pyrophoric. Silicon-containing fines can have an average particle size of about 0.1 to about 200 microns with at least 2% copper by weight in the elemental or chemically combined state.
As shown in the aforementioned U.S. Pat. No. 5,274,158, a procedure which can be used to render pyrophoric silicon-containing fines substantially non-reactive in air is to subject them to a heat treatment in an inert atmosphere at a temperature in the range of about 900°-1500° C.
Early studies also showed that SiCl 4 and HSiCl 3 can be made by contacting metallurgical grade silicon powder and HCl in the presence of a copper catalyst at about 300° C. Higher temperature are known to favor the exclusive formation of SiCl 4 . Although various procedures are known for passivating discarded silicon-containing fines to render them more manageable, interest also has been shown in developing techniques for both salvaging and passivating silicon-containing fines to derive some of the silicon and metallic values from the discarded finely divided silicon contact mass.
SUMMARY OF THE INVENTION
The present invention is based on the discovery that contact between silicon-containing fines which would otherwise be discarded and HCl or elemental chlorine at a high temperature simultaneously generates metallic values and passivates silicon from such discarded reactor fines.
Accordingly, the invention is a treatment method for salvaging metallic values and passivating silicon from silicon-containing fines resulting from the reaction of silicon powder with hydrogen chloride or an organic chloride, said method comprising contacting said fines with HCl or elemental chlorine at a temperature in the range of about 500°-1200° C. to form a mixture comprising silicon chlorides and metallic salts.
DETAILED DESCRIPTION OF THE INVENTION
Silicon chlorides which can be generated and salvaged in accordance with the practice of the invention are primarily SiCl 4 and HSiCl 3 . Among the metal chlorides which can be salvaged, there are included chlorides of copper, zinc and tin.
The silicon-containing fines to be treated in accordance with the method of the invention include materials shown in U.S. Pat. Nos. 4,724,122 and 5,000,934. They typically have a particle size in the range of about 0.1-200 microns and a surface area of up to about 25 m 2 /g.
In the practice of the invention, fines recovered, for example, from a fluidized bed organohalosilane reactor, which fines can be stored in a hopper under nitrogen, can be fed into a reactor such as a rotary kiln under batch, semi-batch, or continuous conditions. The fines may be agitated, ordinarily for a period of 1-3 hours, in an HCl or chlorine atmosphere. HCl can be employed, for example, at 0.1-3.0 atmospheres pressure and can be utilized in combination with an inert gas such as nitrogen or helium if desired. Treatment temperatures are in the range of 500°-1200° C.
It is frequently possible, in accordance with the invention, to recover essentially all the silicon present in the fines as valuable silicon chlorides, predominantly silicon tetrachloride. Moreover, copper and other metals present are typically converted to high purity chlorides which are also capable of further use.
In preferred embodiments of the invention, the HCl contact is effected in a first reaction zone and the product thereof is conveyed to one or more zones in which later stages are conducted. These can include a first heat exchange and separation zone employing a vessel having means for heat recovery resulting in steam generation, in which vessel recovery of metal salts, silicon chlorides and passivated contact mass residue, which may include as silicon oxides, silicon carbides and copper silicates, may be achieved. A second heat exchange and steam generation zone in a second similar vessel also can be used if necessary to allow a final stripping operation performed on the product of said first heat exchange and separation zone, for recovery of silicon chlorides and passivated silicon contact mass. Said passivated silicon contact mass is typically substantially nonreactive in air at temperatures to 350° C.
The following examples illustrate the practice of the invention.
EXAMPLE 1
A mixture of 0.1 atm. of HCl and 0.9 atm. of helium was passed over 30 mg of silicon-containing fines recovered from a methylchlorosilane reactor. The fines were in a platinum pan at 900° C. The weight loss of the fines was measured over about a five-hour period. Processing of the fines in the HCl atmosphere resulted in a rapid and substantial weight loss within about 1.5 hours. This was due to conversion to metal chlorides and chlorosilanes. About 1.0% initial weight was lost due to absorbed water.
The above procedure was repeated, except that the fines were processed in a helium atmosphere. It was found that the fines experienced no significant loss of weight except for loss due to absorbed water.
Processed and unprocessed fines were then examined for oxygen reactivity by passing a dilute air mixture over the samples at 300° C. The fines processed at 900° C. showed no weight gain, while weight gain due to formation of metal oxides was observed with unprocessed fines.
EXAMPLE 2
Thirty grams of silicon-containing fines recovered from a methylchlorosilane reactor were heated at 300° C. in a quartz reaction tube under flowing helium to remove any absorbed water. After the silicon-containing fines sample was dry, a condenser system was attached. HCl was introduced into the reactor and the temperature was raised to 900° C. The fines were treated for five hours followed by cooling the furnace under a helium purge.
Although less than one gram of liquid was collected, greater quantities were formed as shown by buildup of a white siloxane residue in a water scrubber. As shown by gas chromatography, the liquid condensate was 95 wt % SiCl 4 and the balance HSiCl 3 . A possible explanation of not retrieving the balance of liquid silanes generated was an inefficient condensation system and poor gas-solid interaction.
The above procedure was repeated at 300° C. for 6.5 hours. No liquid condensate was collected and a loss of 0.18 g of fines resulted.
Subsequent testing of the fines treated at 300° C. and 900° C. also showed significant passivation with respect to evolved hydrogen gas after being mixed with a water-surfactant mixture. Untreated fines generated 700 ml of evolved hydrogen per 10 g of sample, as compared with treatment at 300° and 900° C. which generated 181 and 130 ml, respectively.
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Silicon fines which have been recovered from an organochlorosilane reactor are treated with HCl or elemental chlorine at an elevated temperature to salvage chlorosilane and metal salt values. Passivation is also achieved.
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FIELD OF THE INVENTION
This invention relates to substrates such as films or fabrics and the like, rendered hydrophilic by the presence of a hydrophilic coating on the substrate and especially to porous structures useful in filtration.
BACKGROUND OF THE INVENTION
Recently, a hydrophilic porous fluoropolymer membrane was disclosed in U.S. Pat. No. 5,130,024. In this patent, normally hydrophobic fluoropolymer membrane is rendered hydrophilic by coating the pores with a hydrophilic fluorine-containing copolymer. Increasing the hydrophilicity of filtration membranes increases their efficiency in filtration applications involving filtering aqueous compositions. A typical such copolymer taught by this patent is a copolymer of a) a monomer of the formula CXY=CFZ where Z can be fluorine or hydrogen, and X and Y can be H, F, Cl or CF 3 (preferably they are all F), and b) a monomer of the formula ##STR1##
This copolymer, after saponification of the acetate group to hydroxyl, is coated on the pores of the membrane to provide hydrophilicity to the membrane. The coating is durable because of the fluorocarbon attraction between the membrane CF 2 groups and the copolymer CF bonds. Hydrophilicity is provided by the conversion of the ##STR2## (acetate) side groups in the copolymer to --OH groups, thus forming vinyl alcohol recurring units in the copolymer chain. This copolymer will be referred to hereinafter sometimes as the VOH copolymer.
The VOH copolymer coating on hydrophobic substrates increases their surface free energy significantly. This makes such coated substrates spontaneously wettable by high surface tension liquids such as water, which consequently opens up the use of such substrates to aqueous filtration applications. Some other potential applications are in the area of increased adhesion to high surface energy substrates, and use in biomedical devices, among others.
While the potential for such applications is promising, hydrophilicity of the VOH-copolymer coating suffers from lack of heat resistance at temperatures above 120° C.
When a VOH-copolymer coated membrane is heated at 120° C. and above, it has been observed that the water-wettability of the substrate becomes reduced, i.e., it is either no longer water-wettable or it requires a longer contact time with water or a higher contact pressure in order to become fully wet. Steam sterilization at 120° C. for 0.5 hour also has such a deleterious effect on the water-wettability of the VOH-copolymer coated substrates. Analysis via nuclear magnetic resonance spectroscopy as well as infrared spectroscopy of the VOH-copolymer before and after heating demonstrates that the loss of water-wettability upon heating is not caused by a chemical change in the VOH-copolymer. This leaves the possibility that the deleterious effect on water-wettability is caused by a physical change of the VOH-copolymer. This change could be in the form of C-OH bond rotations. If the hydroxy groups are rotated away from the surface of the substrate into its bulk, the hydroxy groups will no longer be in the optimum orientation for "receiving" and hydrogen bonding with incoming water.
SUMMARY OF THE INVENTION
In this invention, the above problem has been solved by attaching a bulky group to the hydroxy function. Although hydroxy functions are consumed in this reaction, due to the nature of the reactant used, a new hydroxy group can be generated for every hydroxy function consumed. The purpose of the reactions are to generate pendent hydroxy groups that are bonded to bulky groups. The belief is that hydroxy functions bonded to bulky groups will require higher energies to rotate from one side of the polymer backbone to the other, and thus preserve water wettability after exposure to elevated temperatures.
Thus in this invention a hydrophilic composition is provided comprising a substrate, preferably having continuous pores through it, in which at least a portion of the substrate is coated with a copolymer, wherein vinyl alcohol units in the copolymer are reacted with a monofunctional epoxide compound.
Preferably the substrate is a microporous fluorocarbon membrane.
Any epoxide of the formula CH 2 --CH--R wherein R is an organic moiety containing 4 or more carbon atoms is effective, but larger groups are more effective as long as the epoxide can be dissolved in the same solvent as the VOH copolymer.
DESCRIPTION OF THE INVENTION
The substrate is preferably permeable and can be any material that allows fluids, liquid or gas, to pass through. It is a material that contains continuous passages extending through the thickness of the material, and openings on both sides. These passages can be considered as interstices or pores. Preferably the material is flexible and is in the form of a fabric, sheet, film, tube, mesh, fiber, plug, or the like. The material can also be a porous synthetic or natural polymeric film or membrane, where the pores form the interstices or passageways. Representative polymers useful in the material include polyamide, polyurethane, polyester, polycarbonate, polyacrylic, polyolefins such as polyethylene and polypropylene, or fluorinated polymers such as polyvinylidene fluoride or polytetrafluoroethylene, polyvinyl chloride and the like. The material will generally be from about 1 to about 200 micrometers thick. In order to promote adherence of the coating to the substrate, the coating should have groups or moieties that have an affinity for the substrate. In other words, if the substrate contains fluorocarbon groups, then a coating material that contains fluorocarbon groups will be more likely to adhere and be an effective coating. Preferably, the substrate is expanded porous polytetrafluoroethylene (ePTFE) sheet made as described in U.S. Pat. No. 3,953,566 by stretching PTFE resin. The resulting product has a microstructure of nodes interconnected with fibrils. The PTFE resin is stretched so that the micropores or voids that form allow for good gas or air flow while providing liquid water resistance. These porous PTFE sheets, which can be referred to as membranes or fibers preferably have a Gurley number of between 0.1 second and 80 seconds, depending on pore size and pore volume.
When the material is polytetrafluoroethylene it will have a porosity volume ranging usually from 15% to 95%, preferably from 50% to 95%.
The copolymers used to coat the substrate can be made by first copolymerizing a fluorine-containing ethylenically unsaturated monomer and a non-fluorinated vinyl acetate, followed by converting the acetate to hydroxyl by saponification. The resulting copolymer is subsequently reacted with a monoepoxide.
The fluorine-containing ethylenically unsaturated monomer will be a vinyl monomer such as, for example, tetrafluoroethylene, vinyl fluoride, vinylidene fluoride, monochloro-trifluoroethylene, dichlorodifluoroethylene, hexafluoropropylene, perfluoropropylvinyl ether, and the like. Preferably, the fluorine-containing vinyl monomer can be described as XCY=CFZ wherein Z can be fluorine or hydrogen and X and Y can each be selected from hydrogen, fluorine, chlorine, or --CF 3 .
Once the vinyl acetate-containing copolymer is prepared, the acetate groups are saponified to hydroxyl groups. In this case, not all of the acetate groups contained in the copolymer need be replaced by hydroxyl groups. The conversion of acetate groups into hydroxyl groups need only be carried out to the extent needed to provide the copolymer with hydrophilic properties.
The fluorine content of the fluorine-containing hydrophilic copolymer to be used as the coating in the present invention may range usually from 2% to 40%, preferably from 10% to 40%, and most preferably 20%-30% on a weight basis. If the fluorine content of the fluorine-containing hydrophilic copolymer becomes too high, the hydrophilic properties of the polymer may be lessened.
Representative monoepoxides include glycidyl isopropyl ether, i.e., ##STR3## t-butyl glycidyl ether, 1-oxaspiro(2.5)octane, styrene oxide, or the like. The formula of the oxaspiro octane is ##STR4##
These epoxides can react with the --OH of the VOH copolymer with no net loss of --OH moieties, since the epoxide rings open to form --OH groups.
The coated compositions of the invention may be prepared by dissolving the VOH copolymer, the epoxide, and catalyst in an organic solvent, such as methyl alcohol, and then applying the solution to the porous substrate by immersion or spraying or transfer coating. The coated product is then dried in an oven, e.g. at about 80° C., or can be air-dried. Reaction of copolymer with the epoxide occurs during the drying process.
Suitable solvents are those which will dissolve the copolymer, e.g. alcohols.
In the following examples, the copolymer employed was a copolymer of tetrafluoroethylene and vinyl alcohol of approximately 25% (by weight) alcohol functionality.
EXAMPLE 1
A treatment solution was prepared which contained, by weight, 1% TFE/VOH, 0.43% glycidyl isopropyl ether, 0.2% potassium hydroxide in methanol/ethanol (4:1).
Sample 1.1: A microporous PTFE laminate obtained from W. L. Gore & Associates, Inc., with an average nominal pore size of 0.45 microns was immersed in the above solution for 5 minutes. It was then placed in a vacuum oven at 65°-70° C., 30 inches mercury pressure for 10 minutes.
Sample 1.2: A microporous PTFE laminate with an average nominal pore size of 0.1 microns was immersed in the treatment solution for 5 minutes. It was then placed in a vacuum oven at 65°- 70° C., 30 inches mercury, for 10 minutes.
Both samples were immediately and completely wettable in water. Water wettability was determined by immersion in water. A transparent material indicated good water wettability.
Testing the Durability of Water-wettability to Steam Heat
Both the above samples were autoclaved at 120° C. for 90 minutes. After autoclaving, both samples were completely water-wettable. Prior experience had demonstrated that TFE/VOH coated microporous PTFE would lose water-wettability in autoclave conditions such as the above.
Testing the Durability of Water-wettability to Dry Heat
Portions of Sample 1.1 were separately heat tested in a vacuum oven. Temperatures of testing were 120° C., 150° C., 160° C. Heat exposure time was 5 minutes in each case. Water-wettability of the materials after this exposure to dry heat was complete and immediate.
EXAMPLE 2
Control Sample 2.1: A microporous PTFE laminate of 1 micron average nominal pore size was immersed in a 1% TFE/VOH solution (solvent: methanol/ethanol 4:1) for 1 minute. It was then dried at room temperature overnight.
Sample 2.2: The treatment solution was 1% TFE/VOH, 1.9% tert-butyl glicidyl ether, 0.1% potassium hydroxide in methanol/ethanol (4:1). an untreated sample of the same 1 micron average nominal pore size PTFE laminate as mentioned in Sample 2.1 was immersed in this solution for 1 minute. Reaction and drying occurred at room temperature overnight.
Being unheated at this point, both samples were completely and immediately water-wettable.
Testing the Durability of Water-wettability to Dry Heat
Each sample was cut into test strips. Each test strip was subjected to heating at a specific temperature in an oven. Time of exposure to heat for each test strip was 15 minutes. After removing the heated test strips from the oven, the water-wettability of each test strip was measured by placing several 25 microliter water droplets (administered by a pipette) on the surface of the strip and measuring the time required for the areas of contact between PTFE and water to become completely transparent. The results were as follows:
______________________________________Sample TemperatureNo. (°C.) Water-wettability After Dry Heat______________________________________2.1 120 Complete in 60 seconds2.2 120 Immediate and complete2.1 130 Only partially wet up to 300 seconds2.2 130 Complete in 11 seconds2.1 140 Only partially wet up to 300 seconds2.2 140 Completely wet in 100 seconds2.1 150 Hardly any wetting up to 300 seconds2.2 150 Complete in 120 seconds2.1 160 No wetting up to 300 seconds2.2 160 No wetting up to 300 seconds______________________________________
EXAMPLE 3
Control Sample 3.1: A microporous PTFE laminate of 1 micron average nominal pore size was immersed in a 1% TFE/VOH solution (solvent: methanol/ethanol 4:1) for 1 minute. It was then dried at room temperature overnight.
Sample 3.2: The treatment solution was 1% TFE/VOH, 0.81% 1-oxaspiro(2.5)octane, 0.04% potassium hydroxide in methanol/ethanol (4:1). An untreated microporous PTFE laminate (the same as used for Sample 3.1) was immersed in this solution for 1 minute. The reaction and drying was left to occur at room temperature overnight.
Being unheated at this point, both samples were completely and immediately water-wettable.
Testing the Durability of Water-wettability to Dry Heat
Each sample was cut into test strips. Each test strip was heated at a specific temperature in an oven. Time of heating of each test strip was 15 minutes. After removing the heated test strips from the oven, the water-wettability of each test strip was measured by placing several 25 microliter water droplets (administered by a pipette) on the surface of the strip and measuring the time required for the areas of contact between PTFE and water to become transparent. The results were as follows:
______________________________________Sample TemperatureNo. (°C.) Water-wettability After Dry Heat______________________________________3.1 120 Complete in 60 seconds3.2 120 Immediate and complete3.1 130 Only partially wet up to 300 seconds3.2 130 Complete in 2 seconds3.1 140 Only partially wet up to 300 seconds3.2 140 Completely wet in 10 seconds3.1 150 Hardly any wetting up to 300 seconds3.2 150 Complete in 10 seconds3.1 160 No wetting up to 300 seconds3.2 160 Complete in 60 seconds______________________________________
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A fluid filtration material made of a porous substrate, e.g. a membrane or a fabric, that is coated with a fluorinated copolymer that contains recurring vinyl alcohol units that have been reacted with a monoepoxide to aid in preventing loss of hydrophilicity in the coated material.
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CROSS REFERENCE TO RELATED APPLICATIONS
PRIORITY: I hereby claim the benefit under Title 35, U.S.C. § 119(e) of a U.S. Provisional Patent Application filed on Feb. 11, 2002 and having Ser. No. 60/356,279. I hereby claim the benefit under Title 35 U.S.C. § 120 of each of the following: U.S. patent application Ser. No. 10/164,832 filed on Jun. 7, 2002, which is a continuation-in-part of U.S. patent application Ser. No. 09/932,393 filed on Aug. 17, 2001, now U.S. Pat. No. 6,908,662, which is a continuation-in-part of U.S. patent application Ser. No. 09/303,979 filed on May 3, 1999, now U.S. Pat. No. 6,413,458, which is a continuation-in-part of U.S. patent application Ser. No. 08/968,750 filed on Aug. 13, 1997, now U.S. Pat. No. 6,026,527, which is a continuation-in-part of U.S. patent application Ser. No. 08/601,374 filed on Feb. 14, 1996, now U.S. Pat. No. 5,749,111, which is a continuation-in-part of U.S. patent application Ser. No. 08/783,413 filed on Jan. 10, 1997, now U.S. Pat. No. 5,994,450, which claims priority to U.S. Provisional Patent Application Ser. No. 60/021,109 filed on Jul. 1, 1996. I hereby also claim the benefit under Title 35 U.S.C. § '120 of each of the following: U.S. patent application Ser. No. 10/059,101 filed on Nov. 8, 2001, which is a continuation-in-part of U.S. (patent application Ser. No. 09/303,979 filed on May 3, 1999, now U.S. Pat. No. 6,413,458, which is a continuation-in-part of U.S. patent application Ser. No. 08/968,750 filed on Aug. 13, 1997, now U.S. Pat. No. 6,026,527, which is a continuation-in-part of U.S. patent application Ser. No. 08/601,374 filed on Feb. 14, 1996, now U.S. Pat. No. 5,749,111, which is a continuation-in-part of U.S. patent application Ser. No. 08/783,413 filed on Jan. 10, 1997, now U.S. Pat. No. 5,994,450, which claims priority to U.S. Provisional Patent Application Ser. No. 60/021,109 filed on Jul. 1, 1996. I hereby also claim the benefit under Title 35 U.S.C. § 120 of each of the following: U.S. patent application Ser. No. 09/952,035 filed on Sep 11, now U.S. Pat. No. 6,797,765, which is a continuation-in-part of U.S. patent application Ser. No. 09/932,393 filed on Aug. 17, 2001, now U.S. Pat. No. 6,865,759; which is a continuation-in-part of U.S. patent application Ser. No. 09/303,979 filed on May 3, 1999, now U.S. Pat. No. 6,413,458, which is a continuation-in-part of U.S. patent application Ser. No. 08/968,750 filed on Aug. 13, 1997, now U.S. Pat. No. 6,026,527, which is a continuation-in-part of U.S. patent application Ser. No. 08/601,374 filed on Feb. 14, 1996, now U.S. Pat. No. 5,749,111, which is a continuation-in-part of U.S. patent application Ser. No. 08/783,413 filed on Jan. 10, 1997, now U.S. Pat. No. 5,994,450, which claims priority to U.S. Provisional Patent Application No. 60/021,109 filed on Jul. 1, 1996. Each of the foregoing is hereby incorporated by reference.
BACKGROUND
Prior art 3-dimensional blocks and letters, such as those used in children's play, were typically made from wood or hard, rigid plastic, providing an unpleasant texture and feel and even posing physical danger for children playing with them.
SUMMARY
Jelly blocks and letters are disclosed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 depict jelly blocks and letters respectively.
DETAILED DESCRIPTION
Referring to FIG. 1 , an example set of jelly blocks 101 is depicted. A plurality of elastomer gel blocks 102 and 103 are depicted in a stacked configuration. The elastomer gel from which the blocks are made is soft, has shape memory, and is stretchable, providing a fun and safe object for children to play with. Even if children strike each other with the jelly blocks, they are very unlikely to be injured. The elastomer gel can be formulated so that the exterior of the blocks is tacky so that the blocks will tend to stay together in a desired structure once assembled. This is helpful to small children who would like to build constructs using blocks but lack the coordination to assemble low-friction wooden or plastic blocks.
Referring to FIG. 2 , an example set of jelly letters 201 is depicted. The jelly letters will exhibit the same softness, shape memory and stretchability of the blocks. The jelly letters may be made tacky so that they will stick to a desired surface such as a refrigerator. Or they may be made non-tacky if desired. In a tacky formulation, the jelly letters will readily stick to a desired surface such as a refrigerator door and can be peeled off without leaving a residue. The tacky formulations of the elastomer gel may attract dirt and lint, but can be readily washed. The elastomer gel will be solid and nonflowable at room temperatures. The jelly blocks and jelly letters may be packaged as sets as children's toys or educational items. They may also be used by adults for various purposes.
Elastomeric gel as used herein shall mean any elastomeric gel as exemplified by gels of the several patents and patent applications to which priority is cited above, and others which may be known or become known at a later date. As an example, such gels may include combination of an elastomer and a plasticizer. The elastomer may be any appropriate elastomer, including but not limited to A-B-A triblock copolymers such as SEPS, SEBS, SEEPS and others. Elastomer gels used to make the body of jelly pens as described herein may be of any desired softness or rigidity, but some examples will be in the durometer range of from less than 0 to about 50 on the Shore A scale.
KRATON and SEPTON are examples of trade names used to identify some A-B-A triblock copolymers that may be used to make elastomer gels. Suitable plasticizers for elastomer gels include oils such as mineral oils, resins, rosins and others. Other components may be used in the gel as well, such as antioxidants, colorants, bleed reducing additives, microspheres and other components. The elastomer gel or gelatinous elastomer can be made quite tacky by the addition of resins and other sticky or tacky plasticizers. The elastomer gel may be manufactured by solvent blending, melt blending or compounding under heat and pressure such as by use of a single screw or twin screw compounding machine or otherwise. The finished jelly blocks or jelly letters may be constructed by injection molding, casting or another desired process.
Example elastomeric gels that can be considered for discussion purposes herein include, in parts by weight:
Example Elastomer Gel Formula
EXAMPLE ELASTOMER GEL FORMULA 20 parts Septon 4055 SEPS tri-block copolymer, available from Kurary of Japan 60 parts Duoprime 90 white paraffinic mineral oil available from Lyondell of Houston, Texas 60 parts Regalrez resin available from Hercules (resin which is hard at room temperature 0.3 parts blaze orange aluminum lake pigment available from Day-Glo Corporation of Twinsburg, Ohio 0.1 parts Irgannox 1076 antioxidant available from Ciba Geigy of Basel, Switzerland ANOTHER EXAMPLE ELASTOMER GEL FORMULA 20 parts Septon 4044 SEPS triblock copolymer, available from Kuraray of Japan 20 parts Septon 4055 SEPS triblock copolymer, available from Kuraray of Japan 70 parts Duoprime 90 white paraffinic mineral oil available from Lyondell of Houston, Texas 70 parts Regalrez resin available from Hercules (resin which is hard at room temperature) 0.1 part aluminum lake blue pigment 0.1 part Irgannox 1076 antioxidant A THIRD EXAMPLE ELASTOMER GEL FORMULA 40 parts Septon 4055 SEPS triblock copolymer, available from Kuraray of Japan 60 parts Duoprime 90 white paraffinic mineral oil available from Lyondell of Houston, Texas 60 parts Regalrez resin available from Hercules (resin which is hard at room temperature) 0.1 part aluminum lake blue pigment 0.1 part Irgannox 1076 antioxidant A FOURTH EXAMPLE ELASTOMER GEL FORMULA 20 parts Septon 4,055 SEPS triblock copolymer, available from Kuraray of Japan 20 parts Septon 4,077 SEPS triblock copolymer, available from Kuraray of Japan 140 parts Duoprime 90 white paraffinic mineral oil available from Lyondell of Houston, Texas 140 parts Regalrez: resin available from Hercules (resin which is hard at room temperature) 0.1 part aluminum lake blue pigment 0.1 part Irgannox 1076 antioxidant
Elastomer gels used to make the devices may be of any desired softness or rigidity, but some examples will be in the durometer range of from less than 0 to about 50 on the Shore A scale.
The manufacture of a gelatinous elastomer can be as disclosed in the patents and patent applications to which priority is claimed and may include any of melt blending, solvent blending or compounding by use of heat and pressure such as by using a single screw or twin screw compounding machine, or otherwise.
Elastomer Component
Compositions of elastomer gels maybe low durometer (as defined below) thermoplastic elastomeric compounds and visco-elastomeric compounds which include an elastomeric block copolymer component and a plasticizer component.
The elastomer component may include a triblock polymer of the general configuration A-B-A, wherein the A represents a crystalline polymer such as a monoalkenylarene polymer, including but not limited to polystyrene and functionalized polystyrene, and the B is an elastomeric polymer such as polyethylene, polybutylene, poly(ethylene/butylene), hydrogenated poly(isoprene), hydrogenated poly(butadiene), hydrogenated poly(isoprene+butadiene), poly(ethylene/propylene) or hydrogenated poly(ethylene/butylene+ethylene/propylene), or others. The A components of the material link to each other to provide strength, while the B components provide elasticity. Polymers of greater molecular weight are achieved by combining many of the A components in the A portions of each A-B-A structure and combining many of the B components in the B portion of the A-B-A structure, along with the networking of the A-B-A molecules into large polymer networks.
An example elastomer for making the elastomer gel material is a very high to ultra high molecular weight elastomer and oil compound having an extremely high Brookfield Viscosity (hereinafter referred to as “solution viscosity”). Solution viscosity is generally indicative of molecular weight. “Solution viscosity” is defined as the viscosity of a solid when dissolved in toluene at 25-30 degrees C., measured in centipoises (cps). “Very high molecular weight” is defined herein in reference to elastomers having a solution viscosity, 20 weight percent solids in 80 weight percent toluene, the weight percentages being based upon the total weight of the solution, from greater than about 20,000 cps to about 50,000 cps. An “ultra high molecular weight elastomer” is defined herein as an elastomer having a solution viscosity, 20 weight percent solids in 80 weight percent toluene, of greater than about 50,000 cps. Ultra high molecular weight elastomers have a solution viscosity, 10 weight percent solids in 90 weight percent toluene, the weight percentages being based upon the total weight of the solution, of about 800 to about 30,000 cps and greater. The solution viscosities, in 80 weight percent toluene, of the A-B-A block copolymers useful in the elastomer component of the gel are substantially greater than 30,000 cps. The solution viscosities, in 90 weight percent toluene, of the A-B-A elastomers useful in the elastomer component of the gel are in the range of about 2,000 cps to about 20,000 cps. Thus, the elastomer component of the gel material may have a very high to ultra high molecular weight.
The elastomeric B portion of the A-B-A polymers has an exceptional affinity for most plasticizing agents, including but not limited to several types of oils, resins, and others. When the network of A-B-A molecules is denatured, plasticizers which have an affinity for the B block can readily associate with the B blocks. Upon renaturation of the network of A-B-A molecules, the plasticizer remains highly associated with the B portions, reducing or even eliminating plasticizer bleed from the material when compared with similar materials in the prior art, even at very high oil:elastomer ratios. The reason for this performance may be any of the plasticization theories explained above (i.e., lubricity theory, gel theory, mechanistic theory, and free volume theory).
The elastomer used may be an ultra high molecular weight polystyrene-hydrogenated poly(isoprene+butadiene)-polystyrene, such as those sold under the brand names SEPTON® 4044, SEPTON® 4055 and SEPTON® 4077 by Kuraray, an ultra high molecular weight polystyrene-hydrogenated polyisoprene-polystyrene such as the elastomers made by Kuraray and sold as SEPTON® 2005 and SEPTON® 2006, or an ultra high molecular weight polystyrene-hydrogenated polybutadiene-polystyrene, such as that sold as SEPTON 8006 by Kuraray. High to very high molecular weight polystyrene-hydrogenated poly(isoprene+butadiene)-polystyrene elastomers, such as that sold under the trade name SEPTON® 4033 by Kuraray, are also useful in some formulations of the gel material because they are easier to process than the ultra high molecular weight elastomers due to their effect on the melt viscosity of the material.
Following hydrogenation of the midblocks of each of SEPTON® 4033, SEPTON® 4045, SEPTON® 4055, and SEPTON® 4077, less than about five percent of the double bonds remain. Thus, substantially all of the double bonds are removed from the midblock by hydrogenation.
SEPTON® 4055 has a very high molecular weight (approximately 300,000, as determined by Applicant's gel permeation chromatography testing). SEPTON® 4077 has a somewhat higher molecular weight, and SEPTON® 4045 has a somewhat lower molecular weight than SEPTON® 4055. Materials which include either SEPTON® 4045 or SEPTON® 4077 as the primary block copolymer typically have lower tensile strength than similar materials made with SEPTON® 4055.
Kuraray Co. Ltd. of Tokyo, Japan has stated that the solution viscosity of SEPTON® 4055, the most A-B-A triblock copolymer for use in gel material, 10% solids in 90% toluene at 25 degrees C., is about 5,800 cps. Kuraray also said that the solution viscosity of SEPTON 4055, 5% solids in 95% toluene at 25 degrees C., is about 90 cps. Although Kuraray has not provided a solution viscosity, 20% solids in 80% toluene at 25 degrees C., an extrapolation of the two data points given shows that such a solution viscosity would be about 400,000 cps.
Applicant confirmed Kuraray's data by having an independent laboratory, SGS U.S. Testing Company Inc. of Fairfield, N.J., test the solution viscosity of SEPTON® 4055. When SGS attempted to dissolve 20% solids in 80% toluene at 25 degrees C., the resulting material did not resemble a solution. Therefore, SGS determined the solution viscosity of SEPTON 4055 using 10% solids in 90% toluene at 25 degrees C., which resulted in a 3,040 cps solution.
Other materials with chemical and physical characteristics similar to those of SEPTON® 4055 include other A-B-A triblock copolymers which have a hydrogenated midblock polymer that is made up of at least about 30% isoprene monomers and at least about 30% butadiene monomers, the percentages being based on the total number of monomers that make up the midblock polymer. Similarly, other A-B-A triblock copolymers which have a hydrogenated midblock polymer that is made up of at least about 30% ethylene/propylene monomers and at least about 30% ethylene/butylene monomers, the percentages being based on the total number of monomers that make up the midblock polymer, are materials with chemical and physical characteristics similar to those of SEPTON® 4055.
Mixtures of block copolymer elastomers are also useful as the elastomer component of some of the formulations. In such mixtures, each type of block copolymer contributes different properties to the material. For example, high strength triblock copolymer elastomers are desired to improve the tensile strength and durability of a material. However, some high strength triblock copolymers are very difficult to process with some plasticizers. Thus, in such a case, block copolymer elastomers which improve the processability of the materials are desirable.
In particular, the process of compounding SEPTON® 4055 with plasticizers may be improved via a lower melt viscosity by using a small amount of more flowable elastomer such as SEPTON® 8006, SEPTON® 2005, SEPTON® 2006, or SEPTON® 4033, to name only a few, without significantly changing the physical characteristics of the material.
In a second example of the usefulness of block copolymer elastomer mixtures in the gel materials, many block copolymers are not good compatibilizers. Other block copolymers readily form compatible mixtures, but have other undesirable properties. Thus, the use of small amount of elastomers which improve the uniformity with which a material mixes are desired. KRATON® G1701, manufactured by Shell Chemical Company of Houston, Tex., is one such elastomer that improves the uniformity with which the components of the gel material mix.
Many other elastomers, including but not limited to triblock copolymers and diblock copolymers are also useful in the elastomer gel. Applicant believes that elastomers having a significantly higher molecular weight than the ultra-high molecular weight elastomers useful in the elastomer gel material increase the softness thereof, but decrease the strength of the gel. Thus, high to ultra high molecular weight elastomers, as defined above, are desired for use in the gel material due to the strength of such elastomers when combined with a plasticizer.
Additives
Polarizable Plasticizer Bleed-Reducing Additives
Some of the elastomer gel materials described herein do not exhibit migration of plasticizers, even when placed against materials which readily exhibit a high degree of capillary action, such as paper, at room temperature. Gel materials with higher plasticizer to polymer ratios may exhibit migration (bleed) and a bleed reducing additive is helpful to address the bleed issue.
A plasticizer bleed-reducing additive that may be useful in the elastomer gel material includes hydrocarbon chains with readily polarizable groups thereon. Such polarizable groups include, without limitation, halogenated hydrocarbon groups, halogens, nitrites, and others. Applicant believes that the polarizability of such groups on the hydrocarbon molecule of the bleed-reducing additive have a tendency to form weak van der Waals bonding with the long hydrocarbon chains of the rubber portion of an elastomer and with the plasticizer molecules. Due to the great length of typical rubber polymers, several of the bleed-reducers will be attracted thereto, while fewer will be attracted to each plasticizer molecule. The bleed-reducing additives are believed to hold the plasticizer molecules and the elastomer molecules thereto, facilitating attraction between the elastomeric block and the plasticizer molecule. In other words, the bleed-reducing additives are believed to attract a plasticizer molecule at one polarizable site, while attracting an elastomeric block at another polarizable site, thus maintaining the association of the plasticizer molecules with the elastomer molecules, which inhibits exudation of the plasticizer molecules from the elastomer-plasticizer compound. Thus, each of the plasticizer molecules is attracted to an elastomeric block by means of a bleed-reducing additive.
The bleed-reducing additives may have a plurality of polarizable groups thereon, which facilitate bonding an additive molecule to a plurality of elastomer molecules and/or plasticizer molecules. It is believed that an additive molecule with more polarizable sites thereon will bond to more plasticizer molecules. Preferably, the additive molecules remain in a liquid or a solid state during processing of the gel material.
The bleed-reducing additives may be halogenated hydrocarbon additives such as those sold under the trade name DYNAMAR® PPA-791, DYNAMAR® PPA-790, DYNAMAR® FX-9613, and FLUORAD® FC 10 Fluorochemical Alcohol, each by 3M Company of St. Paul, Minn. Other additives are also useful to reduce plasticizer exudation from the gel material. Such additives include, without limitation, other halogenated hydrocarbons sold under the trade name FLUORAD®, including without limitation FC-129, FC-135, FC-430, FC-722, FC-724, FC-740, FX-8, FX-13, FX-14 and FX-189; halogentated hydrocarbons such as those sold under the trade name ZONY®, including without limitation FSN 100, FSO 100, PFBE, 8857A, BA-L, BA-N, TBC and FTS, each of which are manufactured by du Pont of Wilmington, Del.; halogenated hydrocarbons sold under the trade name EMCOL by Witco Corp of Houston, Tex., including without limitation 4500 and DOSS; other halogenated hydrocarbons sold by 3M under the trade name DYNAMAR®; chlorinated polyethylene elastomer (CPE), distributed by Harwick, Inc. of Akron, Ohio; chlorinated paraffin wax, distributed by Harwick, Inc.; and others. The bleed reducing additives may be hydrocarbon resins, elastomeric diblock copolymers, polyisobutylene, butyl rubber, or transpolyoctenylene rubber (“tor rubber”).
Detackifiers
The elastomer gel may include a detackifier. Tack is not necessarily desired. However, some of the elastomer gel formulas impart tack to the media.
Soaps, detergents and other surfactants have detackifying abilities and are useful in the gel material. “Surfactants,” as defined herein, refers to soluble surface active agents which contain groups that have opposite polarity and solubilizing tendencies. Surfactants form a monolayer at interfaces between hydrophobic and hydrophilic phases; when not located at a phase interface, surfactants form micelles. Surfactants have detergency, foaming, wetting, emulsifying and dispersing properties. Sharp, D. W. A., DICTIONARY OF CHEMISTRY, 381-82 (Penguin, 1990). For example, coco diethanolamide, a common ingredient in shampoos, is useful in the gel material as a detackifying agent. Coco diethanolamide resists evaporation, is stable, relatively non-toxic, non-flammable and does not support microbial growth. Many different soap or detergent compositions could be used in the material as well.
Other detackifiers include glycerin, epoxidized soybean oil, dimethicone, tributyl phosphate, block copolymer polyether, hydrocarbon resins, polyisobutylene, butyl rubber, diethylene glycol mono oleate, tetraethyleneglycol dimethyl ether, and silicone, to name only a few. Glycerine is available from a wide variety of sources. Witco Corp. of Greenwich, Conn. sells epoxidized soybean oil as DRAPEX®. Dimethicone is available from a variety of vendors, including GE Specialty Chemicals of Parkersburg, W.Va. under the trade name GE SF 96-350. C.P. Hall Co. of Chicago, Ill. markets block copolymer polyether as PLURONIC L-61. C:P. Hall Co. also manufactures and markets diethylene glycol mono oleate under the name Diglycol Oleate—Hallco CPH-I-SE. Other emulsifiers and dispersants are also useful in the gel material. Tetraethyleneglycol dimethyl ether is available under the trade name TETRAGLYME® from Ferro Corporation of Zachary, La. Applicant believes that TETRAGLYME® also reduces plasticizer exudation from the gel material.
Antioxidants
The elastomer gel material may also include additives such as an antioxidant. Antioxidants such as those sold under the trade names IRGANOX® 1010 and IRGAFOS® 168 by Ciba-Geigy Corp. of Tarrytown, N.Y. are useful by themselves or in combination with other antioxidants.
Antioxidants protect the gel materials against thermal degradation during processing, which requires or generates heat. In addition, antioxidants provide long term protection from free radicals. An antioxidant inhibits thermo-oxidative degradation of the compound or material to which it is added, providing long term resistance to polymer degradation.
Heat, light (in the form of high energy radiation), mechanical stress, catalyst residues, and reaction of a material with impurities all cause oxidation of the material. In the process of oxidation, highly reactive molecules known as free radicals are formed and react in the presence of oxygen to form peroxy free radicals, which further react with organic material (hydro-carbon molecules) to form hydroperoxides.
The two major classes of antioxidants are the primary antioxidants and the secondary antioxidants. Peroxy free radicals are more likely to react with primary antioxidants than with most other hydrocarbons. In the absence of a primary antioxidant, a peroxy free radical would break a hydrocarbon chain. Thus, primary antioxidants deactivate a peroxy free radical before it has a chance to attack and oxidize an organic material.
Most primary antioxidants are known as sterically hindered phenols. One example of sterically hindered phenol is marketed by Ciba-Geigy as IRGANOX® 1010, which has the chemical name 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, 2,2-bis [[3-[3,5-bis(dimethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]1,3-propa nediyl ester. The FDA refers to IRGANOX® 1010 as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnimate)]methane. Other hindered phenols are also useful as primary antioxidants in the material.
Similarly, secondary antioxidants react more rapidly with hydroperoxides than most other hydrocarbon molecules. Secondary antioxidants have been referred to as hydroperoxide decomposers. Thus, secondary antioxidants protect organic materials from oxidative degradation by hydroperoxides.
Commonly used secondary antioxidants include the chemical classes of phosphites/phosphonites and thioesters, many of which are useful in the gel material. The hydroperoxide decomposer can be a phosphite known as Tris(2,4-di-tert-butylphenyl)phosphite and marketed by Ciba-Geigy as IRGAFOS® 168.
Primary and secondary antioxidants form synergistic combinations to ward off attacks from both peroxy free radicals and hydroperoxides.
Other antioxidants, including but not limited to multi-functional antioxidants, are also useful in the material. Multifunctional antioxidants have the reactivity of both a primary and a secondary antioxidant. IRGANOX® 1520 D, manufactured by Ciba-Geigy is one example of a multifunctional antioxidant. Vitamin E antioxidants, such as that sold by Ciba-Geigy as IRGANOX® E17, are also useful in the gel material.
The elastomer gel material may include up to about three weight percent antioxidant, based on the weight of the elastomer component, when only one type of antioxidant is used. The material may include as little as 0.1 weight percent of an antioxidant, or no antioxidant at all. When a combination of antioxidants is used, each may comprise up to about three weight percent, based on the weight of the elastomer component. Additional antioxidants may be added for severe processing conditions involving excessive heat or long duration at a high temperature.
The use of excess antioxidants reduces or eliminates tack on the exterior surface of the gel material. Excess antioxidants appear to migrate to the exterior surface of the material following compounding of the material. Such apparent migration occurs over substantial periods of time, from hours to days or even longer.
Flame retardants
Flame retardants may also be added to elastomer gel materials. Flame retardants include but are not limited to diatomaceous earth flame retardants sold as GREAT LAKES DE 83R and GREAT LAKES DE 79 by Great Lakes Filter, Division of Acme Mills Co. of Detroit, Mich. Most flame retardants that are useful in elastomeric materials are also useful in the gel material.
Chemical blowing agents, such as SAFOAM® FP-40, manufactured by Reedy International Corporation of Keyport, N.J. and others are useful for making a gel medium that is self-extinguishing.
Colorants
Colorants may also be used in gel materials. Any colorant which is compatible with elastomeric materials may be used. Aluminum lake colorants such as those manufactured by Warner Jenkinson Corp. of St. Louis, Mo. Are available. Pigments manufactured by Day Glo Color Corp. of Cleveland, Ohio; Lamp Black, such as that sold by Spectrum Chemical Manufacturing Corp. of Gardena, Calif.; and Titanium Dioxide (white) are also available. By using these colorants, the gel material takes on intense shades of colors, including but not limited to pink, red, orange, yellow, green, blue, violet, brown, flesh, white and black.
Paint
The elastomer gel may also be painted.
Other Additives
Melt temperature modifiers useful in the gel include cross-linking agents, hydrocarbon resins, diblock copolymers of the general configuration A-B and triblock copolymers of the general configuration A-B-A wherein the end block A polymers include functionalized styrene monomers, and others.
Melt viscosity modifiers that tend to reduce the melt viscosity of the pre-compounded component mixture of the medium include hydrocarbon resins, transpolyoctenylene rubber, castor oil, linseed oil, non-ultra high molecular weight thermoplastic rubbers, surfactants, dispersants, emulsifiers, and others.
Melt viscosity modifiers that tend to increase the melt viscosity of the pre-compounded component mixture of the gel material include hydrocarbon resins, butyl rubber, polyisobutylene, additional triblock copolymers having the general configuration A-B-A and a molecular weight greater than that of each of the block copolymers in the elastomeric block copolymer component of the material, particulate fillers, microspheres, butadiene rubber, ethylene/propylene rubber, ethylene/butylene rubber, and others.
Tensile strength modifiers which tend to increase the tensile strength of the gel material for use in the gel material include mid block B-associating hydrocarbon resins, non-end-block solvating hydrocarbon resins which associate with the end blocks, particulate reinforcers, and others.
Shrinkage inhibitors, which tend to reduce shrinkage of the gel material following compounding, that are useful in the material include hydrocarbon resins, particulate fillers, microspheres, transpolyoctenylene rubber, and others.
Microspheres
Microspheres may also be added to the gel material. The gel material may contain up to about 90% microspheres, by volume. In one microsphere-containing formulation of the gel material, microspheres make up at least about 30% of the total volume of the material. A second microsphere-containing formulation of the gel material includes at least about 50% microspheres, by volume.
Different types of microspheres contribute various properties to the material. For example, hollow acrylic microspheres, such as those marketed under the brand name MICROPEARL®, and generally in the 20 to 200 micron size range, by Matsumoto Yushi-Seiyaku Co., Ltd. of Osaka, Japan, lower the specific gravity of the material. In other formulations of the gel, the microspheres may be unexpanded DU(091-80), which expand during processing of the gel material, or pre-expanded DE (091-80) acrylic microspheres from Expancel Inc. of Duluth, Ga.
In formulations of the material which include hollow acrylic microspheres, the microspheres have substantially instantaneous rebound when subjected to a compression force which compresses the microspheres to a thickness of up to about 50% of their original diameter or less.
Hollow microspheres also decrease the specific gravity of the gel material by creating gas pockets therein. When a gel material includes microspheres, the microspheres must be dispersed, on average, at a distance of about one-and-ahalf (1.5) times the average microsphere diameter or a lesser distance from one another in order to achieve a specific gravity of less than about 0.50. Other formulations of the gel material have specific gravities of less than about 0.65, less than about 0.45, and less than about 0.25.
MICROPEARL® and EXPANCEL® acrylic microspheres are because of their highly flexible nature, as explained above, which tend to not restrict deformation of the thermoplastic elastomer. Glass, ceramic, and other types of microspheres may also be used in the thermoplastic gel material.
Plasticizer Component
As explained above, plasticizers allow the midblocks of a network of triblock copolymer molecules to move past one another. Thus, Applicant believes that plasticizers, when trapped within the three dimensional web of triblock copolymer molecules, facilitate the disentanglement and elongation of the elastomeric midblocks as a load is placed on the network. Similarly, Applicant believes that plasticizers facilitate recontraction of the elastomeric midblocks following release of the load. The plasticizer component of the gel may include oil, resin, a mixture of oils, a mixture of resins, other lubricating materials, or any combination of the foregoing.
Oils
The plasticizer component of the gel material may include a commercially available oil or mixture of oils. The plasticizer component may include other plasticizing agents, such as liquid oligomers and others, as well. Both naturally derived and synthetic oils are useful in the gel material. The oils may have a viscosity of about 70 SUS to about 500 SUS at about 100 degrees F. Paraffinic white mineral oils having a viscosity in the range of about 90 SUS to about 200 SUS at about 100 degrees F. may be used
One embodiment of a plasticizer component of the gel includes paraffinic white mineral oils, such as those having the brand name DUOPRIME®, by Lyondell Lubricants of Houston, Tex., and the oils sold under the brand name TUFFLO® by Witco Corporation of Petrolia, Pa. For example, the plasticizer component of the gel may include paraffinic white mineral oil such as that sold under the trade name LP-150® by Witco.
Paraffinic white mineral oils having an average viscosity of about 90 SUS, such as DUOPRIME® 90, are used in other embodiments of the plasticizer component. Applicant has found that DUOPRIME® 90 and oils with similar physical properties can be used to impart the greatest strength to the gel material.
Other oils are also useful as plasticizers in compounding the gel material. Examples of representative commercially available oils include processing oils such as paraffinic and naphthenic petroleum oils, highly refined aromatic-free or low aromaticity paraffinic and naphthenic food and technical grade white petroleum mineral oils, and synthetic liquid oligomers of polybutene, polypropene, polyterpene, etc., and others. The synthetic series process oils are oligomers which are permanently fluid liquid non-olefins, isoparaffins or paraffins. Many such oils are known and commercially available. Examples of representative commercially available oils include Amoco.RTM. polybutenes, hydrogenated polybutenes and polybutenes with epoxide functionality at one end of the polybutene polymer. Examples of various commercially available oils include: Bayol, Bernol, American, Blandol, Drakeol, Ervol, Gloria, Kaydol, Litetek, Marcol, Parol, Peneteck, Primol, Protol, Sontex, and the like.
Resins
Resins useful in the plasticizer component include, but are not limited to, hydrocarbon-derived and rosin-derived resins having a ring and ball softening point of up to about 150 degrees C., or from about 0 degrees C. to about 25 degrees C., and a weight average molecular weight of at least about 300.
Resins or resin mixtures which are highly viscous flowable liquids at room temperature (about 23 degrees C.) may be used. Plasticizers which are fluid at room temperature impart softness to the gel material. Resins which are not flowable liquids at room temperature are also useful in the material.
Some resins used have a ring and ball softening point of about 18 degrees C.; melt viscosities of about 10 poises (ps) at about 61 degrees C., about 100 ps at about 42 degrees C. and about 1,000 ps at about 32.degrees C. One such resin is marketed as REGALREZ® 1018 by Hercules Incorporated of Wilmington, Del. Variations of REGALREZ® 1018 which are useful in the material have viscosities including, but not limited to, 1025 stokes, 1018 stokes, 745 stokes, 114 stokes, and others.
Room temperature flowable resins that are derived from poly-.beta.-pinene and have softenening points similar to that of REGALREZ® 1018 are also useful in the plasticizer component of the medium. One such resin, sold as PICCOLYTE® S25 by Hercules Incorporated, has a softening point of about 25 degrees C.; melt viscosities of about 10 ps at about 80 degrees C., about 100 ps at about 56 degrees C. and about 1,000 ps at about 41 degrees C.; a MMAP value of about 88 degrees C.; a DACP value of about 45 degrees C.; an OMSCP value of less than about −50.degrees C. Other PICCOLYTE® resins may also be used in the gel material.
Another room temperature flowable resin which is useful in the plasticizer component of the material is marketed as ADTAC® LV by Hercules Incorporated. That resin has a ring and ball softening point of about 5 degrees C.; melt viscosities of about 10 ps at about 62 degrees C., about 100 ps at about 36 degrees C. and about 1,000 ps at about 20 degrees C.; a MMAP value of about 93 degrees C.; a DACP value of about 44 degrees C.; an OMSCP value of less than about −40 degrees C.
Resins such as the liquid aliphatic C-5 petroleum hydrocarbon resin sold as WINGTACK® 10 by the Goodyear Tire & Rubber Company of Akron, Ohio and other WINGTACK® resins are also useful in the gel material. WINGTACK® 10 has a ring and ball softening point of about 10 degrees C.; a Brookfield Viscosity of about 30,000 cps at about 25 degrees C.; melt viscosities of about 10 ps at about 53 degrees C. and about 100 ps at about 34 degrees C.; a 1:1 polyethylene-to-resin ratio cloud point of about 89 degrees C.; a 1:1 microcrystalline wax-to-resin ratio cloud point of about 77 degrees C.; and a 1:1 paraffin wax-to-resin ratio cloud point of about 64 degrees C.
Resins that are not readily flowable at room temperature (i.e., are solid, semi-solid, or have an extremely high viscosity) or that are solid at room temperature are also useful in the gel material. One such solid resin is an aliphatic C-5 petroleum hydrocarbon resin having a ring and ball softening point of about 98 degrees C.; melt viscosities of about 100 ps at about 156 degrees C. and about 1000 ps at about 109 degrees C.; a 1:1 polyethylene-to-resin ratio cloud point of about 90 degrees C.; a 1:1 microcrystalline wax-to-resin ratio cloud point of about 77 degrees C.; and a 1:1 paraffin wax-to-resin ratio cloud point of about 64 degrees C. Such a resin is available as WINGTACK® 95 and is manufactured by Goodyear Chemical Co.
Polyisobutylene polymers are an example of resins which are not readily flowable at room temperature and that are useful in the gel material. One such resin, sold as VISTANEX® LM-MS by Exxon Chemical Company of Houston, Tex., has a Tg of −60.degrees C., a Brookfield Viscosity of about 250 cps to about 350 cps at about 350 degrees F., a Flory molecular weight in the range of about 42,600 to about 46,100, and a Staudinger molecular weight in the range of about 10,400 to about 10,900. The Flory and Staudinger methods for determining molecular weight are based on the intrinsic viscosity of a material dissolved in diisobutylene at 20 degrees C.
Glycerol esters of polymerized rosin are also useful as plasticizers in the gel material. One such ester, manufactured and sold by Hercules Incorporated as HERCULES® Ester Gum 10D Synthetic Resin, has a softening point of about 116 degrees C.
Many other resins are also suitable for use in the gel material. In general, plasticizing resins are those which are compatible with the B block of the elastomer used in the material, and non-compatible with the A blocks.
In some formulations, tacky materials may be desirable. In such formulations, the plasticizer component of the gel material may include about 20 weight percent or more, about 40 weight percent or more, about 60 weight percent or more, or up to about 100 weight percent, based upon the weight of the plasticizer component, of a tackifier or tackifier mixture.
Plasticizer Mixtures
The use of plasticizer mixtures in the plasticizer component of the gel material is useful for tailoring the physical characteristics of the gel material. For example, characteristics such as durometer, tack, tensile strength, elongation, melt flow and others may be modified by combining various plasticizers.
For example, a plasticizer mixture which includes at least about 37.5 weight percent of a paraffinic white mineral oil having physical characteristics similar to those of LP-150 (a viscosity of about 150 SUS at about 100 degrees F., a viscosity of about 30 centistokes (cSt) at about 40 degrees C., and maximum pour point of about −35 degrees F.) and up to about 62.5 weight percent of a resin having physical characteristics similar to those of REGALREZ® 1018 (such as a softening point of about 20 degrees C.; a MMAP value of about 70 degrees C.; a DACP value of about 15 degrees C.; an OMSCP value of less than about −40 degrees C.; all weight percentages being based upon the total weight of the plasticizer mixture, could be used in a gel. When compared to a material plasticized with the same amount of an oil such as LP-150, the material which includes the plasticizer mixture has decreased oil bleed and increased tack.
When resin is included with oil in a plasticizer mixture of the gel the material exhibits reduced oil bleed. For example, a formulation of the material which includes a plasticizing component which has about three parts plasticizing oil (such as LP-150), and about five parts plasticizing resin (such as REGALREZ® 1018) exhibits infinitesimal oil bleed at room temperature, if any, even when placed against materials with high capillary action, such as paper.
The plasticizer:block copolymer elastomer ratio, by total combined weight of the plasticizer component and the block copolymer elastomer component in some formulations ranges from as low as about 1:1 or less to higher than about 25:1. In applications where plasticizer bleed is acceptable, the ratio may as high as about 100:1 or more. Plasticizer:block copolymer ratios in the range of about 2.5:1 to about 8:1 may be more common. A ratio such as 5:1 provides the desired amounts of rigidity, elasticity and strength for many typical applications. A plasticizer to block copolymer elastomer ratio of 2.5:1 has a high amount of strength and elongation.
Compounding Methods
Compounding may be carried out by melt blending, solvent blending, or compounding under heat and pressure such as by use of a single screw or twin screw compounding machine.
While the devices, materials and methods have been described and illustrated in conjunction with a number of specific examples, those skilled in the art will appreciate that variations and modifications may be made without departing from the principles herein illustrated, described, and claimed. The present invention, as defined by the appended claims, may be embodied in other specific forms without departing from its spirit or essential characteristics. The configurations of lights described herein are to be considered in all respects as only illustrative, and not restrictive. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
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Jelly blocks and jelly letters are disclosed. The jelly blocks and jelly letters may be made from an elastomer gel resulting in a soft, stretchable children's toy that has shape memory. The jelly blocks and jelly letters may be made from an elastomer gel that is formulated for tackiness to permit stacking of the blocks or sticking of the letters to a desired surface. The blocks and letters may be soft enough that a child could be struck with them without suffering injury.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to a system and method for detecting flashback events in a combustor of a gas turbine engine and, more particularly, to a fiber optic distributed sensing system employing Rayleigh backscattering and swept-wavelength interferometry for measuring temperature and detecting flashback events at many locations within a combustor of a gas turbine engine.
[0003] 2. Discussion of the Related Art
[0004] The world's energy needs continue to rise which provides a demand for reliable, affordable, efficient and environmentally-compatible power generation. A gas turbine engine is one known machine that provides efficient power, and often has application for an electric generator in a power plant, or engines in an aircraft or a ship. A typically gas turbine engine includes a compressor section, a combustion section and a turbine section. The compressor section provides a compressed airflow to the combustion section where the air is mixed with a fuel, such as natural gas. The combustion section includes a plurality of circumferentially disposed combustors that receive the fuel to be mixed with the air and ignited to generate a working gas. The working gas expands through the turbine section and is directed across rows of blades therein by associated vanes As the working gas passes through the turbine section, it causes the blades to rotate, which in turn causes a shaft to rotate, thereby producing mechanical work
[0005] Each combustor includes a fuel injector, orifices for receiving compressed air and an igniter for igniting the fuel/air mixture to create a flame in a combustion basket The pressure and volume of both the injected fuel and the air are carefully controlled for a particular combustor so that the flame is propelled forward into a transition duct to the turbine section. As the operating conditions of the turbine engine vary and change, a failure mode could occur where the pressure and flow volume of the fuel and/or air causes a flashback condition where the flame travels backwards in a direction away from the turbine section. If the engine operating parameters are not immediately changed to remove the flashback condition, the flame flashback could cause damage to components upstream of the combustion area in the combustion basket because many of those components are not designed for such high temperatures.
[0006] It is known in the art to provide various types of sensors, such as high temperature thermocouples or optical detectors, such as fiber Bragg grating (FBG) sensors, strategically positioned behind the combustion area in the combustion basket of a combustor to detect flame flashback by detecting higher than normal temperatures. If flame flashback is detected by one of the detectors, then the system engine controller will take some immediate action, possibly system shutdown, to remove the flashback condition. However, the number of thermocouples and/or optical sensors that can be provided in the combustor is limited because of limits of the ability to configure and position multiple thermocouple sensors in the combustion basket or the spatial resolution of the optical detectors provided in an optical sensor. Because the resolution is limited, the ability to quickly detect a flashback condition and specifically identify the location of the flashback condition is correspondingly limited. For example, the flame may flash back to a location in the combustion basket where a sensor does not exist, thus limiting the ability to detect that flashback condition.
SUMMARY OF THE INVENTION
[0007] The present disclosure describes a distributed sensing system for detecting a flashback condition in a combustor for a gas turbine engine, where the system is based on Rayleigh backscattering that can be detected at a very high spatial resolution The distributed sensing system employs swept-wavelength interferometry to measure temperature using the Rayleigh backscattering and reliably identify the location of the flashback condition. A fiber optic cable supporting the Rayleigh backscattering is specially fabricated to have a high temperature resistance suitable for those temperatures existing during flashback conditions. The fiber optic cable can be wrapped on an inside of a combustion basket or on an outside of the combustion basket, and in a serpentine manner or otherwise
[0008] Additional features of the present invention will become apparent from the following description and appended claims, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a cut-away, isometric view of a gas turbine engine,
[0010] FIG. 2 is a cut-away, cross-sectional type view of a portion of a combustor in the combustion section of the gas turbine engine;
[0011] FIG. 3 is an illustration of a distributed sensing system including a fiber optic cable; and
[0012] FIG. 4 is a block diagram of a flashback engine control system.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0013] The following discussion of the embodiments of the invention directed to a distributed sensing system employing a fiber optic cable and Rayleigh backscattering for detecting temperature and a flashback condition in a combustor for a gas turbine engine is merely exemplary in nature, and is in no way intended to limit the invention or its applications or uses.
[0014] FIG. 1 is a cut-away, isometric view of a gas turbine engine 10 including a compressor section 12 , a combustion section 14 and a turbine section 16 all enclosed within an outer housing or casing 30 , where operation of the engine 10 causes a central shaft or rotor 18 to rotate, thus creating mechanical work. The engine 10 is illustrated and described by way of a non-limiting example to provide context to the invention discussed below. Those skilled in the art will appreciate that other gas turbine engine designs can also be used in connection with the invention Rotation of the rotor 18 draws air into the compressor section 12 where it is directed by vanes 22 and compressed by rotating blades 20 to be delivered to the combustion section 14 , where the compressed air is mixed with a fuel, such as natural gas, and where the fuel/air mixture is ignited to create a hot working gas. More specifically, the combustion section 14 includes a number of circumferentially disposed combustors 26 each receiving the fuel that is injected into the combustor 26 by an injector (not shown), mixed with the compressed air and ignited by an igniter 24 to be combusted to create the working gas, which is directed by a transition component 28 into the turbine section 16 . The working gas is then directed by circumferentially disposed stationary vanes (not shown in FIG. 1 ) in the turbine section 16 to flow across circumferentially disposed rotatable turbine blades 34 , which causes the turbine blades 34 to rotate, thus rotating the rotor 18 . Once the working gas passes through the turbine section 16 it is output from the engine 10 as an exhaust gas through an output nozzle 36 .
[0015] Each group of the circumferentially disposed stationary vanes defines a row of the vanes and each group of the circumferentially disposed blades 34 defines a row 38 of the blades 34 . In this non-limiting embodiment, the turbine section 16 includes four rows 38 of the rotating blades 34 and four rows of the stationary vanes in an alternating sequence. In other gas turbine engine designs, the turbine section 16 may include more or less rows of the turbine blades 34 It is noted that the most forward row of the turbine blades 34 , referred to as the row 1 blades, and the vanes, referred to as the row 1 vanes, receive the highest temperature of the working gas, where the temperature of the working gas decreases as it flows through the turbine section 16 .
[0016] FIG. 2 is a cut-away, cross-sectional type view of a portion of one of the combustors 26 coupled to one of the transition components 28 . The combustor 26 includes a fuel injection system 40 mounted to a cover plate 42 enclosing a combustion shell 44 . The fuel injection system 40 includes fuel nozzles 46 and a pilot nozzle 48 An end of the fuel injection system 40 proximate the pilot nozzle 48 is coupled to a funnel-shaped combustion basket 50 including orifices 52 that allow pressurized air from the compressor section 12 to enter the combustion basket 50 . A combustion monitoring and control system 56 controls the fuel injection system 40 to cause the desired amount of fuel to be injected into the combustion basket 50 through the fuel nozzles 46 for a particular operating condition of the engine, where the fuel is mixed with the air and is ignited by the pilot flame to provide a high intensity flame. The flame generates the hot working gas that flows through the transition component 28 towards the first row of vanes in the turbine section 16 , represented here by vane 58 .
[0017] The present invention proposes a distributed sensing system that employs swept-wavelength interferometry for detecting Rayleigh backscattering in a fiber optical cable to detect elevated temperatures in a region in the combustor 26 upstream from the location where the fuel/air is ignited in the combustion basket 50 to generate the hot working gas, which could be an indication of a flashback condition. The distributed sensing system includes one or more fiber optic cables of a certain length strategically coupled to the combustion basket 50 , the pilot nozzle 48 , or some other suitable location in the combustor 26 . In this non-limiting example, a sensing fiber optic cable 60 is mounted to an inside surface of the combustion basket 50 upstream of the orifices 52 and thus upstream of the location where the main combustion event occurs. Additionally, or alternately, a distributed sensing fiber optic cable 62 is provided within the pilot nozzle 48 . The cables 60 and 62 provide Rayleigh backscatter reflectometry that will be measured using swept wavelength interferometry. In one non-limiting embodiment, the fiber 60 is about 1 meter long which can provide sub-millimeter spatial resolution and a high accuracy with a fast response time.
[0018] The fiber 60 can be mounted to the combustion basket 50 , or other suitable combustor component, in any desired strategic manner that allows it to effectively detect temperature depending on the particular combustor design. For example, the fiber 60 can be wound around an internal surface of the combustion basket 50 or wound around an external surface of the combustion basket 50 . Further, the cable 60 can be mounted to the inside or outside wall of the combustion basket 50 in a serpentine manner to provide even a higher degree of resolution for a particular application. By providing a single fiber in this manner, and internal to the combustion basket 50 , only a single hole needs to be drilled into the wall of the combustion basket 50 to allow the cable 60 to placed therein, where as with the tradition thermocouple sensors, a separate hole needed to be drilled for each separate thermocouple sensor The fiber optical cable 60 can be mounted to the wall of the combustion basket 50 in any suitable manner, such as by a high temperature adhesive or thermo-bonding
[0019] FIG. 3 is a representation of a distributed sensing system 70 including a distributed sensing fiber optic cable 72 of the type that can be used for the fiber optic cables 60 and 62 discussed above The fiber optic cable 72 includes an optical fiber core 74 surrounded by an outer cladding layer 76 . The index of refraction of the cladding layer 76 is greater than the index of refraction of the fiber core 74 so that a light beam at a low enough angle of incidence propagating down the fiber core 74 is reflected off of the transition between the fiber core 74 and the cladding layer 76 and is trapped therein. In one embodiment, the fiber core 74 is about 10 μm in diameter, which provides a multi-mode fiber for propagating multiple optical modes. Because the fiber optic cable 72 will be used in a high temperature environment, the fiber optic cable 72 is made of a high temperature material, such as quartz, so as not to be damaged in the high temperature environment. Further heat resistance can be provided by coating the cladding layer 76 with a high temperature coating 78 , such as gold, so as to withstand temperatures up to about 800° C.
[0020] The general idea of employing swept wavelength interferometry for detecting Rayleigh backscattering along the length of a fiber optic cable to detect temperature change is known to those skilled in the art. An analyzer 82 includes a swept wavelength interferometer having an optical reference path of a known length and an optical sensing path, which is the fiber optic cable 72 The analyzer 82 sends an optical signal of a predetermined wavelength down the core 74 . Rayleigh backscattering of the optical signal as it propagates along the cable 72 is caused by random profile fluctuations along the length of the cable 72 . The temperature of the cable 72 creates a particular reflection spectrum of the backscattering along the length of the fiber cable 72 , where changes in the temperature of the cable 72 cause a shift in that spectrum. The profile of the backscattering spectrum can be analyzed in segments along the length of the fiber cable 72 by Fourier transforming the spectrum to give the spatial resolution In one non-limiting embodiment, the backscattering analysis can provide a spatial resolution of about 0.5 mm and the analyzer response time of about 0.1 seconds
[0021] FIG. 4 is a block diagram of a distributed sensing control system 90 for responding to a flame flashback condition as discussed above. The system 90 includes a box 92 representing the gas turbine engine, which provides a signal to an analyzer 94 representing the optical signal from the distributed sensing fiber cable. Based on the numerous reflections from the sensing locations in the fiber optic cable, the analyzer 94 is able to determine if flame flashback is occurring, and if so, the location of the flashback, the intensity of the flashback and the rate of propagation of the flashback The analyzer 94 provides a signal indicative of all of these parameters to an engine control system 96 that will change the operating parameters of the engine 92 , including shutting the engine 92 down, if necessary, to limit the flashback condition if it exists. The engine control system 96 likely will provide a signal to the combustion monitoring and control system 56 for the particular combustor 26 that is experiencing the flashback condition.
[0022] The foregoing discussion discloses and describes merely exemplary embodiments of the present invention. One skilled in the art will readily recognize from such discussion, and from the accompanying drawings and claims, that various changes, modifications and variations can be made therein without departing from the scope of the invention as defined in the following claims
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A distributed sensing system for detecting a flashback condition in a combustor for a gas turbine engine The distributed sensing system includes one or more strategically positioned fiber optic cables provided upstream of the combustion area in the combustor. The distributed sensing system employs Rayleigh backscattering and swept-wavelength interferometry to measure temperature and reliably identify the location of the flashback condition The fiber optic cable is specially fabricated to have a high temperature resistance suitable for those temperatures existing during flashback conditions. The fiber optic cable can be wrapped on an inside of a combustion basket or on an outside of the combustion basket, and in a serpentine manner or otherwise.
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TECHNICAL FIELD
[0001] The present invention relates to a semiconductor integrated circuit interconnect structure and method of forming a multi-layered seed layer of the interconnect structure to minimize electromigration, utilizing sequential catalytic chemical vapor deposition.
BACKGROUND
[0002] Semiconductor devices include a plurality of circuit components (i.e., transistors, resistors, diodes, capacitors, etc.) connected together to form an integrated circuit fabricated on a semiconductor substrate. A complex network of semiconductor integrated circuit interconnects (interconnects) are routed to connect the circuit components distributed on the surface of the substrate. Efficient routing of these interconnects, across semiconductor devices, requires formation of multi-level or multi-layered patterning schemes, such as single or dual damascene interconnect structures.
[0003] An interconnect structure includes metal vias that run perpendicular to the semiconductor substrate. The metal vias are disposed in trench areas. In addition, an interconnect structure includes metal lines that are disposed in the trench areas, wherein the trench areas are formed in dielectric material. The metal vias are connected to the metal lines, and the metal lines run parallel to the semiconductor substrate. Thus, both the metal lines and metal vias are disposed proximately to the dielectric material having a dielectric constant of less than 5.0, which enhances signal speed and minimizes signal crosstalk (i.e., crosstalk refers to a signal being transmitted through a metal line, and affecting another signal being transmitted through a separate metal line, and/or affecting other parts of circuitry in an undesired manner).
[0004] Furthermore, interconnect structures that are copper (Cu) based, when compared with aluminum (Al) based interconnect structures, provide higher speed signal transmission between large numbers of transistors on a complex semiconductor chip. Accordingly, when manufacturing integrated circuits, copper (i.e., a metal conductor) is typically used for forming the semiconductor integrated circuit's interconnects because of copper's low resistivity and high current carrying capacity. Resistivity is the measure of how much a material opposes electric current, due to a voltage being placed across the material. However, when copper is utilized to form interconnects electromigration may occur. Electromigration can result in void formation, as well as extrusion/hillock formation. Integrated circuit manufacturers generally have electromigration requirements that should be satisfied as part of an overall quality assurance validation process, but thereafter electromigration may still persist during the lifetime of an integrated circuit in a user's computer (i.e., when current flows through the semiconductor integrated circuit's interconnect structure).
[0005] Specifically, electromigration is the gradual displacement of atoms of a metal conductor, due to high density of current passing through the metal conductor, and electromigration is accelerated when the temperature of the metal conductor increases. Since a semiconductor integrated circuit's interconnect structure is generally formed using copper, which is a metal conductor susceptible to electromigration, electromigration presents a problem when utilizing integrated circuits with copper based interconnects.
[0006] Electromigration (i.e., the gradual displacement of metal atoms from one location to another location throughout a metal conductor, due to the high density of current flow) can result in void formation, as well as extrusion/hillock formation in a semiconductor integrated circuit's interconnect structure. The voids can result in an open circuit if one or more voids formed are large enough to sever the interconnect structure, and the extrusions/hillocks can result in a short circuit if one or more extrusions/hillocks are sufficiently long to form a region of abnormally low electrical impedance. Accordingly, void formation and extrusion/hillock formation, due to electromigration, can reduce integrated circuit performance, decrease reliability of interconnects, cause sudden data loss, and reduce the useful life of semiconductor integrated circuit products.
SUMMARY
[0007] The present invention relates to a semiconductor integrated circuit interconnect structure (interconnect structure) and method of forming the interconnect structure to minimize electromigration. Minimizing electromigration can improve integrated circuit performance, enhance reliability of interconnect structures, minimize sudden data loss, and enhance the useful lifetime of semiconductor integrated circuit products.
[0008] A first aspect of the present invention provides an interconnect structure comprising: one or more openings in a dielectric layer; a barrier metal layer disposed on the dielectric layer; a multi-layered seed layer disposed on the barrier metal layer, wherein the multi-layered seed layer comprises at least three layers; an electroplated copper layer disposed on the multi-layered seed layer; a planarized surface, wherein a portion of the barrier metal layer, the multi-layered seed layer, and the electroplated copper layer are removed; and a capping layer disposed on the planarized surface.
[0009] A second aspect of the present invention provides a method of performing a sequential catalytic chemical vapor deposition (CVD) process by utilizing a catalytic CVD apparatus, the method comprising the steps of: forming one or more openings in a dielectric layer; forming a barrier metal layer disposed on the dielectric layer; forming a multi-layered seed layer disposed on the barrier metal layer, wherein the multi-layered seed layer comprises at least three layers; forming an electroplated copper layer disposed on the multi-layered seed layer; forming a planarized surface, wherein a portion of the barrier metal layer, the multi-layered seed layer, and the electroplated copper layer are removed; and forming a capping layer disposed on the planarized surface.
[0010] A third aspect of the present invention provides a catalytic chemical vapor deposition apparatus comprising: a catalytic chemical vapor deposition (CVD) processing chamber, wherein the catalytic CVD processing chamber comprises a heatable metal wire, a heatable plate; and a heatable tank operatively coupled to the catalytic CVD processing chamber.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0011] The subject matter which is regarded as an embodiment of the present invention is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. One manner in which recited features of an embodiment of the present invention can be understood is by reference to the following detailed description of embodiments, taken in conjunction with the accompanying drawings in which:
[0012] FIG. 1 is a pictorial representation (i.e., cross-sectional view) of a semiconductor illustrating the formation of trench areas and via holes (i.e., vias) according to one embodiment of the present invention.
[0013] FIG. 2 depicts a top view of an array of trench areas and via holes (i.e., vias) according to one embodiment of the present invention.
[0014] FIGS. 3A-3D are pictorial representations (i.e., cross-sectional views) illustrating the formation of trench areas and via holes with a barrier metal layer, a multi-layered seed layer, an electroplated copper layer, and a dielectric capping layer according to one embodiment of the present invention.
[0015] FIG. 4 depicts a cross-sectional view of a catalytic chemical vapor deposition (CVD) processing chamber and heatable tank adapted to deliver metal ions and precursor gases to a substrate according to one embodiment of the present invention.
[0016] FIG. 5 is a method flow block diagram illustrating a method for forming a multi-layered seed layer of a semiconductor integrated circuit interconnect structure according to one embodiment of the present invention.
[0017] The drawings are not necessarily to scale. The drawings, some of which are merely pictorial and schematic representations, are not intended to portray specific parameters of the invention. The drawings are intended to depict only typical embodiments of the invention, and therefore should not be considered as limiting the scope of the invention. In the drawings, like numbering represents like elements.
DETAILED DESCRIPTION
[0018] Exemplary embodiments now will be described more fully herein with reference to the accompanying drawings, in which exemplary embodiments are shown. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of this disclosure to those skilled in the art. In the description, details of well-known features and techniques may be omitted to avoid unnecessarily obscuring the presented embodiments.
[0019] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of this disclosure. As used herein, the singular forms “a”, “an”, and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Furthermore, the use of the terms “a”, “an”, etc., do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced items. It will be further understood that the terms “comprises” and/or “comprising”, or “includes” and/or “including”, when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
[0020] In addition it will be understood that when an element as a layer, region, or substrate is referred to as being “on” or “over”, or “disposed on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being “directly on”, “directly over”, or “disposed proximately to” another element, there are no intervening elements present. It will also be understood that when an element is referred to as being “connected” or “coupled” to another element, it can be directly connected or directly coupled to the other element, or intervening elements may be present. In contrast, when an element is referred to as being “directly connected” or “directly coupled” to another element, there are no intervening elements present.
[0021] Embodiments of the present invention provides a semiconductor integrated circuit interconnect structure (interconnect structure) that minimizes electromigration, which thereby can minimize void formation and extrusion/hillock formation. Minimizing electromigration can improve integrated circuit performance, enhance reliability of interconnect structures, minimize sudden data loss, and enhance the useful lifetime of semiconductor integrated circuit products.
[0022] FIG. 1 illustrates a cross-sectional view of semiconductor 100 comprising a substrate 102 , transistor area layer 104 , first dielectric layer 106 , first metal layer 108 , second dielectric layer 110 , and openings in the second dielectric layer 110 for trench areas 112 - 114 and via hole 116 . Specifically, dielectric layer 106 is formed on transistor area layer 104 , wherein transistor area layer 104 is formed on substrate 102 . Subsequent to a chemical-mechanical planarization (CMP) process of the first dielectric layer 106 with first metal layer 108 , a second dielectric layer 110 is formed over first metal layer 108 and first dielectric layer 106 . Moreover, trench areas 112 - 114 and a via hole 116 are formed in second dielectric layer 110 . Specifically, via hole 116 is formed in trench area 113 . Consequently, a dual damascene structure, which includes trench areas 112 - 114 and a via hole 116 , is formed.
[0023] FIG. 2 is a top view of an array of trench areas and via holes. Specifically, FIG. 2 depicts an array of trench areas 215 - 218 and via holes 206 - 211 . A trench may not have any via holes such as trench area 215 . However, trench areas can have one or more via holes such as depicted in trench areas 216 - 218 . Moreover, via holes can be distributed uniformly in a trench area as illustrated in trench area 216 , wherein in via hole 206 is formed symmetrically opposite to via hole 207 , in trench area 216 . Alternatively, via holes can be distributed non-uniformly in a trench area as illustrated in trench areas 217 - 218 . Lastly, there are one or more via holes at each level of semiconductor interconnects in order for all levels of the semiconductor interconnects to be electrically connected.
[0024] FIG. 3A depicts a cross-sectional view of substrate 102 , transistor area layer 104 , first dielectric layer 106 , first metal layer 108 , second dielectric layer 110 , trench areas 112 - 114 , via hole 116 (shown in FIG. 1 ), barrier metal layer 302 , first copper seed layer 306 , second seed layer 307 , and second copper seed layer 308 .
[0025] Specifically, the barrier metal layer 302 is disposed on trench areas 112 - 114 . The barrier metal layer 302 prevents conducting material, such as copper, from diffusing into the dielectric layer 110 . A multi-layered seed layer is formed directly on barrier metal layer 302 . The multi-layered seed layer comprises a first copper seed layer 306 , a second seed layer 307 , and a second copper seed layer 308 . The first copper seed layer 308 is formed utilizing a sequential catalytic chemical vapor deposition (CVD) process. Utilizing the sequential catalytic CVD process allows for trench areas and via holes to be filed, and minimizes pinch-offs, void formation, and extrusion/hillock formation. Specifically, to form first copper seed layer 306 , copper(II) chloride and hydrogen gases are utilized in the sequential catalytic CVD process, wherein first copper seed layer 306 is disposed on barrier metal layer 302 .
[0026] Next, second seed layer 307 is disposed on first copper seed layer 306 utilizing the sequential catalytic CVD process. Specifically, to form the second seed layer 307 , hydrogen gas, ammonia gas, and carrier gas argon are utilized with manganese amidinate precursor. In the present embodiment manganese is utilized to form second seed layer 307 , but in alternative embodiments aluminum, tin, or titanium may be utilized to form second seed layer 307 . After the second seed layer 307 is formed, second copper seed layer 308 is formed utilizing the sequential catalytic CVD process, wherein the second copper seed layer 308 is disposed on second seed layer 307 . Accordingly, the multi-layered seed layer is formed.
[0027] FIG. 3B illustrates the formation of an electroplated copper layer 309 . Specifically, the electroplated copper layer 309 is disposed on the second copper seed layer 308 . As a result, unfilled trench areas 112 - 114 (shown in FIG. 3A ) and via hole 116 (shown in FIG. 1 ) are filled with copper, utilizing an electroplating technique. In addition, post plating anneal 320 occurs causing copper grain growth. However, the post plating anneal 320 does not result in much diffusion of the multi-layered seed layer.
[0028] FIG. 3C illustrates an end result of a chemical-mechanical planarization (CMP) process. The purpose of the CMP process is to remove a portion of layers 302 and 306 - 308 , which provides for the formation of a quality interconnect structure, and clears the way for forming a dielectric layer capping layer and/or a selective metal capping layer.
[0029] FIG. 3D illustrates the formation of a dielectric capping layer. In the present embodiment, dielectric capping layer 312 is formed after the CMP process illustrated in FIG. 3C . The dielectric capping process occurs at temperatures high enough (i.e., between about 350° C.-400° C.) to enhance copper grain growth of first copper seed layer 306 (shown in FIG. 3C ) and second copper seed layer 308 (shown in FIG. 3C ), and enhance diffusion of second seed layer 307 (shown in FIG. 3C ) with seed layer 306 , seed layer 308 , and with electroplated copper layer 309 (shown in FIG. 3C ). As a result, second seed layer 307 diffuses with first copper seed layer 306 , diffuses with second copper seed layer 308 , and diffuses with electroplated copper layer 309 , which causes layers 306 - 309 to merge, forming a single second metal layer 314 comprising a copper-manganese alloy. Furthermore, as a result of the diffusion process, triggered by the formation of dielectric capping layer 312 , a high concentration of manganese remains at the interface between dielectric capping layer 312 and second metal layer 314 . Accordingly, the high concentration of manganese forms a segregated manganese-containing layer 316 at the interfaces between dielectric capping layer 312 and second metal layer 314 . Additionally, a via hole opening can be created in dielectric capping layer 312 to provided connectivity to a subsequent metal layer. In alternative embodiments, a selective metal capping layer may be deposited over segregated manganese-containing layer 316 , wherein subsequently a dielectric capping layer 312 may be deposited over the selective metal capping layer, and wherein the capping process occurs at temperatures between about 350° C.-400° C.
[0030] FIG. 4 depicts a schematic cross-sectional view of a chemical deposition apparatus 400 comprising a catalytic chemical vapor deposition (CVD) processing chamber 418 and heatable tank 434 , adapted to deliver metal ions and precursor gases to a substrate, and adapted to form a multi-layered seed layer. Gas line 404 is utilized to deliver copper(II) chloride gas 402 into gas line 414 . The gas line 404 is connected to a mass flow controller 406 , and a gas line 414 . The copper(II) chloride gas 402 passes through gas line 404 , mass flow controller 406 , and then into the gas line 414 . The purpose of a mass flow controller is to control the rate of gas flow through a gas line. Gas line 410 is utilized to deliver hydrogen gas 408 into gas line 414 . The gas line 410 is connected to a mass flow controller 412 , and the gas line 414 . The hydrogen gas 408 passes through gas line 410 , mass flow controller 412 , and then into the gas line 414 . In one embodiment, a gas line 410 is utilized to deliver hydrogen gas 408 into gas line 414 , wherein gas line 404 is simultaneously utilized to deliver the copper(II) chloride gas 402 into gas line 414 .
[0031] Accordingly, gas lines 404 and 410 merge into one gas line 414 , wherein gas line 414 is connected to inlet 416 of catalytic CVD processing chamber 418 . Gas line 414 contains both copper(II) chloride gas 402 and hydrogen gas 408 , which are introduced into the inlet 416 of catalytic CVD processing chamber 418 . In one embodiment catalytic CVD processing chamber 418 comprises an inlet 416 , a heated metal wire 420 , a side inlet 454 , a heatable plate 426 , a wafer 424 , and a gas discharge outlet 458 for gases to exit by turbo molecular pumping 460 . In addition, a barrier metal layer 302 (shown in FIG. 3A ) is disposed on the surface of wafer 424 , wherein in the barrier metal layer 302 is deposited utilizing physical vapor deposition prior to entering catalytic CVD processing chamber 418 . However, the barrier metal layer 302 can be deposited in a separate chamber by utilizing other processes, which include atomic layer deposition (ALD).
[0032] After the copper(II) chloride gas 402 and hydrogen gas 408 pass through gas line 414 and are introduced into inlet 416 , the copper(II) chloride gas 402 and hydrogen gas 408 are then heated by metal wire 420 . Metal wire 420 comprises tungsten, but can be made of other useful materials which include ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, silver, mercury, rhenium, copper or a combination thereof. At the surface of heated metal wire 420 the copper(II) chloride gas 402 reacts with the hydrogen gas 408 , and the copper(II) chloride gas 402 decomposes into copper radicals 422 . The copper radicals 422 are then deposited directly on to the surface of the barrier metal layer 302 , to form first copper seed layer 306 (shown in FIG. 3A ). Although the wafer 424 is directly on heatable plate 426 , the plate is not very hot. Typically, CVD needs to occur at a high temperature, however in the present embodiment copper decomposition happens as a result of the heated metal wire 420 , which forms copper radicals 422 . Therefore, heatable plate 426 does not have to be heated to as a high temperature as other CVD processes may require. Specifically, the temperature of the heatable plate 426 may be between about 20° C.-150° C.
[0033] After first copper seed layer 306 is deposited on wafer 424 , the catalytic CVD processing chamber 418 is cleaned. Next, gas line 428 is utilized to deliver a carrier gas 426 into heatable tank 434 . In the present embodiment, the carrier gas argon 426 is utilized, but other gases may be used including nitrogen gas (N 2 ). Subsequently, gas line 428 delivers carrier gas argon 426 through a mass flow controller 430 , and through inlet 432 of heatable tank 434 , wherein the heatable tank 434 holds a manganese amidinate precursor 436 . Thus, the carrier gas 426 is delivered into the manganese amidinate precursor 436 . The manganese amidinate precursor 436 becomes liquid vaporized, which forms a vapor 438 . The vapor 438 is discharged through outlet 440 of heatable tank 434 , and introduced into gas line 444 . The vapor 438 includes manganese amidinate precursor 436 . Pressure gauge 442 is connected to gas line 444 , and can be utilized to determine how much manganese amidinate precursor is in vapor 438 . In the present embodiment, the manganese amidinate precursor 436 is utilized, but in alternative embodiments other liquid solutions may be utilized, which include carbonyl precursors.
[0034] Next, ammonia (NH 3 ) and hydrogen (H 2 ) gases 446 are introduced into gas line 448 . The ammonia and hydrogen gases 446 pass through a mass flow controller 450 . Gas line 448 merges with gas line 444 forming gas line 452 , wherein gas line 452 is connected to side inlet 454 of catalytic CVD processing chamber 418 . As a result, the vapor 438 flowing through gas line 444 merges with the ammonia and hydrogen gases 446 flowing through gas line 448 , wherein the combined vapor 438 and ammonia and hydrogen gases 446 then flow through gas line 452 . Gas line 452 delivers the combined vapor 438 and ammonia and hydrogen gases 446 into catalytic CVD processing chamber 418 , through side inlet 454 forming a stream of gas flow 456 . At the top surface of first copper seed layer 306 the combined vapor 438 and ammonia and hydrogen gases 446 cause the manganese amidinate precursor 436 in vapor 438 to decompose, wherein the manganese atoms of the manganese amidinate precursor 436 are separated from the nitrogen atoms of the manganese amidinate precursor 436 . Thus, the manganese atoms are deposited directly on the top surface of first copper seed layer 306 , forming a second seed layer 307 . The ammonia and hydrogen gases 446 and nitrogen atoms, wherein the nitrogen atoms were once bonded to the manganese, are evacuated from processing chamber 418 through the gas discharge outlet 458 by utilizing a turbo molecular pumping 460 . Accordingly, a second seed layer 307 (shown in FIG. 3C ) is disposed on the top surface of first copper seed layer 306 . In the present embodiment manganese is utilized to form precursor 436 and second seed layer 307 , but in alternative embodiments aluminum, tin, or titanium may be utilized to form precursor 436 and second seed layer 307 .
[0035] After second seed layer 307 is disposed on the top surface of first copper seed layer 306 , the catalytic CVD processing chamber 418 is cleaned. Next, copper(II) chloride gas 402 is introduced into gas line 404 , and hydrogen gas 408 is introduced into gas line 410 . The copper(II) chloride gas 402 passes through mass flow controller 406 and the hydrogen gas 408 passes through mass flow controller 412 .
[0036] Next, gas lines 404 and 410 merge into one gas line 414 , wherein gas line 414 is connected to inlet 416 of catalytic CVD processing chamber 418 . Thus, gas line 414 contains both copper(II) chloride gas 402 and hydrogen gas 408 , which are introduced into the inlet 416 of catalytic CVD processing chamber 418 . In one embodiment catalytic CVD processing chamber 418 comprises an inlet 416 , a heated metal wire 420 , a side inlet 454 , a heatable plate 426 , a wafer 424 , and a gas discharge outlet 458 for gases to exit by turbo molecular pumping 460 .
[0037] After the copper(II) chloride gas 402 and hydrogen gas 408 pass through gas line 414 and are introduced into inlet 416 , the copper(II) chloride gas 402 and hydrogen gas 408 are then heated by metal wire 420 . The metal wire 420 may be heated between about 1000° C.-1500° C. Metal wire 420 comprises tungsten. At the surface of heated metal wire 420 the copper(II) chloride gas 402 reacts with the hydrogen gas 408 , and the copper(II) chloride gas decomposes into copper radicals 422 . The copper radicals 422 are then deposited directly on the surface of the second seed layer 307 , to form second copper seed layer 308 (shown in FIG. 3A ). Although the wafer 424 is directly on heatable plate 426 , the plate is not very hot. Typically, CVD needs to occur at a high temperature, however in the present embodiment copper decomposition happens as a result of the heated metal wire 420 , which forms copper radicals 422 . Therefore, heatable plate 426 does not have to be heated to as a high temperature as other CVD processes may require. After forming of the second copper seed layer 308 , the formation of the multi-layered seed layer is completed. Next an electroplated copper layer is formed in a separate chamber. Subsequently, in the present embodiment, processes such as chemical-mechanical planarization and the formation of dielectric capping layer 312 (shown in FIG. 3D ) may be initiated. In alternative embodiments, a selective metal capping layer may be deposited over segregated manganese-containing layer 316 , wherein subsequently a dielectric capping layer 312 may be deposited over the selective metal capping layer, and wherein the capping process occurs at temperatures between about 350° C.-400° C.
[0038] Referring now to FIG. 5 , a method for forming a semiconductor integrated circuit interconnect structure with a multi-layered seed layer is depicted. In step 500 , source gases which include copper(II) chloride gas 402 (shown in FIG. 4 ) and hydrogen gas 408 (shown in FIG. 4 ) are provided. In step 502 , the source gases are released into a catalytic chemical vapor deposition chamber 418 (shown in FIG. 4 ), wherein the catalytic CVD processing chamber 418 includes a wafer directly on a heatable plate 426 (shown in FIG. 4 ). In step 504 , a metal wire 420 (shown in FIG. 4 ) is heated. Next, in step 506 the metal wire 420 that is sufficiently heated causes the copper(II) chloride gas 402 to react with the hydrogen gas 408 , at the surface of metal wire 420 , such that the copper(II) chloride gas 402 decomposes into copper radicals 422 (shown in FIG. 4 ). In step 507 , a determination is made as to whether a second seed layer 307 (shown in FIG. 3A ) has been formed. Since a second seed layer 307 has not been formed the process will proceed to step 508 . In step 508 , the copper radicals 422 are deposited directly on a barrier metal layer 302 (shown in FIG. 3A ), wherein in the barrier metal layer 302 is disposed on the surface of the wafer 424 (shown in FIG. 4 ), and wherein a first copper seed layer 306 (shown in FIG. 3A ) is formed. In step 510 , a determination is made as to whether a second copper seed layer has been formed. Since a second copper seed layer 308 (shown in FIG. 3A ) has not been formed the process will proceed to step 512 , wherein the catalytic CVD processing chamber 418 is cleaned in preparation for the next step in the formation of the multi-layered seed layer.
[0039] In step 514 , a carrier gas argon 426 (shown in FIG. 4 ), and ammonia and hydrogen gases 446 (shown in FIG. 4 ) are provided. In step 516 , the carrier gas argon 426 is released into a heatable tank 434 (shown in FIG. 4 ), wherein the heatable tank 434 contains manganese amidinate precursor 436 (shown in FIG. 4 ). In step 518 , a vapor 438 (shown in FIG. 4 ) is formed inside of heatable tank 434 , and the vapor 438 includes the manganese amidinate precursor 436 . In step 520 , the vapor 438 is discharged out of heatable tank 434 and combines with the ammonia and hydrogen gases 446 . In step 522 , the combined vapor 438 , and ammonia and hydrogen gases 446 are released into the catalytic chemical vapor deposition chamber 418 . In step 524 , the manganese amidinate precursor 436 is decomposed at the top surface of copper seed layer 306 . Specifically, in step 524 , at the top surface of copper seed layer 306 the combined vapor 438 and ammonia and hydrogen gases 446 cause the manganese amidinate precursor 436 to decompose, wherein the manganese atoms of the manganese amidinate precursor 436 are separated from the nitrogen atoms of the manganese amidinate precursor 436 . Thus, the manganese atoms are deposited directly on the top surface of first copper seed layer 306 , forming a second seed layer 307 . Next, in step 526 , nitrogen, and ammonia and hydrogen gases 446 are evacuated from the catalytic CVD processing chamber 418 by utilizing turbo molecular pumping 460 . In step 528 , the catalytic CVD processing chamber 418 is cleaned. In the present embodiment manganese is utilized to form the precursor 436 and the second seed layer 307 , but in alternative embodiments aluminum, tin, or titanium may be utilized to form the precursor 436 and the second seed layer 307 .
[0040] In step 528 , after the catalytic CVD processing chamber 418 is cleaned, the method of forming a semiconductor integrated circuit interconnect structure with a multi-layered seed layer proceeds back to step 500 . In step 500 , source gases which include copper(II) chloride gas 402 and hydrogen gas 408 are provided. In step 502 , the source gases are released into a catalytic chemical vapor deposition chamber 418 , wherein the catalytic CVD processing chamber 418 includes a wafer directly on a heatable plate 426 . In step 504 , a metal wire 420 is heated. Next, in step 506 the metal wire 420 that is sufficiently heated causes the copper(II) chloride gas 402 to react with the hydrogen gas 408 , at the surface of metal wire 420 , such that the copper(II) chloride gas 402 decomposes into copper radicals 422 . In step 507 , a determination is made as to whether a second seed layer 307 has been formed. Since a second seed layer 307 has been formed the process will proceed to step 509 . In step 509 , the copper radicals 422 are deposited directly on the second seed layer 307 , wherein a second copper seed layer 308 (shown in FIG. 3A ) is formed. In step 510 , a determination is made as to whether a second copper seed layer has been formed. Since the second copper seed layer 308 has been formed the process will end at step 530 , wherein the formation of the multi-layered seed layer is completed.
[0041] The method flow diagram depicted in FIG. 5 illustrates a method for forming a multi-layered seed layer of a semiconductor integrated circuit interconnect structure, according to various embodiments of the present invention. It should also be noted that, in some alternative implementations, the process steps noted in the blocks may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be performed substantially concurrently, or the blocks may sometimes be performed in the reverse order, depending upon the process involved. It will also be noted that each block of the block diagram and/or flowchart illustration, and combinations of blocks in the block diagram and/or flowchart illustration, can be implemented by special purpose hardware-based systems that perform the specified processes or acts, or combinations of special purpose hardware and computer instructions.
[0042] Furthermore, those skilled in the art will note from the above description, that presented herein is a novel apparatus and method for forming a multi-layered seed layer to minimize electromigration, utilizing sequential catalytic chemical vapor deposition. Lastly, the foregoing description of various aspects 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, obviously, many modifications and variations are possible. Such modifications and variations that may be apparent to a person skilled in the art are intended to be included within the scope of the invention as defined by the accompanying claims.
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An interconnect structure and method for forming a multi-layered seed layer for semiconductor interconnections are disclosed. Specifically, the method and structure involves utilizing sequential catalytic chemical vapor deposition, which is followed by annealing, to form the multi-layered seed layer of an interconnect structure. The multi-layered seed layer will improve electromigration resistance, decrease void formation, and enhance reliability of ultra-large-scale integration (ULSI) chips.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Phase Application of International Application No. PCT/EP2007/060158, filed on Sep. 25, 2007, which claims the benefit of and priority to European patent application no. EP 06 121 267.6, filed on Sep. 26, 2006. The disclosures of the above applications are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] The invention relates to a method of producing a piston for internal combustion engines from two pre-fabricated parts which, having been pre-fabricated, are connected together to form the piston. As well as this, the invention also relates to a piston which is produced in a corresponding manner from two parts.
BACKGROUND
[0003] Pistons for internal combustion engines are usually produced by casting or forging processes. Production by casting has the advantage that it allows pistons of complex shape and low weight to be produced. However, what has to be accepted at the same time is that the production involves considerable cost and complication. This is particularly true when a steel material is to be used as the material for producing pistons able to withstand especially high stresses.
[0004] Depending on their size and intended purpose, forged steel pistons may both be of a one-piece form and may also be composed of two or more parts. In the case of multi-piece pistons assembled from two or more parts, the individual parts are usually connected together, by suitable joining processes, by friction, bonding, or positive fit in such a way that they will withstand the forces acting on them in practical use. What is suitable for this purpose is for example welding or screwing together of the separate parts of the piston.
[0005] An example of a multi-piece piston for an internal combustion engine is known from DE 102 44 513 A1. This piston has, on the one hand, a head part which is forged from steel and integrally formed in which are formed dishing for the combustion chamber, an annular wall and a cooling passage in the form of a groove. On the other hand the piston has a skirt part which carries the head part of the piston and in which are formed bosses to receive a piston pin which connects the piston to the connecting rod. To produce this piston, the head part and skirt part of the piston are pre-shaped by forging in separate operations and are then machined by stock-removing machining to finish them. The finish machining of the head part of the piston also includes in this case the stock-removing machining of the portions of wall adjoining the cooling passage, by means of which portions of wall a joint is then made to the skirt part of the piston by physical union by welding or brazing.
[0006] It is true that multi-piece construction of this kind allows the piston which is formed from the two parts to be made of a complex shape. However, apart from the problems relating to load-bearing capacity which arise from its multi-piece nature, the cost and complication its production involves are considerable.
[0007] Disadvantages of the production of one-piece pistons are the high weight of the blank for the piston, as a result of which processing and handling equipment of particularly large dimensions is required, and the expense involved in the mechanical post-processing which is inevitably required in present-day practice. Despite the advantages that one-piece pistons have, as far as their load-bearing capacity is concerned, the disadvantages mentioned mean that when production is conventional one-piece pistons can only be produced at increased production costs.
[0008] One possible way of connecting together, by forging, a piston formed from two previously manufactured parts is known from JP 03-267552 A. In this piece of prior art, a piston-skirt blank whose basic shape is that of a cylinder is produced by sintering a metal powder. A projection which is of a circular disc-like shape is produced on the end-face of the piston-skirt blank when this is done.
[0009] In addition to the skirt part of the piston, what is also produced by the known method is a head part of the piston which is likewise of a disc-like basic shape. The diameter of the skirt part of the piston corresponds to the diameter of the head part of the piston in this case. Formed in the end-face of the head part of the piston is a recess whose opening is so defined by an encircling portion which projects into the recess that an undercut is formed between the said portion and the floor area of the recess. To allow the skirt part and head part of the piston to be joined together, the head part of the piston is first placed in a die whose inside diameter corresponds to the outside diameter of the skirt part and head part of the piston. The recess in the head part of the piston faces towards the opening of the die while the said head part of the piston is supported at its other end-face by means of a punch. The piston-skirt blank is then introduced into the die until its projection is seated in the recess in the head part of the piston. The head part of the piston then has a forging force applied to it by means of a shaping punch, which force causes the material of the skirt part of the piston to flow into the recess in the head part of the piston and to fill the undercut which is formed in the latter. The skirt part of the piston is given its cup-like final configuration at the same time.
[0010] The piston which is produced by the method from JP 03-267552 A is of an outside shape which is, in essence, completely cylindrical. Formed in the circumferential surface of the skirt part of the piston in this case, closely adjacent to the head part of the piston which is carried by the skirt part of the piston, are grooves for piston rings. Neither the skirt part of the piston nor the head part of the piston have, in this case, any additional configurational features which would make them suitable for a modern-day internal combustion engine. In particular, the known piston does not have any special shaping of the head part of the piston of the kind which is nowadays required if optimum use is to be made of the energy from the fuel which is burnt in the given internal combustion engine. It is also found that simple designs of piston of the kind described in JP 03-267552 A are not equal to the thermal demands which arise in modern-day internal combustion engines.
[0011] Comparable possible ways of producing pistons from two parts by means of a positive fit between the parts produced by forging are known from DE 725 761 C, JP 54-021945 A, GB 2 080 485 A or U.S. Pat. No. 3,075,817 A1. However, what all these pieces of prior art have in common is that the pistons which are assembled in a known manner from two parts are each of a simple shape which no longer meets the modern-day demands that are made of pistons for internal combustion engines.
SUMMARY OF THE INVENTION
[0012] Against the background of the prior art explained above, an aspect underlying the invention is therefore to provide a method which makes possible the inexpensive production even of pistons of complex shape for internal combustion engines. Another aspect is also to specify a piston for internal combustion engines which can be produced inexpensively with great accuracy of manufacture despite its being of complex shape.
[0013] In accordance with the invention, the connection between the two parts of the piston is made by means of a mechanical connection in which the material of the projection on one part is clamped by the material surrounding the recess in the other part in such a way that the two parts are indissolubly connected together. For this purpose, there is formed in the region of the recess in one part an undercut which, on the two parts being compressed, is filled by the material of the projection which flows into it. There is formed in this way a mechanical locking system which operates in essence by positive inter-engagement and which ensures that the two parts of the piston produced in accordance with the invention are held solidly together in a durable way. A major advantage of the invention lies in this case in the fact that the individual parts from which the piston is assembled, which are composed of a steel material for example, can be preformed in a completely finished form and the connection between the parts can be made without any additional connecting members such as screws or bolts. The mechanical connection which is provided in accordance with the invention, which is made by material of the two parts interlocking by positive fit, makes it possible in this case for the at least two individual parts from which a piston according to the invention is assembled to be accurately pre-shaped. When they are put together to form the piston, they are therefore of a minimized weight, which means that only low forces have to be applied to handle the workpieces. What is more, due to the joining process according to the invention, there is no change in the basic shape of the piston and a consequence of this is that, at least as a rule, only a very much reduced amount of mechanical post-processing of the fully joined piston is utilized.
[0014] Something which proves to be particularly advantageous in this connection is that the way in which the two parts of the piston are connected in accordance with the invention makes it possible for the piston to be produced by hot-forging operations alone. In this way, as well as the two parts of the piston being pre-fabricated by hot forging, the undercut which is formed in one part may also be produced by hot-forging steps.
[0015] For this purpose, a projection is first formed on the first part by means of a shaping tool, which projection is directed substantially in the opposite direction from that in which the tool acts. A lateral force which is directed in the direction of the receptacle is then applied to this projection to form the undercut. When the undercut is produced in such a way in two stages, a projection which has no undercut and from which the forging tool can be separated again by a simple lifting movement is first formed on the first part by means of a suitable tool. Then, by the lateral application of force, the projection is sloped in the direction of the receptacle of the first part in such a way that the projection makes an angle of less than 90° between its free end and the bottom of the receptacle. Any additional stock-removing machining to make the undercut can be avoided in this way.
[0016] What is more, with the manner of production in accordance with the invention there is no longer any need for the parts of the pistons to be heated to their melting point locally. With a piston according to the invention there is likewise no longer any risk of changes in microstructure or of stresses arising in the piston which such heating involves.
[0017] Another significant aspect of the invention is that the at least two parts are connected together by a simple operation comparable to a forging step. The apparatus required for this purpose can be designed to be simple and hence inexpensive because a special die or comparable aids which determine the flow of the material and prevent the components from deforming are not required in the region of the connecting zone and instead the desired filling of the recess in one part of the piston by the material of the projection on the other part of the piston is ensured by the fact that the projection is plugged into the recess in the other part and the flow of material which then occurs when pressure is applied is determined by the shape of the recess itself.
[0018] The outcome is that the invention thus makes available a method which, in a simple and inexpensive way, makes it possible for pistons for internal combustion engines to be produced which are very accurately shaped and, at the same time, able to carry high stresses. Their configuration is selected in such a way in this case that they can be joined together from two parts with simple means without the need for expensive and complicated apparatus or excessively high forces. An embodiment of the invention which is particularly right for practical requirements is characterized in that the recess and the projection are formed at respective end-faces of the parts respectively associated with them. In this embodiment, all that is required to cause the desired flow of material is a compressive force acting in the direction of the longitudinal axis of the piston which is to be produced. At the same time, what is ensured in the case of this arrangement is a connection which is optimum with regard to the stresses which occur in practical use.
[0019] A particularly simple form for the parts of the piston and a variant of the method according to the invention which can be carried out in an equally simple way are obtained when one part forms the head of the piston to be produced and the other part forms the skirt thereof.
[0020] Basically, it is immaterial to the success of the invention which of the parts the projection and recess are respectively associated with. In this way, in cases where one part forms the piston skirt to which the given connecting rod is coupled in practical use and which guides the piston in the bore of the cylinder and where the other part forms the piston head in whose end-face remote from the piston skirt a dishing for the combustion chamber is usually formed, it is possible for the projection to be formed on the head part of the piston and the recess to be formed in the skirt part thereof. However, from the production point of view it has proved to be particularly practical for the projection to be associated with the skirt part of the piston and the recess with the head part thereof.
[0021] Something which also makes a contribution to simplifying that part of the piston which is provided with the recess in the course of previous manufacture is for the recess concerned to have a circular opening.
[0022] The undercut which is provided in accordance with the invention in the region of the recess can easily be produced by making the opening of the recess an area which is smaller than the projected floor area of the recess, which projected floor area is situated opposite the opening. With sizing of this kind, the area of the opening is always smaller than the floor area when the latter is projected into the plane of the area of the opening. What this means is that, when the floor area is seen in plan, at least a portion or portions of the edge of the opening are arranged to be offset from the edge of the floor area towards the center of the floor area, which means that an undercut is necessarily formed at the portions in question as the edge of the opening changes to the edge of the floor area. The undercut may be formed in this case by, starting from the floor area of the recess, aligning at least a portion or portions of the circumferential surface surrounding the recess to be inclined towards the area of the opening.
[0023] Basically, it is conceivable for the parts which together form the piston to be connected together by cold forming. However, a considerable simplification of the complication which this kind of forming involves can be achieved by, when force is applied to make the positive fit connection between the first and second parts, heating the part which is provided with the projection to forging temperature at least in the region of the projection. When this is the case, the first, cold, part acts, by means of its receptacle, as a die for the forming of the projection on the second part, which projection is inserted into the receptacle and is at forging temperature, which means that there is an assurance of even and complete filling of the undercut region of the receptacle by the material of the projection in the course of the deformation of the projection which occurs as a result of force being applied.
[0024] The support which one part of the fully assembled and joined piston has on its other part may be boosted by forming a shoulder at the transition from the projection to the main portion of the part associated with the projection. The other part is able to support itself on this shoulder at least by the wall which defines its recess.
[0025] Something that has proved particularly apt for practical requirements is an embodiment of the invention in which at least a portion or portions of the recess are defined by a freely projected collar portion. This collar portion on the one hand forms the shaping element by which the undercut which is filled with the material of the projection on the other part is formed in the region of the recess. On the other hand, the flow of material which occurs in the course of the application of pressure can be steered in such a way that the collar portion ensures that the two parts are clamped together reliably, securely and durably by engaging comparatively deeply into the material of the part of the piston which is provided with the projection and by virtue of the fact that the material of the part provided with the projection surrounds at least a portion or portions of the collar portion.
[0026] The security with which the two parts of the piston according to the invention are held together even under the heating-up which occurs in operation can be optimized, while at the same time not changing the simple assembly process, by making the volume of the projection on one part of a size such that, taking into account the thermal expansion of the two parts, the material of the projection completely fills the recess in the other part even in the cooled-down state. For this purpose the shape of the circumference of the projection on one part may be matched to the shape of the opening of the recess in the other part in such a way that the projection is able to be slid into the opening when it is in the state where it is heated to hot-forging temperature, and in such a way that the height of the projection is greater than the depth of the recess.
[0027] A significant advantage of the invention lies in the fact that the manner in accordance with the invention of producing a piston allows the respective materials which are selected for the two parts from which the piston is assembled to be ones which are optimally matched to the stresses which act on the respective parts in operation. In this way, the invention makes it possible, when selecting the respective materials, for allowance to be made not only for the respective mechanical stresses but also for stresses which arise as a result of, for example, thermal or chemical effects to which a piston according to the invention is exposed in practical use.
[0028] It is therefore proposed in a particularly advantageous embodiment of the invention that one part of a piston according to the invention be manufactured from a first material and that the other part be manufactured from a second material which is different from the first material. As a function of the particular area of use, the first part for example may therefore be previously manufactured from steel of a first grade and the second part from steel of a second grade, or the first part from a grade of steel and the second part from another metallic material and in particular a light metal, or the first part from a ceramic and the second part from a metallic material. As well as hot forging being used as a method of previous manufacture for forgeable materials, previous manufacture by sintering may also be used in accordance with the invention at least for the head part of the piston. The starting material for the head part of the piston is then powdered metal for sintering.
[0029] The invention also allows the individual parts from which a piston is assembled in the manner according to the invention to be differently heat-treated or differently treated in some other way to allow for the stresses which act on the respective parts in practice.
[0030] The production and configuring in accordance with the invention of a piston for internal combustion engines thus provides a wide range of possible means of optimization which allow pistons of this kind each to be matched to their respective intended uses in the optimum way.
[0031] The piston according to the invention is so designed that, while being able to be produced easily, it meets the demands made of modern-day pistons. In this way, it is assembled from two parts produced by hot forging which are connected together by positive fit. At the same time however, in the region of the transition between the head of the piston and the skirt of the piston, an encircling free space which is known per se by means of which the heat which arises in practical use is dissipated in terms of a cooling passage. To achieve this, there is formed, in accordance with the invention, on one part a receptacle which is surrounded by a circumferential wall and, in this receptacle, a recess which is surrounded by an encircling collar portion which is aligned to be inclined at an angle to the longitudinal axis of the piston in such a way that at least one undercut is formed which is substantially completely filled in order to bring about the positive inter-engagement of material of a projection which is formed on the other part, the said free space being left between the outer circumferential surface of the collar portion and the inner circumferential surface of the circumferential wall.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] The invention is explained in detail below by reference to drawings which show an embodiment. In the drawings, which are each schematic longitudinal sections:
[0033] FIG. 1 shows a piston assembled from two parts.
[0034] FIG. 2 shows the parts from which the piston shown in FIG. 1 is assembled.
[0035] FIG. 3 and FIG. 4 show two of the operating steps which are performed when the first part of the piston is being produced.
DESCRIPTION
[0036] The piston 1 is assembled from a first, head part 2 of the piston which forms its head and a second, skirt part 3 of the piston which forms its skirt, which parts are connected together by positive fit and friction in the region of a joint zone 4 which is formed between the head part 2 of the piston and the skirt part 3 thereof. The head part 2 of the piston, the skirt part 3 of the piston and also the connection by friction and positive fit between the said two parts 2 , 3 are produced in this case by hot-forging operations.
[0037] The head part 2 of the piston is produced from a steel blank by hot forging and is of a disc-like basic shape. Formed in that end-face 5 of the head part 2 of the piston which is associated in practical use with a combustion chamber (not shown) in an engine block (not shown likewise) is a dishing 6 for the combustion chamber. Following on from the end-face 5 there is a circumferential wall 7 which points in the direction of the skirt part 3 of the piston and which surrounds a receptacle 9 which is formed in that end-face 8 of the head part 2 of the piston which is associated with the skirt part 3 of the piston. The area at the bottom of the receptacle 9 is situated opposite the skirt part 3 of the piston and formed in it is a recess 10 .
[0038] To produce the head part 2 of the piston, a preform (not shown) is first produced by simple upsetting from a steel blank (not shown likewise) which is heated to a forging temperature of approximately 1050° C., from which preform a piston-head blank 2 a whose basic shape already corresponds to that of the head part 2 of the piston is then produced by means of a forging tool (also not shown). The recess 10 , in its rough shape, has already been formed in this case in the piston-head blank 2 a by means of the forging tool. At the same time, a non-undercut projection 12 a has been formed on the piston-head blank 2 a by the forging tool, which projection 12 a surrounds the recess 10 in an annular form and is aligned in the opposite direction to that direction R in which the forging tool (not shown) acts. In the case of the piston-head blank 2 a , the face of the inner wall of the recess 10 surrounded by the projection 12 a is thus substantially cylindrical.
[0039] The calibration of the piston-head blank 2 a then takes place in a further forging operating step. For this purpose, the piston-head blank 2 a is placed in a two-piece calibrating tool K whose bottom part K 1 associated with the end-face 5 of the piston-head blank 2 a copies the finished shape of the dishing 6 for the combustion chamber in the head part 2 of the piston. The top part K 2 of the calibrating tool K has, by contrast, on its side associated with the bottom part K 1 of the tool, a projection V which extends round in an annular shape and which is carried by a plate E.
[0040] This projection V is so arranged that, when a piston-head blank 2 a is lying on the bottom part K 1 of the tool by its end-face 5 , the said projection V points into the annular gap S which is present between the projection 12 a and the circumferential wall 7 of the piston-head blank 2 a . Starting from the free end of the projection V, the inner circumferential surface U thereof makes an obtuse angle β of 115-120° with the underside of the plate E which carries the projection V, and the projection V is thus thicker in cross-section in the region of its root which adjoins the plate E than in the region of its free tip. At the same time, the outer circumferential surface of the projection V extends parallel to the inner surface of the circumferential wall 7 .
[0041] When the calibrating tool K 2 is lowered, the projection V engages in the annular gap S and its inner circumferential surface U impacts on the projection 12 a on the piston-head blank 2 a . In this way, a lateral force Q directed into the recess 10 is exerted on the projection 12 a and the material of the projection 12 a is displaced by this lateral force Q towards the recess 10 .
[0042] As soon as the calibrating tool K 2 has reached its lowest position, at which the tip of its projection V is seated against the bottom of the annular gap S, the projection 12 a on the piston-head blank 2 a has been shaped into the collar portion 12 , which is now arranged in a position where it is inclined at an angle α of approximately 25-30° to the longitudinal axis L of the head part 2 of the piston.
[0043] In this way, the circular opening 11 of the recess 10 is surrounded by the encircling collar portion 12 which projects freely into the receptacle 9 and which, starting from the likewise circular floor area 13 of the recess 10 , is aligned towards the longitudinal axis L of the head part 2 of the piston. In this way, the floor area 13 is larger than the area occupied by the opening 11 . At the same time, an undercut 14 is formed in the region of the angle α which is made between the floor area 13 and the collar portion 12 which is arranged to be inclined, which undercut 14 cannot be obtained by a movement which only takes place parallel to the longitudinal axis L.
[0044] The skirt part 3 of the piston is likewise produced from a cylindrical steel blank by a plurality of hot-forging operations. For this purpose, the blank (not shown) was placed in the die of a forging apparatus (not shown likewise) in which, starting from one end-face of the blank and by means of a punch, a recess 15 in the skirt part 3 of the piston was then formed in a first forging step, which recess 15 is at the rear relative to the head part 2 of the piston in the fully assembled state. At the same time, a cylindrical projection 16 and a shoulder 17 which follows on without a step from projection 16 and encircles it were formed in the region of the other end-face of the blank, the shapes of which cylindrical projection 16 and shoulder 17 were preset by the die of the forging apparatus. The blank which had been pre-contoured in this way was then fully shaped in a second forging step. Apart from minor differences, the geometrical dimensions of the skirt part 3 of the piston which is obtained in this way correspond to the final size which is required and there are thus only small amounts of mechanical post-processing which have to be carried out (near net shape production).
[0045] On the skirt part 3 of the piston which is brought to a finished state in this way, the projection 16 which merges into the main portion 18 of the skirt part 3 of the piston without a step via the shoulder 17 is formed on the end-face situated opposite the recess 10 . The main portion 18 comprises in essence an encircling wall in which are formed, amongst other things, the mounting openings (not visible here) for a connecting rod of the internal combustion engine for which the piston 1 is intended. Except that it is undersized, the diameter D of the projection 16 corresponds in this case to the diameter of the opening 11 of the recess 10 in the head part 2 of the piston, thus enabling the projection 16 to be introduced into the recess 10 in the head part 2 of the piston with a small amount of clearance. The transition from the projection 16 to the end-face 19 is formed to be continuous and free of any steps, i.e. is formed not to have a right-angled shoulder. This configuration makes it easier for the projection 16 to be introduced into the recess 10 .
[0046] To simplify the introduction of the projection 16 to an additional degree and at the same time to make it possible for the head part 2 of the piston and the skirt part 3 thereof to be aligned with particular accuracy, the projection 16 may be formed to taper slightly, starting from the shoulder 17 , in the direction of its free end-face 19 .
[0047] The height H of the projection 16 is larger in this case than the depth T of the recess 10 . This being so, the dimensions of the projection 16 on the skirt part 3 of the piston are thus matched, overall, to the dimensions of the recess 10 in the head part 2 of the piston, while allowing for a proportion Vk by which the volume of the projection 16 shrinks as it cools down after the skirt part 3 of the piston has been connected to the head part 2 thereof. Where the skirt part 3 and head part 2 of the piston are produced from steel and where that volume of the recess 10 which is to be filled by the material of the projection 16 is V 1 , this extra volume Vk works out as Vk=V 1 ×0.014.
[0048] To ensure that there is a connection between the parts 2 and 3 which is lastingly solid under all conditions of temperature, the volume V 2 of the projection 16 is therefore V 2 =V 1 +Vk, the additional volume Vk being formed particularly in the region of the projection 16 , which projection 16 is associated with the collar portion 12 of the head part 2 of the piston after the joining of the skirt part 3 and head part 2 of the piston
[0049] To connect the head part 2 of the piston to its skirt part 3 , the skirt part 3 of the piston is first heated to a forging temperature of approximately 1050° C. while the head part 2 of the piston remains at room temperature.
[0050] The two parts 2 , 3 are then positioned in suitably shaped receptacles in a compressing apparatus (not shown) in such a way that their longitudinal axes L are in line with one another and the projection 16 on the skirt part 3 of the piston and the recess 10 in the head part 2 of the piston are facing towards one another. The parts 2 , 3 are then moved towards one another until the free end-face 19 butts against the floor area 13 of the recess 10 . A compressive force P acting in the direction of the longitudinal axis L is then exerted on the head part 2 of the piston and/or on the skirt part 3 thereof. This force is sufficiently large for the material M of the projection 16 on the skirt part 3 of the piston, which has been heated to forging temperature, to flow into the space in the recess 10 which had, up till then, been free in the region of the undercut 14 .
[0051] The compressing process is continued until the free edge of the collar portion 12 is seated in the hollow 20 at which the projection 16 merges into the adjoining shoulder 17 on the skirt part 3 of the piston. In this state, the steel material of the projection 16 completely fills the recess 10 including the undercut 14 . The head part 2 of the piston is now connected to the skirt part 3 by positive fit by the material of the projection 16 which fits behind the collar portion 12 .
[0052] The overfilling of the recess 10 which occurs as a result of the additional volume Vk of the projection 16 is compensated for by elastic deformation of the collar portion 12 . The collar portion 12 , having been deformed in this way, moves back towards its original shape as it cools down and the positive inter-engagement which is created by the filling of the recess 10 is thus supplemented by a frictional engagement which is caused by the interlocking and elastic return of the material of the projection 16 and of the collar portion 12 , which latter is not, or not fully, deformed plastically.
[0053] Because the edge region of the collar portion 12 penetrates slightly into the material of the skirt part 3 of the piston, the head part 2 of the piston is, at the same time, supported on the shoulder 17 by means of the collar portion 12 in such a way that, even when the stresses in the region of the dishing 6 for the combustion chamber are adversely distributed, it is ensured that forces will be evenly transmitted from the head part 2 of the piston to the skirt part 3 thereof.
[0054] Between the outer circumferential surface of the collar portion 12 and the inner circumferential surface of the circumferential wall 7 there is left, in this case, an encircling free space 21 of a channel-like form which is available in practical use to dissipate the heat from the head part 2 of the piston, particularly in the region of the highly stressed circumferential wall 7 .
[0055] For the head part 2 of the piston to be connected to its skirt part 3 , it is, basically, possible for both parts to be heated to hot-forging temperature. It is however enough for only the skirt part 3 of the piston, or even only the projection 16 on the skirt part 3 of the piston, to be heated to hot-forging temperature while no deliberate increase is made in the temperature of the head part 2 of the piston. Regardless of whether the projection 16 is heated on its own or together with the entire skirt part 3 of the piston, the recess 10 in the head part of the piston acts in this case as a forming die for the reshaping of the projection 16 on the skirt part 3 of the piston which is required to connect the skirt part 3 and head part 2 of the piston together. The head part 2 of the piston can then be left in the bottom part K 1 of the tool in this reshaping step. In this way, the bottom part K 1 of the tool can be used not only to calibrate the blank 2 a of the head part 2 of the piston but also as a tool for connecting the head part 2 of the piston to its skirt part 3 . The tooling costs can be reduced in this way and there is also no need for the forging tool to be changed between the individual operations, which, all in all, has a beneficial effect on the costs of production.
REFERENCE NUMERALS
[0000]
1 Piston
2 Head part of piston
2 a Piston-head blank
3 Skirt part of piston
4 Joint zone
5 End-face of the head part 2 of the piston and of the piston-head blank 2 a
6 Dishing for combustion chamber
7 Circumferential wall of the head part 2 of the piston and of the piston-head blank 2 a
8 Second end-face of the head part 2 of the piston
9 Receptacle in the head part 2 of the piston
10 Recess
11 Opening of the recess 10
12 Collar portion
12 a Projection of the piston-head blank 2 a
13 Floor area of the recess 10
14 Undercut
15 Recess at rear of the skirt part 3 of the piston
16 Projection
17 Shoulder
18 Main portion of the skirt part 3 of the piston
19 End-face of the projection 16
20 Groove at the transition from the projection 16 to the shoulder 17
21 Free space
α, β Angles
D Diameter of the projection 16
E Plate
H Height of the projection 16
K 1 Bottom part of calibrating tool K
K 2 Top part of calibrating tool K
K Calibrating tool
L Longitudinal axis of the piston 1 and of the parts 2 , 3
M Material of the projection 16
P Compressive force
R Direction in which the forging tool acts
T Depth of the recess 10
V Projection on part K 1 of the tool
S Annular gap
U Inner circumferential surface of the projection V
Q Force
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A method for producing a piston for internal combustion engines includes the following steps: a first part is pre-fabricated by hot forging and a recess which has an undercut is formed in the first part during pre-fabrication by forming on the first part a projection, to which projection a lateral force is applied to form the undercut; a second part is pre-fabricated by hot forging and a projection is formed on this second part whose dimensions are matched to the dimensions of the recess; the two parts are joined together so that the projection on one part engages in the recess in the other part; and a compressive force is applied to the two parts which is sufficiently large and so aligned that the material of the projection on one part flows into the recess in the other part and completely fills it to connect the parts by positive fit.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to and claims priority from earlier filed U.S. Provisional Patent Application No. 60/694,732, Jun. 28, 2005, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates generally to a flashlight that is configured in a manner that includes an integrated mounting interface. More specifically, the present invention relates to a compact, high intensity flashlight assembly that is highly durable and includes an integrated mounting interface, thereby making the flashlight capable of being utilized as an accessory for a variety of devices such as standard military style rail type mount for example.
In the prior art, flashlights for use in military applications have typically been constructed in a standard fashion utilizing a tubular outer housing. As a consequence, in order to facilitate mounting of the flashlight onto other devices, such as military weapons, a relatively large mounting assembly was required. Usually, the prior art mounting assembly that is used in connection with a flashlight having conventional construction includes a heavy gauge band that is wrapped around the entire outer housing of the flashlight. In addition, these bands include projections from at least one side where a large thumbscrew is positioned to allow a user to tighten the band around the flashlight. The difficulty encountered with this construction is that in some cases it creates a greater opportunity for the flashlight and mounting assembly to be caught on clothing or brush while the firearm is being carried, thereby knocking the flashlight out of alignment, dislodging the flashlight from the firearm or damaging the flashlight. Further, the interface between the outer tubular housing and the mounting band leaves the potential that the flashlight may slide or rotate within the band requiring frequent repositioning. While this may be acceptable for a sport type firearm, it is not acceptable for a firearm employed for field use, such as hunting or combat environments where immediate, fully aligned use of the flashlight assembly is required.
A further drawback associated with the prior art style flashlight mounts is that they do not provide a modular integrated mounting platform that allows the flashlight to be incorporated into a military weapons system. In other words, the prior art systems do not allow quick removal and reattachment of a flashlight with respect to a military firearm system. Additionally, the prior art systems do not include a modular arrangement that in turn allows integration of the flashlight into other environments such as integration for use as a helmet mounted light.
In view of the foregoing disadvantages inherent in the prior art devices, there is a need for a assembly that provides an improved method of compactly and reliably mounting a flashlight onto a firearm. There is a further need for an interfaceable flashlight assembly that provides an improved engagement method for firearms that has the ability to consistently and quickly engage, and provide accurate alignment, while providing a reduced profile, thereby reducing potential interference with other devices and attachments. There is still a further need for an interfaceable flashlight system that is modular in nature allowing for the flashlight to be easily utilized with a variety if different equipment.
BRIEF SUMMARY OF THE INVENTION
In this regard, the present invention provides for a novel modular flashlight assembly that includes an interface integrated into the housing thereof to facilitate mounting of the flashlight to a variety of different equipment. Generally, the flashlight includes at least a pair of engagement surfaces formed on the housing thereof, which are engaged by an interface clamp that in turn facilitates mounting of the flashlight to the desired device. In the preferred embodiment, the engagement surfaces are formed as a pattern of alternating raised ribs and recesses that are radially arranged around the exterior of its housing in a manner that allows the flashlight to have an aesthetic appearance even when being used as a stand alone device. The interface clamp is configured to be mounted onto the desired substrate and includes clamping members that releasably engage the engagement surfaces on housing of the flashlight. In this manner, the ribs on the flashlight housing provide the engagement surface by which the flashlight can be clamped without the need for a band that extends entirely around the barrel of the flashlight as was the case in the prior art.
The novel clamping arrangement and the manner in which it engages the housing of the flashlight allows for the flashlight to be easily mounted onto any variety of different modular interface systems such as the interface rail that is integrated onto modern type firearms. In the alternative, clamping assemblies may be provided in other locations, such as mounted to the side of a military style helmet thereby allowing the flashlight to be transferred between mounting positions both on the firearm and on the user's helmet.
Accordingly, it is an object of the present invention to provide a flashlight having a housing that includes a mounting interface that is integrated into the construction of its housing. It is a further object of the present invention to provide a flashlight having at least two recesses formed in the housing thereof to facilitate engagement of the flashlight using a clamping assembly. It is still a further object of the present invention to provide a mounting interface that is received as a modular accessory in a military weapon system and serves to releasably engage and retain a flashlight in the desired location adjacent the barrel of a firearm. It is yet a further object of the present invention to provide a modular mounting system using a base member that is configured to engage a substrate and includes releasable clamping means for receiving and retaining a flashlight.
These together with other objects of the invention, along with various features of novelty that characterize the invention, are pointed out with particularity in the claims annexed hereto and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated a preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings which illustrate the best mode presently contemplated for carrying out the present invention:
FIG. 1 is a front perspective view of the flashlight interface system of the present invention;
FIG. 2 is a cross sectional view of the assembly taken along line 2 - 2 of FIG. 1 with the flashlight received in the mounting interface and the interface in a disengaged position;
FIG. 3 is a cross sectional view of the assembly taken along line 2 - 2 of FIG. 1 with the flashlight received in the mounting interface and the interface in an engaged position;
FIG. 4 is a cross sectional view of an alternate embodiment mounting interface with the interface rotated to a disengaged position;
FIG. 5 is a cross sectional view of the mounting interface of FIG. 4 with the interface rotated to an engaged position;
FIG. 6 depicts the flashlight interface system mounted onto a standard issue military rifle; and
FIG. 7 depicts the flashlight interface system clamp mounted to the side of a helmet.
DETAILED DESCRIPTION OF THE INVENTION
Now referring to the drawings, the flashlight mounting assembly is shown and generally illustrated at 10 in the figures. In particular, the principal components of the flashlight mounting assembly 10 can be seen in FIG. 1 . The flashlight mounting assembly 10 generally includes a flashlight 12 with engagement surfaces 14 disposed on its housing 16 and a mounting interface 18 having a first side 20 that is configured to releasably engage the flashlight 12 via the engagement surfaces 14 and a second side 22 that is configured to engage a receiving surface as will be discussed in greater detail below.
The flashlight 12 component of the present invention could be any type of flashlight known in the art having a housing 16 that is constructed in accordance with the teachings of the present invention. More particularly, the flashlight 12 generally includes a housing 16 , a light source, a power source and a means for selectively completing a circuit between the light source and power source in order to energize the light source. The light source may be any suitable type of light source commonly found in flashlights including but not limited to incandescent, xenon, halogen, standard light emitting diodes, high output light emitting diodes and any multiple or combination thereof. The light output of the light source may fall anywhere within the visible color range and may also include infrared or ultraviolet. Preferably, the output will be in the visible white range either by using an Indium Gallium Nitride/Gallium Nitride chip with a phosphor coating such as a Nichea white LED. Similarly, as would be obvious in the art other white LED's could easily be substituted for the same effect. For example, an Aluminum Indium Gallium Arsenide LED could easily be substituted.
The flashlight 12 may also include auxiliary lighting functions in combination with or in place of the white light element. The present invention may also include a red light diode for night vision operations, an infrared diode for use in conjunction with night vision goggles or a laser diode for automated firing or targeting systems. Any of these features may be included either alone or in combination in the flashlight 12 of the present invention. Further, the power source may be any suitable power source for use in conjunction with portable lighting devices such as alkaline batteries, lithium batteries, rechargeable batteries of any known chemistry and/or chemical fuel cells. In certain applications, the flashlight 12 may also derive its power from a remote power source such as may be provided on a military weapons system.
The flashlight housing 16 and the mounting interface 18 may be milled or cast from metallic materials. Similarly, the housing 16 and mounting interface 18 may be molded from high strength polymer materials. Finally, the housing 16 and mounting interface 18 may be insert molded using a combination of metallic and polymer components as may be necessary to create the durability and strength demanded by the application.
As was stated above, in the context of the present invention, it is important that the housing 16 of the flashlight 12 include at least two engagement surfaces 14 to facilitate engagement between the flashlight 12 and the mounting interface 18 . Turning now to FIGS. 2 and 3 , the relationship between the flashlight 12 and the mounting interface 18 is depicted, with the flashlight 12 being shown in a mounted position relative to the mounting interface 18 . The first side 20 of the mounting interface 18 into which the flashlight housing 16 is received and retained can be seen to include a first clamping arm 24 and a second clamping arm 26 extending therefrom. Further detents 28 extend inwardly at the ends of the first and second clamping arms 24 , 26 to engage the interface surfaces 14 . The first and second clamping arms 24 , 26 cooperate to retain the flashlight 12 by engaging the engagement surfaces 14 on the housing 16 of the flashlight 12 with the detents 28 on the ends of the first and second clamping arms 24 , 26 when the first and second clamping arms 24 , 26 are in the engaged position as depicted in FIG. 3 .
It can be seen by viewing both FIGS. 2 and 3 in conjunction that the first and second clamping arms 24 , 26 can be deflected relative to one another to allow insertion and/or removal of the flashlight housing 16 therebetween. The clamping arms 24 , 26 may be deflected relative to one another in any manner known to one skilled in the art. For example, the mounting interface 18 may be formed to include limited flexibility in either the base portion or in the clamping arms 24 , 26 so that the clamping arms 24 , 26 can be deflected simply by flexing the mounting interface 18 . Alternatively, the first clamping arm 24 may be rigid relative to the base portion of the mounting interface 18 while the second clamping arm 26 is linearly displaceable between an engaged position as shown in FIG. 3 and a disengaged position as is shown in FIG. 2 . The displaceable second clamping arm 26 may be spring biased towards the engaged position and can also be seen to include a locking mechanism 30 in the form of a threaded fastener or throw lever that prevents displacement of the second clamping arm 26 once the flashlight 12 is installed and the first and second clamping arms 24 , 26 are in the engaged position.
Turning to FIGS. 4 and 5 the second clamping arm 26 A is shown as being displaceable through rotation relative to the base portion of the mounting interface 18 . In this embodiment, the second clamping arm 26 A is attached to the mounting interface 18 using a pin 32 around which the second clamping arm 26 A can rotate. As was stated above, a locking mechanism 30 is provided in the form of a threaded fastener or throw lever that prevents displacement of the second clamping arm 26 A once the flashlight 12 is installed and the first and second clamping arms 24 , 26 A are in the engaged position.
Regardless of the form that the second side 22 mounting interface 18 takes or the receiving surface to which the mounting interface 18 will be attached, the interaction between the mounting interface 18 and the flashlight 12 remains the same. The flashlight housing 16 , as was stated earlier, includes at least two interface surfaces 14 formed thereon. The interface surfaces 14 are configured and arranged in a manner so as to be inclined at a slight oblique angle relative to one another. The reason for angling the engagement surfaces 14 relative to one another is that once the flashlight 12 is engaged in the mounting interface 18 , the angled interface surfaces 14 firmly lock the flashlight 12 between the clamping arms 24 , 26 and prevent the flashlight 12 from being knocked therefrom. In the preferred embodiment, the flashlight housing 16 includes at least two ribs 34 extending from the exterior surface of the housing 16 wherein the ribs 34 are disposed at an oblique angle relative to one another. It is still more preferred that the ribs 34 are arranged radially relative to the flashlight housing 16 such that the engagement surfaces 14 are parallel to a line extending through the center of the flashlight housing 16 . It is most preferred that the engaging surfaces 14 be formed as an array of alternating ribs 34 and recess 36 uniformly arranged in a radial array around the exterior surface of the flashlight housing 16 . In this configuration, the engagement surfaces 14 are provided in a manner that allows the flashlight 12 to be installed into the mounting interface 18 reliably and in virtually any orientation. In addition, the formation of the ribs 34 and recesses 36 provide for a flashlight housing 16 that is effective for mounting yet still appears as aesthetically pleasing for stand alone use while also including a rugged grip pattern that makes the flashlight 12 easy to hold when not received in the mounting interface 18 .
The second side 22 of the mounting interface 18 in its simplest form may be flat and attached to a receiving surface using threaded fasteners 38 as are depicted in FIG. 1 . The second side 22 of the mounting interface 18 may also be formed as is depicted in the figures to include an interface suitable for engagement with a dovetail rail. In FIG. 6 there is shown an outline of a conventional combat firearm 100 having a conventional stock 102 , upper receiver 104 with flattop, lower receiver 106 , barrel 108 , pistol grip 110 , and magazine 112 . The barrel 108 is joined to the upper receiver 104 . The barrel 108 defines the forward portion of the firearm 100 and the stock 102 defines the rearward portion of the firearm 100 . The longitudinal axis of the firearm 100 runs from stock 102 through receiver 104 , 106 to barrel 108 . The barrel 108 is joined to the forward portion of the upper receiver 104 , i.e., the upper receiver “receives” the barrel. The stock 102 is joined to the rear portion of the upper receiver 104 . The barrel 108 has protective hand guards 114 about its circumference.
Generally, such modern type firearms include an interface rail 116 integrated therein for the mounting of auxiliary devices. The rail 116 is known in the art as a Weaver type interface and takes the form of a rail 116 having a dovetail cross-sectional profile that extends over the upper receiver 104 of the firearm 100 . Additionally, there are several supplemental rail systems that mount onto such firearms 100 by interfacing with the Weaver rail 116 on the firearm 100 and extending along the barrel 108 to provide additional interface rails 116 both along the top of the firearm 100 as well as at the 3, 6 and 9 o'clock positions around the barrel 108 . All of the interface rails 116 are provided having a standardized profile and are configured specifically for the mounting of various accessories depending on the type environment in which the firearm 100 will be used. Accordingly, the formation of the dovetail profile on the second side 22 of the mounting interface 18 allows the mounting interface 18 to be received and retained on the interface rail 116 provided on the firearm 100 .
When the flashlight assembly 10 is mounted onto a firearm 100 the lower portion 22 dovetail may be formed as a rigid profile that is simply slid onto the firearm 100 accessory rail 116 and retained in place using setscrews. In the alternative, the dovetail interface may be formed as a clamping assembly to engage the accessory rail 116 on the firearm 100 . In this configuration, the mounting interface 18 may include a single tightening mechanism that engages both the second clamping arm 26 that engages the flashlight 12 and the rail interface clamp at the same time. Similarly, the mounting interface 18 may have a separate dedicated clamping member for the dovetail interface. The tightening mechanism for both the clamping arm 26 and the dovetail interface may be set screws, thumb screws, quick release type mechanisms or combinations thereof to allow easy mounting and demounting of the flashlight 12 relative to the firearm 100 .
FIG. 7 depicts the mounting interface 18 with an alternative clamping 38 assembly on the second side 22 thereof. The alternative clamping assembly 38 allows the mounting interface 18 to be fastened onto a helmet 40 such as a standard issue military helmet. The first side 20 of the mounting interface 18 is formed as described above and is configured to receive and engage a flashlight 12 in the same manner as described earlier. In this manner, the same flashlight 12 can be easily used in conjunction with a military rifle 100 or helmet 40 and may also be moved between these locations easily.
It can therefore be seen that the present invention provides a novel flashlight assembly 10 that includes integrated mounting surfaces that allow the flashlight 12 to be received into a durable low profile mounting interface 18 . Further, the present invention can be modified to accommodate a number of standard mounting environments through simple changes to the second side 22 of the mounting interface 18 while maintaining a standard configuration on the first side 20 of the mounting interface 18 thereby allowing modular use of a single flashlight 12 design. For these reasons, the instant invention is believed to represent a significant advancement in the art, which has substantial commercial merit.
While there is shown and described herein certain specific structure embodying the invention, it will be manifest to those skilled in the art that various modifications and rearrangements of the parts may be made without departing from the spirit and scope of the underlying inventive concept and that the same is not limited to the particular forms herein shown and described except insofar as indicated by the scope of the appended claims.
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A modular flashlight assembly is provided that includes an integrated interface to facilitate mounting of the flashlight to a variety of different equipment. The flashlight mounting system includes a pattern of engagement surfaces on an exterior surface of the flashlight housing and a mounting bracket. The mounting bracket is configured to be mounted onto the desired substrate and includes clamping members that releasably engage the engagement surfaces on the flashlight housing. In this manner, the engagement surfaces on the flashlight housing provide a surface by which the flashlight can be clamped without the need for a band that extends entirely around the barrel of the flashlight. Further, by releasably clamping the flashlight into a modular system, the flashlight can easily mounted onto any variety of different modular interface systems such as the interface rail that is integrated onto modern type firearms.
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CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application 61/027,795, filed Feb. 11, 2008.
FIELD OF THE INVENTION
[0002] The present invention relates to a multipurpose support device for supporting an item such as a laptop computer or a book. The multipurpose support device of the present invention is used while attached to a structural support, such as a mobile cart, a desk, a sofa or a wall.
BACKGROUND OF THE INVENTION
[0003] Many people spend a lot of time using a laptop computer. Most people use a laptop computer by leaving it on the top of a desk and read information on a laptop computer screen with their neck straight or bent downward depending on the position of the computer screen. This posture causes a lot of stress and strain on the user's neck. In addition, people tend to lean forward and keep their back away from the back of the chair. This posture causes a lot of stress and strain on the back and shoulder. People place their forearms, hands and wrists on top of the desk when they type on the keyboard of the laptop or use the mouse panel of the laptop. This type of posture causes a lot of stress on all joints of upper extremities. Working with a laptop computer for several hours a day with this unhealthy posture could make a person feel tired easily with pain at their neck, shoulder, back and wrists. This could lead to an injury of the spine, back, shoulder, neck, and wrists.
[0004] To avoid the aforementioned kind of pain or injury, a person should use a laptop computer in a relaxed posture with the least amount of stress and strain to the neck, back, shoulder and wrists. The most relaxed posture for using a laptop computer is sitting on a chair at a reclined angle. The laptop computer is placed in a proper holder with comfortable forearm and wrist supports, so that the user can see the laptop computer screen easily while sitting at a reclined angle with the neck and back rested on the chair back and user's elbows, wrists and hands rested on proper supports. This relaxed posture causes the least amount of stress to the spine, neck, shoulder, hands and wrists.
[0005] Similarly, it is important to adopt a proper posture when reading a book. Users often position a book on their laps or on top of a desk and bend over the book in order to read it. Oftentimes, a user will hold the spine of the book with one hand, while turning the pages with the other. In addition to creating fatigue and stress for the neck and shoulders, reading a book can also cause fatigue of the hands and fingers because of the need to grip the book and turn the pages.
[0006] Devices that are currently available in the marketplace provide a support for a laptop computer or book, but however do not allow the device to be adjusted in order to promote good posture of the user. In other words, the presently available commercial devices do not address the bad posture problems of users of laptop computers and readers of books. Hence, it is desirable to have a support device that is capable of holding a laptop computer or a book, while also promoting good posture.
SUMMARY OF THE INVENTION
[0007] An embodiment of the invention is directed to a multipurpose support device comprising: a base comprising a substantially horizontal surface; and a first support member that is coupled to the base, wherein the plane of the first support member is substantially perpendicular to the base, and wherein the base is movably connected to a structure, said structure providing a means for holding the multipurpose support device in a specified position. In an additional embodiment of the invention, a second support member is connected to the first support member wherein the second support member is movable relative to the base and the first support member, and the second support member comprises a plurality of wrist supports. In certain embodiments of the invention, the second support member is immovable relative to the base and the first support member.
[0008] An embodiment of the invention is directed to a method for using a multipurpose support device having a base comprising a substantially horizontal surface; a first support member coupled to the base, and a second support member that is connected to the first support member, and wherein the second support member comprises a plurality of wrist supports; the method comprising the following steps: positioning the bottom edge of a laptop computer on the first support member; positioning the top edge of the lap top on the base; resting the user's forearms on the forearm supports of the second support member; extending the wrist supports of the second support member towards the surface of the laptop computer; and resting the user's wrists on the wrist supports of the second support member.
[0009] An additional embodiment of the invention is directed to a method for using a multipurpose support device having a base comprising a substantially horizontal surface; a first support member coupled to the base, wherein the plane of the first support member is substantially perpendicular to the base, and wherein the base is movably connected to a structure, said structure providing a means for holding the multipurpose support device in a specified position, and further comprising securing members at the lateral outer edge of the base to which are attached flexible extender members; the method comprising the following steps: positioning an open book on the base; securing each lateral side of the book with the securing members; and positioning one or more selected pages of the book under the flexible extenders.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a diagrammatic perspective view illustrating an embodiment of the multipurpose support device of the invention.
[0011] FIG. 2 is a diagrammatic top view illustrating an embodiment of the multipurpose support device of the invention.
[0012] FIG. 3 is a diagrammatic side view illustrating an embodiment of the multipurpose support device of the invention.
[0013] FIG. 4 is a diagrammatic perspective view illustrating an embodiment of the multipurpose support device of the invention.
[0014] FIG. 5 is a diagrammatic perspective view illustrating an embodiment of the multipurpose support device of the invention.
[0015] FIG. 6 is a diagrammatic perspective view illustrating an embodiment of the multipurpose support device of the invention.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0016] As seen in FIG. 1 , a multipurpose support device 10 is shown holding a laptop computer 12 . The support device 10 comprises a member or base 14 that serves as the platform upon which a portion of the laptop computer 12 rests. The support device 10 further comprises a first support member 15 that is substantially perpendicular to base 14 and immovably connected to base 14 . The first support member 15 provides a surface upon which the bottom portion of the laptop computer may be placed. The multipurpose support device 10 further comprises a second support member 16 that is movably connected to member 15 . In order to prevent the bottom portion of the laptop computer from sliding off the surface of member 15 , a plurality of restraints 19 such as hooks may be employed. The location of the restraints may be changed to allow for better support of a laptop computer by allowing rearrangement of the restraints 19 on member 15 . Member 16 comprises a plurality of wrist supports 17 that may be extended by a user and placed on top of the laptop computer 12 , when the multipurpose support device 10 is in use. The position of member 16 may be adjusted so that the angle of member 16 relative to member 15 can be changed either along a vertical plane or a horizontal plane in accordance with a user's comfort. When the multipurpose support device is not in use, the wrist supports 17 may be placed within recessed spaces 18 located on member 16 . Additionally, the second support member 16 provides a user with a surface to rest their forearms. Member 16 may optionally comprise a strip of padded material (not shown) to promote comfort of the forearms when they are resting on member 16 . In certain embodiments of the invention, the second support member 16 may be immovably connected to member 15 .
[0017] As seen in FIG. 2 , the location and position of a first arm member 21 that is attached to the posterior surface, i.e., opposite surface to where the laptop computer would rest, of the base 14 is shown. The first arm member 21 functions to position the multipurpose support device 10 at an angle that is comfortably suitable for the user and which allows the user to maintain the proper posture when using the multipurpose support device. The first arm member 21 is movably connected to a second arm member 20 , which in turn may be connected to additional arm members, a surface such as a desk, a cart or a vertical member (not shown) to facilitate the fixed anchoring of the multipurpose support device 10 .
[0018] FIG. 3 shows a side elevation view of the multipurpose support device 10 with first arm member 21 connected to base 14 and second arm member 20 connected to first arm member 21 .
[0019] FIG. 4 is a perspective view of the multipurpose support device 10 comprising a first arm member 21 and a second arm member 20 , wherein the second arm member is connected to a vertical member 22 . The vertical member is contained within a housing 26 which comprises a shelf-like member 23 to which the vertical member 22 is connected by its base 24 . The bottom end of the housing comprises a floor 25 , to which are connected a plurality of wheels 27 . The wheels 27 allow a user to transport the multipurpose support device 10 and housing 26 to a convenient location. In the event that wheels 27 are employed, it is desirable to provide a mechanism to fix or lock the wheels (not shown) when the multipurpose support device 10 is conveniently positioned for use.
[0020] The presence of the first arm member 21 and second arm member 20 permits the user to adjust the position of the multipurpose support apparatus 10 , so that the user may comfortably position a laptop computer at a convenient distance and position in a manner while maintaining good posture. The profile of vertical member 22 may have a straight shape (as shown in FIG. 4 ) or a curved shape (not shown).
[0021] The multipurpose support device 10 is positioned relative to the user in a seated position so that the keyboard is approximately at the same plane as the user's forearms when typing. Additionally, the user's wrists are at the level of the wrist supports 17 . At the same time, the user's posture is that of a relaxed, reclining nature. In addition to the wrist supports 17 , an additional forearm support, such as a padded support (not shown) may be included with member 16 , so that the user's forearms may comfortably rest on the surface of member 16 , while the user's wrists are supported by the wrist supports 17 .
[0022] It will be seen from the following description, that the multipurpose support device 10 , particularly base 14 may be horizontally adjustable toward and away from the user, i.e., translationally. Moreover, the multipurpose support device is simultaneously pivotal along a horizontal axis parallel to base 14 . One embodiment of the multipurpose support device 10 for providing both translational and pivotal or rotational movement of the base 14 may comprise a first arm member 21 fixedly attached to the bottom surface of base 14 and having a plurality of sliding dovetail members (not shown). As will be appreciated by those persons of ordinary skill in the art, sliding dovetails are only exemplary of mechanical arrangements that permit base 14 to be movable relative to the housing 26 and the vertical member 22 .
[0023] From the above description it will be apparent that the multipurpose support device, on which the laptop computer 12 rests, may be moved relative to the user both pivotally and translationally, as well as vertically, thus accommodating users of different height, girth, and personal preference for the position of the laptop computer during keyboarding or using mouse panel as well as for maintaining the display at an appropriate height and angle for viewing.
[0024] It may be desirable when using a laptop computer 12 with the present invention to connect the computer to a source of AC power through an in-line transformer (not shown) and/or connect it to a printer (not shown). To accommodate the cords to the printer and/or power it may be desirable to hold the cords in a convenient position. For example, a channel or trough (not shown) could be formed in one surface of a solid stanchion or if the stanchion is hollow, such as a pipe, suitable holes could be provided through which the ends of the cord could enter and exit near the member 14 and the floor 25 of the housing 26 . Alternatively, a simple clamp or Velcro belt could be used to hold the cords in place (not shown).
[0025] In certain embodiments of the invention, one or more sliding plates (not shown) may be added to the back of the base 14 , which can be slid out to enable the user to place books or sheets of paper on the sliding plates when using the multipurpose support device 10 .
[0026] As shown in FIG. 5 , a user 30 can place the laptop on the anterior surface of base 14 , sit on a chair with a slightly reclined angle 31 , rest the back and neck on the chair, pull and adjust the multipurpose support device 10 to a comfortable position and angle to rest the elbows on the chair arms and rest the forearms on member 16 and rest the wrists on the wrist supports 17 . With this posture, the user's neck, back, elbows, forearms, and wrist are fully supported and rested on various supports, thus reducing the chance of pain and injury to the users.
[0027] In certain embodiments of the invention, a plurality of adjustable sliding plates of suitable dimensions (not shown) can be added to the anterior surface of the base 14 to raise the bottom portion of the laptop computer away from base 14 in order to make room for a power cord or other wires to be plugged into the back end of the laptop computer.
[0028] In an embodiment of the invention, two side clamps are added to the surface of the base 14 to enable the user to use the multipurpose support device for reading a book or magazine. In FIG. 6 , the base 101 is analogous to the base 14 depicted in FIGS. 2-5 .
[0029] As best illustrated in FIG. 6 , the book holder embodiment of the multipurpose support device of the invention 100 comprises a base 101 having an upper edge member 104 , a lower edge 106 , a first side edge 108 , a second side edge 110 , a front side 112 and a back side 114 . Attached to the lower edge 106 , is a first support member 113 that is fixedly connected to the lower edge 106 and is substantially perpendicular to the base 101 . The upper edge member 104 and the first support member 113 each have a slot 116 present therein. Each of the slots 116 generally extends along the length of the upper edge member 104 and member 113 . Each of a pair of vertical plates 118 is removably extended into the slots 116 . Each of the plates 118 has an outer edge 120 biased outwardly away from the center of the base 101 . The plates 118 also each have an inner edge 124 biased towards the center of the base 101 . The inner edges 124 of the plates 118 face one another. To each of the plates 118 , a movable plate 119 is attached via connectors 121 . The plates 119 are capable of being moved along a vertical plane along the plates 118 .
[0030] Each of a pair of securing members 126 is attached to the outer edges 120 of the plates 118 . The securing members 126 are adapted for attaching a book to the plates 118 . Each of the securing members 126 preferably comprises a clip 133 biased towards the inner edge 124 of the plates 118 . The clip 133 is used to clamp down the lateral edge of the book pages on to the base 101 . In certain embodiments of the invention, the clip 133 may be transparent, which allows the user to be able to see and read the content on the portion of the page that is clamped under the clip 133 .
[0031] In use, the plates 118 are extended outwardly from the base 101 so that the base 101 is of a size required for a book to be fixed on the base 101 . The securing members 126 are used to attach a book or other reading material to the plates 118 so that the book is placed in an open position. Each of the securing members comprises a vertical rod 128 to which is attached a flexible finger-like extender 130 . The flexible extenders 130 may be used to maintain the pages of the book in place during use. Each of the plates 119 can be moved along a vertical plane, i.e., up and down in order to accommodate tall or short books.
[0032] The securing member 126 on one side of the device may be used to secure the pages that have already been read. The securing member 126 on the opposite side of the panel may be used to secure those pages that are not anticipated to be read during a particular session. The collection of pages to be read in a particular session may be positioned between the securing member 126 and the flexible extender 130 . Adjustments of amounts of pages positioned under the securing members 126 and the amounts of pages comprising reading-session pages positioned under the flexible extender 130 are made as desired in relation to reading times or anticipated reading periods. Lastly, during reading, the user can slide a page out from under one flexible extender 130 and slide it under the opposite flexible extender 130 . Optionally, a string or wire 132 can be extended from the upper edge 104 of the panel 101 across the center line of the book and locked at the lower edge 106 . Conversely, the string 132 may be extended from the lower edge 106 , across the center line of the book and locked at the upper edge 104 . The center string 132 is especially useful when the user reads the book on the supporting surface in a lying-down and facing-up position.
[0033] The first arm member 21 and second arm member 20 , as well as other structures that the second arm member may be connected to (as set forth in FIGS. 2-5 ), such as a desk, a cart or a vertical member are the same as previously described for the laptop support embodiment of the invention may be incorporated in the embodiment of the invention shown in FIG. 6 .
[0034] From the various embodiments described and shown herein, it will be obvious that many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that the invention may be practiced otherwise than as specifically described in the various embodiments in this specification and that the scope of the invention is to be defined by the appended claims.
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The invention is directed multipurpose support device for supporting an item such as a laptop computer or a book. The support device has a base that is adapted to be coupled to a structural support, such as a mobile cart, a desk, a sofa or a wall.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2005-261029, filed Sep. 8, 2005, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a viewing recommendation apparatus and method, which make recommendation of programs the user might want to view based on broadcast programs and stored content (stored programs) in a TV reception, storage, and playback system which allows the user to view multi-channel broadcast programs, and comprises a storage device such as a hard disk drive (HDD) or the like which can store previous broadcast programs.
2. Description of the Related Art
In recent years, direct broadcasting by satellite has prevailed in addition to terrestrial TV broadcasting, and TV broadcasting has entered a full-scale multi-channel era. Conventionally, programs to view are searched by browsing the TV schedule in the newspaper or program guides. However, with this method, programs that the user wants to view may often be missed. Using an electronic program guide (EPG) provided by the broadcast signal or a web site (iEPG) that allows the user to browse the EPG on the Internet, programs are searched using a genre- or keyword-based search function provided by the EPG or iEPG. On some iEPG sites, a push function that notifies programs which match genres and keywords registered in advance via e-mail is implemented.
Simultaneously with the multi-channel era, recorders which comprise a large-capacity storage such as an HDD have prevailed in place of the conventional VTR. There are two roles of the recorder at home: (1) an archiver used to view already viewed programs later again and (2) temporary storage of programs which cannot be viewed due to absence, program clash, other business to attend to, and the like at the time of broadcasting. Since a new recorder with a large-capacity storage is convenient, i.e., it does not require tape exchange, and has much higher recording quality than the VTR, it produces a large change in the role of (2). That is, in the era of VTR, a negative use “to be obliged to store programs that cannot be viewed at the time of broadcast” has prevailed, but a positive use style “to store programs to view them at a convenient time more than the time of broadcasting” is being established.
Using these techniques, an automatic recording function can be obviously implemented, and products have already been released. More specifically, genres and keywords are registered in advance, and programs which match them are automatically recorded. In some products, by analyzing the history of manual program recording of the user without registering any explicit genres or keywords, the genres and keywords that the user has an interest in are estimated, and automatic recording is done based on them.
Also, an apparatus which determines the priority in consideration of congeniality to a user's taste, the value of information depending on time, and economical efficiency of storage, and automatically stores information that matches the user's taste is available (for example, see Jpn. Pat. Appln. KOKAI No. 11-196389).
However, the conventional program recommendation function is basically a recording assistant function, and helps to select programs to be kept in a storage device from a large amount of broadcast programs, but it is not helpful about the viewing order of stored content. The assistant functions include, e.g., genre-dependent sort, recording date and time order sort, recording recommendation score order sort, and the like. However, these functions are merely obvious list display methods of stored content.
Also, no method of equally evaluating broadcast programs and stored content, and selecting a program or content that the user might want to view now is provided. Put simply, the user cannot select a program or content to view “now” from broadcast TV programs which are streamed in large quantities from multi-channels, and contents stored in large quantities in a large-capacity HDD.
BRIEF SUMMARY OF THE INVENTION
In accordance with a first aspect of the invention, there is provided a viewing recommendation apparatus comprising: an acquisition unit configured to acquire first broadcast program information for each of first broadcast programs to be broadcasted; a storage unit configured to store a plurality of previously broadcasted second broadcast programs in correspondence with second broadcast program information; a calculation unit configured to calculate an urgency in accordance with the first broadcast program information and the second broadcast program information to obtain a plurality of urgencies, the urgency indicating a degree to view a broadcast program earlier; and a generation unit configured to generate a recommendation list of broadcast programs to be viewed based on levels of the urgencies.
In accordance with a second aspect of the invention, there is provided a viewing recommendation method comprising: acquiring first broadcast program information for each of first broadcast programs to be broadcasted; preparing a storage unit configured to store a plurality of previously broadcasted second broadcast programs in correspondence with second broadcast program information; calculating an urgency in accordance with the first broadcast program information and the second broadcast program information to obtain a plurality of urgencies, the urgency indicating a degree to view a broadcast program earlier; and generating a recommendation list of broadcast programs to be viewed based on levels of the urgencies.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a block diagram of a viewing recommendation apparatus according to an embodiment of the present invention;
FIG. 2 is a flowchart showing an operation example when the user uses the viewing recommendation apparatus shown in FIG. 1 ; and
FIG. 3 is a flowchart showing processing when the viewing recommendation apparatus shown in FIG. 1 generates a combined viewing recommendation list.
DETAILED DESCRIPTION OF THE INVENTION
A viewing recommendation apparatus and method according to an embodiment of the present invention will be described in detail hereinafter with reference to the accompanying drawings.
Important points of the viewing recommendation apparatus and method according to the embodiment of the present invention will be briefly explained first. The viewing recommendation apparatus of this embodiment appends one or more viewing recommendation indices, which are determined depending on elapsed time periods from original broadcasting times unlike recording recommendation indices, to broadcast programs and stored content (“stored content” corresponds to “stored programs” in FIG. 1 ) based on genres and the like of them. A viewing recommendation index indicates a viewing urgency determined for each program genre, and is obtained by rating knowledge such that it should be large for news and sports, relatively large for a drama series, middle for others, and so forth. Also, another viewing recommendation index is a viewing time limit of each of broadcast programs and stored content determined for each program genre (in case of stored content, a period until the significance of viewing of each stored content is substantially lost or time limit), and 24 hours or the like for a regular news program.
The viewing recommendation apparatus of this embodiment recommends a broadcast program or stored content to view at a specific time (viewing recommendation request time) by mainly using an arbitrary combination of the viewing recommendation indices or a combination of the recording recommendation index and viewing recommendation index. The viewing recommendation apparatus presents a viewing recommendation list including both broadcast programs and stored content by mainly using the viewing urgency which has a broadcast time as the viewing recommendation request time or a combination of it and the recording recommendation index for broadcast programs, and using the viewing time limit for stored content. Also, the apparatus recommends the storage device to erase stored content based on the viewing time limits, thus achieving effective use of the storage.
The arrangement of the viewing recommendation apparatus of this embodiment will be described below with reference to FIG. 1 . FIG. 1 is a block diagram of the viewing recommendation apparatus according to the embodiment of the present invention.
The viewing recommendation apparatus of this embodiment comprises an EPG acquisition unit 101 , recording recommendation score calculation unit 102 , urgent viewing demand level calculation unit 103 , program viewing time limit calculation unit 104 , stored program viewing recommendation score calculation unit 105 , stored program with viewing recommendation score database (DB) 106 , erase recommendation unit 107 , broadcast program viewing recommendation score calculation unit 108 , EPG with viewing recommendation score database 109 , combined recommendation list calculation unit 110 , and control unit 111 . Although not clearly specified in FIG. 1 , the viewing recommendation apparatus of this embodiment has some recording recommendation indices, already stores previous storage content in a large-capacity storage based on the indices automatically or manually, and allows the user to view broadcast programs in large quantities.
The EPG acquisition unit 101 acquires EPG data by utilizing terrestrial digital broadcasting, direct broadcasting by satellite, cable broadcasting, Internet, and the like. The EPG acquisition unit 101 acquires EPG data periodically (e.g., once per day). In this case, the unit 101 acquires EPG data for 24 hours. Each EPG describes the program start times, program end times, program titles, program content, and the like.
The recording recommendation score calculation unit 102 calculates a recording recommendation score (R) for each broadcast program included in the acquired EPG data. The recording recommendation score (R) is defined depending on whether or not keywords are included in text that describes each broadcast program content. For example, when a specific keyword is described in the broadcast program content, this broadcast program has R=1; otherwise, it has R=0. The user may register keywords in advance in a database (not shown). The recording recommendation score calculation unit 102 (or control unit 111 ) may store a user's viewing history in a database, and may adopt words with a highest frequency of occurrence as keywords with reference to the viewing history.
The recording recommendation score calculation unit 102 may assign a recording recommendation score (R) with reference to the genre of each broadcast program included in the EPG data. In this case, the recording recommendation score (R) is defined depending whether or not the genre of each broadcast program matches a given genre. For example, when the genre of a broadcast program matches a specific genre, this broadcast program has R=0.9; otherwise, it has R=0.1.
Furthermore, the recording recommendation score calculation unit 102 may obtain a recording recommendation score (R) by computing the product of a score value calculated based on keywords and that calculated based on a genre. In the above example, if a keyword is described in the broadcast program content, and the genre of a broadcast program matches a given genre, this broadcast program has R=1×0.9=0.9; if a keyword is described in the broadcast program content, but the genre of a broadcast program does not match a given genre, it has R=1×0.1=0.1.
Note that upon checking keyword descriptions and matching of genres, the recording recommendation score calculation unit 102 may search, e.g., a database of a synonymous dictionary (not shown) for words which are considered as synonyms of prepared keywords and genre names, and may calculate a recording recommendation score (R) based on the keywords and genre names including the words which are considered as synonyms.
The urgent viewing demand level calculation unit 103 calculates a viewing urgency (Im) for each broadcast program included in the acquired EPG data. The viewing urgency (Im) is a numerical value indicating a degree to view earlier, irrespective of an elapsed time period from the broadcast time of that broadcast program, and assumes, e.g., 0<Im≦1. The urgent viewing demand level calculation unit 103 calculates a viewing urgency (Im) according to a genre name assigned in correspondence with each program included in the EPG data.
For example, a table that specifies in advance values like 1 for a broadcast program to view immediately, 0.8 for a broadcast program which need not be viewed immediately compared to the former program but should be viewed relatively earlier, and 0.7 for a broadcast program which is considered to have an invaluable program content value irrespective of an elapsed time period from the broadcast time is generated. Note that broadcast programs to view immediately include news programs, and sports live programs, and broadcast programs to view relatively earlier include a drama series. Also, broadcast programs which are considered to have a invaluable program content value irrespective of an elapsed time period include movie programs and culture programs.
The urgent viewing demand level calculation unit 103 calculates a viewing urgency (Im) of each broadcast program with reference to the genre of each broadcast program included in the acquired EPG data and such table that specifies values in advance.
Note that upon checking matching of genres, the urgent viewing demand level calculation unit 103 may search, e.g., a database of a synonymous dictionary (not shown) for words which are considered as synonyms of genre names, and may calculate a viewing urgency (Im) based on the genre names including the words which are considered as synonyms.
The program viewing time limit calculation unit 104 calculates a viewing time limit index (E) for each broadcast program included in the acquired EPG data. The viewing time limit index (E) is determined depending on an elapsed time period from the broadcast time, and is a numerical value that meets 0<E≦1. As the value is larger, the viewing time limit index (E) indicates a higher viewing worth of a broadcast program. The program viewing time limit calculation unit 104 calculates a viewing time limit index (E) at the time of acquisition of EPG data. For all broadcast programs included in the acquired EPG data, the unit 104 sets 1 as an initial value of the viewing time limit index (E). That is, broadcast programs which have not been broadcasted yet have a viewing time limit index (E)=1.
The program viewing time limit calculation unit 104 re-calculates E for stored content which have already been stored and those whose recording is underway. Upon making this re-calculation, the program viewing time limit calculation unit 104 calculates a viewing time limit index (E) according to a formula already determined for each genre with reference to genre information included in the EPG data. Let d* be the broadcasting day, and d be today. Then, when EPG data is acquired at a fixed time once per day, formulas can be determined for respective genres as:
News: E= 1/( d−d*+ 1) 2
Sports: E =max(( d*−d )/5+1, 0.01)
Movie: E=1
Others: E =max(( d*−d )/30+1, 0.1)
As in this example, the viewing time limit index (E) of a stored content that places an importance on the degree of freshness rapidly becomes smaller along with elapsed time. Also, the viewing time limit index (E) of a stored content which is considered to have the degree of freshness that remains unchanged becomes invaluable with respect to time.
The formulas determined for respective genres must be changed depending on the acquisition time interval of EPG data by the EPG acquisition unit 101 . For example, when the EPG acquisition unit 101 acquires EPG data twice or more per day, the formula determined for each genre must include time as a variable.
The stored program viewing recommendation score calculation unit 105 receives the recording recommendation score (R), viewing urgency (Im), and viewing time limit index (E), which are respectively calculated by the recording recommendation score calculation unit 102 , urgent viewing demand level calculation unit 103 , and program viewing time limit calculation unit 104 , for each stored content, and calculates a viewing recommendation score (V) for each stored content by combining these effects. A stored content has a higher degree to view urgently by the user with increasing viewing recommendation score (V). The viewing recommendation score (V) is given by, e.g.:
V=R×Im×E
According to the aim of the recommendation to be made, the recording recommendation score (R), viewing urgency (Im), and viewing time limit index (E) may be respectively weighted or may undergo nonlinear conversion. For example, the score (V) is given by, e.g., V=R 2 ×10×Im×E 1/2 .
The stored program with viewing recommendation score database 106 stores each viewing recommendation score (V) calculated by the stored program viewing recommendation score calculation unit 105 in correspondence with a stored content as an object of this score.
The erase recommendation unit 107 prompts the user to erase unnecessary ones of the stored content and viewing recommendation scores (V) stored in the stored program with viewing recommendation score database 106 from the stored program with viewing recommendation score database 106 . Whether or not a stored content is unnecessary is determined based on its viewing time limit index (E). A value Eth (which satisfies 0<Eth<1 in the above example) is set in advance, and the erase recommendation unit 107 compares this Eth with the viewing time limit index (E) stored in correspondence with each stored content. If the viewing time limit index (E) is smaller than Eth, the unit 107 prompts the user to erase the stored content having this index. The erase recommendation unit 107 may automatically erase this unnecessary stored content and corresponding viewing recommendation score (V) without prompting the user to erase.
The broadcast program viewing recommendation score calculation unit 108 receives the recording recommendation score (R) and viewing urgency (Im), which are respectively calculated by the recording recommendation score calculation unit 102 and urgent viewing demand level calculation unit 103 , for each broadcast program, and calculates a viewing recommendation score (V) for each broadcast program by combining these effects. The viewing recommendation score (V) corresponds to the viewing recommendation score (V) in case of E=1 calculated by the stored program viewing recommendation score calculation unit 105 . Since broadcast programs to be handled by the broadcast program viewing recommendation score calculation unit 108 are all future programs, a viewing time limit index (E) is set to “1”.
The EPG with viewing recommendation score database 109 stores each viewing recommendation score (V) calculated by the broadcast program viewing recommendation score calculation unit 108 in correspondence with a broadcast program as an object of this score. Information stored in the EPG with viewing recommendation score database 109 is updated every time the EPG acquisition unit 101 acquires EPG data.
The combined recommendation list calculation unit 110 accepts a user's instruction that requests presentation of recommended broadcast programs or recommended stored content, and acquires broadcast programs together with their viewing recommendation scores (V) in descending order of viewing recommendation score (V) from those which will be broadcasted from the present time until a near future (e.g., during today) with reference to the EPG with viewing recommendation score database 109 at the time of acceptance of this instruction. Furthermore, the combined recommendation list calculation unit 110 acquires stored content together with their viewing recommendation scores (V) from the stored program with viewing recommendation score database 106 in descending order of viewing recommendation score (V). The combined recommendation list calculation unit 110 generates a list (combined viewing recommendation score list; also called “broadcast program and stored program mixed recommendation list”) in descending order of viewing recommendation score (V) of the broadcast programs and stored content which are acquired from the stored program with viewing recommendation score database 106 and EPG with viewing recommendation score database 109 , and presents the generated list to the user. As a matter of course, the numbers of broadcast programs and stored content to be presented to the user and the like are design items, and can be changed as needed.
The control unit 111 controls respective units of the viewing recommendation apparatus. For example, the control unit 111 automatically records broadcast programs with high recording recommendation scores (R) from those included in the acquired EPG data. The control unit 111 may set a threshold Rth of the recording recommendation score (R) as an index indicating whether or not to record. When the value of the recording recommendation score (R) calculated for a given broadcast program by the recording recommendation score calculation unit 102 exceeds Rth, the control unit 111 may automatically record this broadcast program.
The operation executed when the user uses the viewing recommendation apparatus of this embodiment will be described below with reference to FIG. 2 .
The combined recommendation list calculation unit 110 accepts a viewing recommendation request from the user (step S 21 ). The viewing recommendation request is used to request a list which informs the user of broadcast programs or stored content which are assumed to be currently viewed best by the user and is to be presented to the user. The viewing recommendation request may be generated by an explicit user's operation (e.g., depression of a given button of a remote controller) or may be automatically generated in response to, e.g., an end event of the previous recommended broadcast program or previous recommended stored content.
Upon acceptance of the viewing recommendation request in step S 21 , the combined recommendation list calculation unit 110 recommends programs to view by the user from stored content, on-air programs, and programs which will begin to be broadcasted in the near future (e.g., within 30 minutes), and typically presents them to the user in the form of a list (step S 22 ).
The user selects a broadcast program or stored content from the list (step S 23 ), and the viewing recommendation apparatus executes appropriate processing depending on whether the selected broadcast program or stored content is a stored content, on-air program, or pre-broadcast program (step S 24 ). The apparatus executes playback, time-shift playback, or viewing reservation processing depending on whether the selected broadcast program or stored content is a stored content, on-air program, or pre-broadcast program. Note that details of such processing may change depending on whether or not the viewing recommendation apparatus has an automatic recording function. In steps S 23 and S 24 , the control unit 111 controls the processing.
The flow of processing executed when the viewing recommendation apparatus of this embodiment generates a combined recommendation list will be described below with reference to FIG. 3 .
Assume that a database (not shown) which can hold various attribute values for respective broadcast programs or stored content, which are calculated by the viewing recommendation apparatus, in addition to EPG information is provided. Also, assume that meta information of each of manually or automatically recorded stored content are kept held until the corresponding stored content is erased from the stored program with viewing recommendation score database 106 . Furthermore, assume that a series of processes described in FIG. 3 are periodically executed once per day.
The EPG acquisition unit 101 acquires EPG data for 24 hours ahead (step S 31 ). The recording recommendation score calculation unit 102 calculates recording recommendation scores (R) for respective acquired broadcast programs (step S 32 ). If the viewing recommendation apparatus has an automatic recording function, the control unit 111 executes processing for automatic recording in this step.
The urgent viewing demand level calculation unit 103 calculates viewing urgencies (Im) for respective acquired broadcast programs (step S 33 ). Next, the program viewing time limit calculation unit 104 calculates viewing time limit indices (E) for respective acquired broadcast programs. Initially, the program viewing time limit calculation unit 104 sets 1 as an initial value of a viewing time limit index (E) for all the broadcast programs included in the acquired EPG data (step S 34 ). The program viewing time limit calculation unit 104 re-calculates E using the above formulas for stored content which are already stored and those whose recording is underway (step S 35 ).
With the above processes, since the recording recommendation scores (R), viewing urgencies (Im), and viewing time limit indices (E) can be calculated for all broadcast programs and all stored content (i.e., programs whose recording is underway and which are already recorded for 24 hours ahead), the combined recommendation list calculation unit 110 calculates viewing recommendation scores (V) based on combinations of them (step S 36 ).
Since the viewing recommendation apparatus of this embodiment must calculate recommendation scores which change depending on a time, a method of periodically re-calculating scores (some of them), and a method of calculating scores on-demand in response to a recommendation request may be used. In the aforementioned example, a periodic calculation per day has been exemplified as a most feasible method based on the performance of currently available hardware and the viewing life styles of general users. However, if advanced hardware is available, a method of calculating scores on-demand may be adopted.
According to the aforementioned embodiment, contents the user might want to view can be recommended from broadcast programs and stored content in consideration of features of respective content. According to this embodiment, in consideration that the degree to view each content may change depending on the time, recommended broadcast programs or recommended stored content at the time of the recommendation request can be presented based on the request time of them by the user. Since contents can be appropriately erased, the usability of the system can be prevented from dropping due to a large quantity of viewing worthless content stored in the large-capacity storage.
Therefore, according to this embodiment, not only recording is assisted, but also content to view are presented in response to a user's viewing request, thus improving the user's true viewing satisfaction level.
According to the viewing recommendation apparatus and method of the embodiment of the present invention, contents the user might want to view can be recommended from broadcast content and stored content.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
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A viewing recommendation apparatus includes an acquisition unit configured to acquire first broadcast program information for each of first broadcast programs to be broadcasted, a storage unit configured to store a plurality of previously broadcasted second broadcast programs in correspondence with second broadcast program information, a calculation unit configured to calculate an urgency in accordance with the first broadcast program information and the second broadcast program information to obtain a plurality of urgencies, the urgency indicating a degree to view a broadcast program earlier, and a generation unit configured to generate a recommendation list of programs to be viewed based on levels of the urgencies.
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[0001] This application claims priority from German patent application serial no. 10 2008 001 537.7 filed May 5, 2008.
FIELD OF THE INVENTION
[0002] The invention concerns a multi-group transmission of a motor vehicle and a method for operating a multi-group transmission of a motor vehicle.
BACKGROUND OF THE INVENTION
[0003] Multi-group transmissions consist of two or more transmission groups, usually arranged in series, by combining which a large number of gears can be produced. Increasingly, they are designed as automated gearshift transmissions consisting, for example of an input group, a main group and a downstream range group. Such transmissions are used in particular in utility vehicles since they provide an especially fine gradation of gears, for example with 12 or 16 gears, and are highly efficient. For a smaller number of gears configurations with only a main group and an input group or a main group and a range group are also possible. Furthermore, compared with manual gearshift transmissions they are characterized by high operating comfort and, compared with automatic transmissions, their production and operating costs are particularly economical.
[0004] By virtue of their structure conventional multi-group gearshift transmissions, like all manual or automated gearshift transmissions not shifted under load, undergo a traction force interruption during gearshifts since the flow of force from the drive motor is always interrupted by disengaging a clutch in order to disengage the engaged gear without load, to synchronize the transmission and the drive motor in a neutral position to a connection speed, and then to engage the target gear. Since the vehicle is rolling during the traction force interruption, undesired speed increases or speed decreases can occur. In addition the fuel consumption can increase. Whereas with passenger motor vehicles the traction force interruption, which affects the driving dynamics, is as a rule perceived only as annoying, for example during upshifts in a driving style of sporty orientation, in the case of medium-weight or heavy utility vehicles the driving speed can be reduced to the point where an upshift is made impossible and, on uphill stretches, undesired downshifts, creep-driving or even additional starting operations may be necessary.
[0005] From DE 10 2006 024 370 A1 by the present applicant a traction-force-supported automated multi-group transmission with a splitter group as its input transmission, a main group as its basic transmission and a range group as its output or downstream transmission is known. The structure of this known multi-group transmission with its input group and the main group enables a direct gear to be engaged as an intermediate gear during a gear change. For this, a direct connection is temporarily formed between an input shaft of the input transmission and a main shaft of the main transmission by means of a change-under-load clutch. This renders the main transmission and the splitter group free from load, so that the engaged gear can be disengaged, the transmission synchronized and the target gear engaged, during all of which the starting clutch remains engaged. The change-under-load clutch transmits the motor torque to the transmission output, and a dynamic torque that is released during a speed reduction between the original and target gears is used to a large extent to compensate the traction force interruption. The change-under-load clutch can be positioned between the input transmission and the main transmission or between the starting clutch and the input transmission. The gear ratio of the intermediate gear is determined by the direct connection of the input shaft to the main shaft. A shift in the range group is not necessarily traction-force-supported without adopting other measures.
[0006] Moreover, from DE 198 44 783 C1 a method for shifting a gear-change transmission with interlock-type gearwheel clutches is known in which, by means of a gear-synchronizing transmission integrated in the speed-change transmission, optionally by means of a gear stage with ratio i>1 or a gear stage with ratio i<1 a drive connection can be formed between a transmission input shaft and a transmission output shaft. A respective friction clutch is associated with each of the gear stages, which are used during a gearshift operation to adapt the speed of the input shaft to the respective synchronous speed. By controlling the frictional connection between the input and output shafts and/or the drive motor, the speed of the input shaft and the torque variation at the output shaft during the gear change are influenced. A frictional starting element arranged between the drive motor and the input shaft remains engaged during the gearshift operation. Thus, the gearshift is comparable to a change-under-load. The method can be used, by virtue of a suitable alternating use of the frictional connections via one or the other gear stage of the synchronizing transmission, for upshifts or downshifts in traction and thrust operation.
[0007] From EP 1 096 172 A2 an automated change-under-load transmission with unsynchronized gearshift clutches is known. Again, two friction clutches are provided for synchronization. A common flywheel is arranged as a clutch input component between a crankshaft of the drive motor and a transmission input shaft. One synchronization clutch is coupled to the lowest gear stage and used for thrust gearshifts and as a starting element. The other synchronization clutch is coupled to the highest gear stage and used for traction gearshifts. The synchronization clutches are connected on one side via the thrust or traction gears to a transmission output shaft and on the other side via the clutch input component to the transmission input shaft. Synchronization during a gearshift operation, i.e. equalization of the speed of the transmission input shaft with the speed of the gearset of the target gear, takes place by engaging or disengaging the thrust or traction synchronization clutch. During a traction shift the synchronization clutches and the gearshift clutches are actuated in a shift sequence which ensures the transmission of a drive torque to the transmission output shaft, so that the gearshift takes place with no interruption of the traction force. In contrast to the known, traction-force-supported, sequentially shifted double clutch transmissions, this transmission also enables shifts with gear intervals over more than one step to be carried out.
[0008] The two last-mentioned publications each describe a change-speed transmission with change-under-load characteristics. The synchronization clutches described therein, which maintain a torque flow to the drive output, are respectively coupled to the lowest and highest gear stage of the change-speed transmission. However, this solution cannot be easily transferred to a multi-group transmission with a number of transmission groups arranged one after another in the flow of force, and its shift sequence.
SUMMARY OF THE INVENTION
[0009] Against this background the purpose of the present invention is to indicate a multi-group transmission and a method for operating a multi-group transmission which, with comparatively small demands in terms of cost, design and construction effort, and structural space, enable traction-force-maintaining gearshifts to be carried out with further improved shifting comfort.
[0010] The invention is based on the recognition that with the help of electromagnetic clutches, gears, gear constants and/or gear ranges of individual groups of an automated multi-group transmission can be shifted under load or bridged by means of additional gearsets through power-branched intermediate gears in the force flow, in order to compensate or avoid traction force interruptions in shift operations of these groups, so that with such a transmission greater operational comfort is achieved without actuating a starting element during the gear change or even when a separate starting element is omitted entirely.
[0011] Accordingly, the invention starts from a multi-group transmission of a motor vehicle, with at least two transmission groups arranged in the drivetrain, in which means are provided for supporting the traction force during gearshift operations. To achieve the stated objective the invention also provides that at least one electromagnetic clutch made as a change-under-load means is provided, by virtue of which, while bypassing the force flow of at least a main group made as a gear-change transmission, an active connection can be formed between a driveshaft and a main transmission shaft or a transmission output shaft.
[0012] A gearshift is understood to mean a shift operation in which an original gear is disengaged and a target gear is engaged, including also the special case in which the target gear is the same as the original gear so that no gear ratio change takes place. An electromagnetic clutch is understood to be a clutch that can be actuated by the magnetic force of an electromagnet.
[0013] In addition the invention starts from a method for operating a multi-group transmission of a motor vehicle, with at least two transmission groups arranged in a drivetrain, in which traction force supporting means are activated during a gearshift operation. In relation to the method, the stated objective is achieved in that at least by means of an electromagnetic clutch made as a change-under-load means, an active connection can be temporarily formed or maintained between a driveshaft and a main transmission shaft or a transmission output shaft.
[0014] According to the invention, particularly in automated multi-group transmissions with a splitter group having two gear constants as the upstream transmission, a three- or four-gear main group as a basic transmission of countershaft design and a range group of planetary structure as its downstream transmission, for example in a heavy utility vehicle, electromagnetic clutches can be used to good advantage for supporting the traction force. They are noted in particular for their accurate controllability, quick response time and compact structure. Furthermore no additional or large-size oil pump, as sometimes needed with hydraulic clutches for supporting the traction force, is required for actuating the clutch.
[0015] Preferably a transmission of this type is designed with two countershafts, so that in the embodiments described below—when “one” or “at least one” countershaft is mentioned—the sense of this should be extended to two countershafts. Correspondingly, the power is branched via two countershafts.
[0016] According to the invention, during a gearshift an electromagnetic clutch can engage an additional gearset as an intermediate gear, this intermediate-gear gearset being driven by at least one countershaft. In this case the electromagnetic clutch advantageously comprises a pot-like rotor on the drive input side, which encloses an axially displaceable, disk-shaped armature on the drive output side and an electric energizing magnet, such that the rotor mounted to rotate on a shaft on the drive output side is connected in a rotationally fixed manner at its outer wall to a loose wheel of the intermediate-gear gearset and has frictional means on its inner wall on the clutch input side.
[0017] The armature and clutch output side frictional means are arranged fixed on the drive output shaft and the frictional means can move axially relative to one another, so that depending on the current in the energizing magnet or an embedded energizing coil, axial displacement of the armature under the action of magnetic force can bring the frictional means into active contact with one another so that the electromagnetic clutch can transfer torque in a slipping or in a friction-locked mode. An end face of the energizing magnet can function as a pressure plate of the clutch packet, and in that case to increase the contact pressure force a ball ramp device known per se can advantageously be provided. In principle, other electromagnetically actuated clutch structures are also possible.
[0018] The intermediate-gear gearset with the electromagnetic clutch can be arranged downstream from the main group, and a fixed wheel fitted in a rotationally fixed manner on the countershaft is in that case engaged with a loose wheel mounted to rotate on a main transmission shaft, such that the loose wheel can be connected in a rotationally fixed manner by means of the electromagnetic clutch to the said main transmission shaft on the drive output side of the main group. This arrangement is structurally particularly compact.
[0019] Also advantageous is an arrangement in which, by virtue of axially extended countershafts, the intermediate-gear gearset with the electromagnetic clutch are arranged downstream from the range group, and in that case a fixed wheel mounted rotationally fixed on the countershaft is engaged with a loose wheel mounted to rotate on the transmission output shaft, the said wheel being able to be connected rotationally fixed to the transmission output shaft by means of the electromagnetic clutch. In this case the traction force support also includes a shifting of the range group during the gear change, regardless of whether or not the range group is designed to be able to change under load or whether or not the main transmission shaft is directly connected to the transmission output shaft.
[0020] Furthermore it can be provided that the splitter group has two gear constants, a further respective electromagnetic clutch being associated with each gear constant, by means of which the gear constants can be shifted under load. The electromagnetic clutches replace the usual synchronized shift mechanisms for engaging the gear constants. In this way, on the one hand a traction force interruption while shifting between the gear constants is avoided. On the other hand the electromagnetic clutches of the splitter group can also be used as starting elements so that a separate, conventional starting element can be omitted, this additionally having a cost, space and weight saving effect.
[0021] The shift-under-load function and the starting function can advantageously be obtained if the electromagnetic clutch of the first gear constant on the motor side, has an armature arranged so that it can be axially displaced on the driveshaft and a rotor surrounding the armature, which is connected in a rotationally fixed manner to a loose wheel of the first gear constant and arranged together with the wheel to rotate on the driveshaft, and an energizing magnet, while the electromagnetic clutch of the second gear constant, on the transmission side, has an axially displaceable armature arranged on the driveshaft and a rotor surrounding the armature, which is connected in a rotationally fixed manner to a loose wheel of the second gear constant and arranged together with the wheel to rotate on the driveshaft, and an energizing magnet, such that on the driveshaft respective frictional means arranged on the clutch input side, and on the rotors respective frictional means arranged on the clutch output side, can be brought into mutual frictional engagement, so that the loose wheels can be connected, selectively and alternately, in a rotationally fixed manner to the driveshaft. For this, the electromagnetic clutches can be engaged or disengaged one after the other or with an overlap.
[0022] In a preferred embodiment of the method according to the invention it is provided that in a gearshift involving a shift operation within the main group, the intermediate-gear gearset is engaged as an intermediate gear by means of the associated electromagnetic clutch, whereby the intermediate gear, bypassing the force flow of the main group, forms an active connection between the driveshaft and the main transmission shaft or the transmission output shaft. This enables traction upshifts or downshifts to be carried out with no interruption of the traction force. By engaging the intermediate gear the main transmission is rendered free from load and can therefore be shifted. The gearshift clutch of the original gear in the main transmission preferably remains engaged until the shift to the target gear has been made. Rather, the electromagnetic clutch on the additional, intermediate-gear gearset supports the motor torque at the drive output in its slipping condition, while the motor speed is adapted to the target gear selected.
[0023] Since by means of an appropriate intermediate gear the rotating masses to be synchronized can be braked, the transmission brake usually provided for braking those masses during upshift processes can be omitted, whereby further costs, space and weight are saved. Only for a shift process is the gearshift clutch of the original gear engaged in the main transmission disengaged, and the desired target gear is engaged when the synchronous speed has been reached. Thereafter the electromagnetic clutch is disengaged again and the force flow is then transmitted via the new gear.
[0024] Such traction-force-supported gear changes are also possible with gear intervals covering two or more gear steps. Since the drivetrain remains under load throughout the gear change by virtue of the intermediate gear, fluctuations and jerky shifts are also reduced, which results in an additional improvement of the shifting comfort.
[0025] In further preferred version of the method according to the invention it is provided that during a gear change involving a shift operation within the splitter group, a shift is carried out by means of the associated electromagnetic clutches between the gear constants, such that an active connection is preserved between the driveshaft and the main transmission shaft or the transmission output shaft. Accordingly, gear changes in which shifting only occurs between the gear constants are carried out directly under load by means of the electromagnetic clutches of the splitter group, so that in this case an engagement of an intermediate gear can be omitted.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] To clarify the invention the description of a drawing with two example embodiments is attached. The drawings show:
[0027] FIG. 1 : Transmission layout of a multi-group transmission of a motor vehicle with electromagnetic clutches for traction-force-supported shift operations
[0028] FIG. 2 : A second embodiment of a multi-group transmission with electromagnetic clutches
[0029] FIG. 3 : Schematic representation of an electromagnetic clutch for engaging an intermediate gear, drawn on a larger scale, and
[0030] FIG. 4 : Two more electromagnetic clutches for shifting a splitter transmission, drawn on a larger scale.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0031] FIG. 1 shows an automated multi-group transmission designed as a dual-countershaft transmission 1 , with two parallel rotating countershafts 8 , 9 and three transmission groups 2 , 3 and 4 arranged one after another, as can be provided for example in the drivetrain of a truck. Such a transmission, as such, i.e. without traction force support, is known in particular from the ZF-AS Tronic series, and with traction-force-supporting direct gear engagement from DE 10 2006 024 370 A1 by the present applicant, mentioned earlier.
[0032] The first transmission group 2 , located on the motor side, is formed as a two-gear splitter group. The second, central transmission group 3 consists of a three-gear main or basic transmission. The third, output-side transmission group 4 is a two-gear range group arranged on the downstream side.
[0033] The splitter group 2 has two gear constants i k1 , i k2 , each comprising a fixed wheel 10 , 12 or 13 , 15 respectively arranged rotationally fixed on the first countershaft 8 and on the second countershaft 9 , these wheels meshing with a respective loose wheel 11 or 14 . To engage the gear constants i k1 , i k2 , in each case an electromagnetic clutch 5 or 7 , to be described in detail later, is provided, by means of which the loose wheels can optionally be connected rotationally fixed to a driveshaft 6 of a drive motor (not shown). By means of these electromagnetic clutches 5 , 7 the splitter group can be shifted under load, i.e. the gear constants i k1 , i k2 can be switched between without interruption of the drive input. The electromagnetic clutches can also be used as starting elements and are therefore correspondingly sized.
[0034] The main transmission 3 has three forward gears i 1 , i 2 and i 3 and a reverse gear i R . The 1 st and 2 nd gears each have two fixed wheels 18 , 20 or 21 , 23 and a loose wheel 19 or 22 . The 3 rd gear is produced in combination with the second gear constant i k2 , of the splitter transmission 2 . The reverse gear comprises two fixed wheels 24 , 28 , a loose wheel 26 and two rotating intermediate wheels, 25 , 27 for reversing the rotation direction, which mesh on one side with the respective associated fixed wheel 24 or 28 and on the other side with the loose wheel 26 . To engage the 1 st gear and the reverse gear a shift device 29 with shifting claws is provided, by means of which the associated loose wheel 19 or 26 can selectively be connected rotationally fixed to a main transmission shaft 30 . To engage the 2 nd gear and the 3 rd gear a claw-type shift device 31 is provided, by means of which the respective associated loose wheel 14 or 22 can selectively be coupled rotationally fixed to the main transmission shaft 30 .
[0035] The downstream range transmission 4 is made as a planetary transmission.
[0036] In it, a planetary gearset 32 is guided by a planetary gear carrier 33 . The planetary gearwheels mesh on one side with a central sun gear 34 and on the other side with an outer ring gear 35 . The sun gear 34 is connected to the main transmission shaft 30 and the planetary gear carrier 33 to a transmission output shaft 36 . To shift the range transmission 4 a shifting device 37 , preferably with synchronization, is provided. In a first shift position this shifting device 37 connects the ring gear 35 to a housing 38 , so that the planetary gears rotate between the ring gear 35 and the sun gear 34 and, in accordance with the gear ratio, the transmission output shaft 36 is driven by the planetary gear carrier 33 in the same direction as the main transmission shaft 30 . In a second shift position the ring gear 35 is locked to the planetary gear carrier 33 , so that the planetary transmission 4 and hence the transmission output shaft 36 rotate directly at the same speed as the main transmission shaft 30 .
[0037] The combination of the transmission groups 2 , 3 and 4 shown in the transmission layout illustrated gives a total of 2×3×2=12 gears. The force flow of the transmission 1 branches according to a shift sequence in which, beginning with the 1 st gear in the main transmission 3 , first the splitter transmission 2 and the main transmission 3 are shifted through in alternation so that, in succession, 2×3=6 gears of a lower gear range “1 st to 6 th gears” are engaged. When the 6 th gear is reached the range transmission 4 is shifted over, and the main transmission 3 and splitter transmission 2 are again shifted through in alternation so that, again 2×3=6 gears, but this time in an upper gear range. “7 th to 12 th gears” are engaged. The upstream splitter group 2 also engages the reverse gear ratio i R in alternation, so that in addition two reverse gears are available.
[0038] Between the main transmission 3 and the range transmission 4 is arranged an additional gearset 17 as an intermediate gear, which can be engaged by means of an electromagnetic clutch 16 . The intermediate-gear gearset 17 comprises two fixed wheels 39 and 41 mounted on the countershafts 8 and 9 , which are engaged with a loose wheel 40 on the main transmission shaft 30 . The loose wheel 40 is connected to the electromagnetic clutch 16 by which it can be connected in a rotationally fixed manner to the main transmission shaft 30 .
[0039] FIG. 2 shows a comparable dual-countershaft transmission 1 ′ with an intermediate-gear gearset 17 ′ and an electromagnetic clutch 16 ′, which are arranged behind the range group 4 , i.e. directly on the transmission output. In addition the countershafts 8 ′, 9 ′, are extended axially beyond the range group 4 . The intermediate-gear gearset 17 ′ comprises two fixed wheels 39 ′, 41 ′ mounted on the countershafts 8 ′, 9 ′, which engage with a loose wheel 40 ′ on the transmission output shaft 36 . The loose wheel 40 ′ is connected to the electromagnetic clutch 16 ′ by means of which it can be connected in a rotationally fixed manner to the transmission output shaft 36 .
[0040] FIGS. 3 and 4 show the electromagnetic clutches 5 , 7 , 16 , 16 ′ in detail. FIG. 3 shows the electromagnetic clutch 16 , 16 ′ of the intermediate-gear gearset 17 , 17 ′. The clutch drive, i.e. its input side, is formed as a pot-like rotor 42 connected in a rotationally fixed manner to the loose wheel 40 , 40 ′ of the intermediate-gear gearset 17 , 17 ′. On its inside the rotor 42 has an annular friction disk 43 . The clutch output, i.e. the output side, is made as a disk-shaped armature 44 mounted in a rotationally fixed manner but able to move axially on the main transmission shaft 30 or the transmission output shaft 36 . In addition, two friction disks 45 , 46 , are arranged so that they axially enclose the input-side friction disk 43 . The corresponding friction disks 43 , 45 , 46 can move axially relative to one another.
[0041] Coaxially thereto is arranged a cup-shaped energizing magnet 47 with an energizing coil (not shown), with a ball ramp device 48 arranged in front of one end to increase the contact pressure. The rotor 42 , armature 44 , frictional means 43 , 45 , 46 and energizing magnet 47 together form a clutch packet, so that when current flows in the energizing magnet 47 a correspondingly strong magnetic field produces an engaged condition in which the frictional means 43 , 45 , 46 are locked together frictionally or, depending on the degree of engagement, they act in a slipping mode, and in the disengaged condition when the magnetic field is switched off, they are separated from one another by restoring means (not shown).
[0042] FIG. 4 shows the electromagnetic clutches 5 , 7 of the splitter group 2 . These are arranged in diametrically mirrored positions on the driveshaft 6 so that one clutch 5 is associated with the first gear constant i k1 and the other clutch 7 with the second gear constant i k2 . The structure of the two splitter group clutches 5 , 7 is comparable to that of the intermediate gear clutch 16 , 16 ′, although the input and output sides are reversed, i.e. the drive input is from the driveshaft 6 and the drive output takes place via the respective loose wheel 11 or 14 of the gear constant i k1 or i k2 .
[0043] The clutch 5 associated with the first gear constant i k1 comprises a rotor 49 with output-side friction means 50 on the outside, which is connected in a rotationally fixed manner to the associated loose wheel 11 , an armature 51 with associated, input-side frictional means 52 , 53 and an energizing magnet 54 with a ball ramp device 55 .
[0044] The clutch 7 associated with the second gear constant i k2 comprises a rotor 56 with friction means 57 on the outside, which is connected in a rotationally fixed manner to the associated loose wheel 14 , an armature 58 with associated, input-side frictional means 59 , 60 and an energizing magnet 61 with a ball ramp device 62 . On the output-side end face facing toward the main group 3 the rotor 56 is connected to the shifting device 31 of the 2 nd and 3 rd gears of the main group 3 (see FIG. 1 ).
[0045] A method according to the invention for operating the multi-group transmission described is based essentially on the engagement of an intermediate gear, by which the traction force of the vehicle is maintained while the main group 3 is in neutral during a gearshift operation. According to this, for example in an upshift with a shift operation in the main group 3 , to engage an intermediate gear the electromagnetic clutch 16 , 16 ′ of the intermediate-gear gearset 17 , 17 ′ is controlled so as to operate in slipping mode. This transmits the motor torque to the main transmission shaft 30 or directly to the transmission output shaft 36 .
[0046] Consequently, the main transmission 3 is freed from load. During this torque transmission by the slipping electromagnetic clutch 16 , 16 ′ of the intermediate-gear the motor speed is reduced to a synchronous speed of a target gear. The torque released by this speed reduction is used for maintaining the traction force. The shift from the original gear to the target gear then takes place, and finally the electromagnetic clutch 16 , 16 ′ is disengaged.
[0047] If the splitter group 2 is not involved in the gearshift operation, drive input takes place via the engaged gear constant, i k1 , i k2 and the countershafts, 8 , 8 ′, 9 , 9 ′ bypassing the main group 3 , to the intermediate-gear gearset 17 , 17 ′. If, however, the shift operation involves a shift in the splitter group 2 , then this takes place under load by virtue of the associated electromagnetic clutches 5 , 7 , i.e. in a change between the gear constants i k1 , i k2 the torque connection to the drive motor is maintained in any case.
[0048] In the case of an intermediate-gear gearset 17 ′ arranged downstream from the range group 4 a shift of the gear range is automatically traction-force-supported.
[0049] On the other hand, if the intermediate-gear gearset 17 is upstream from the range group 4 , additional measures may sometimes be needed for traction force support.
List of indexes
[0000]
1 , 1 ′ Two-countershaft transmission, multi-group transmission
2 Splitter transmission
3 Main transmission
4 Range transmission
5 Electromagnetic clutch
Driveshaft
7 Electromagnetic clutch
8 , 8 ′ Countershaft
9 , 9 ′ Countershaft
10 Fixed wheel
11 Loose wheel
12 Fixed wheel
13 Fixed wheel
14 Loose wheel
15 Fixed wheel
16 , 16 ′ Electromagnetic clutch
17 , 17 ′ Intermediate-gear gearset
18 Fixed wheel
19 Loose wheel
20 Fixed wheel
21 Fixed wheel
22 Loose wheel
23 Fixed wheel
24 Fixed wheel
25 Intermediate wheel
26 Loose wheel
27 Intermediate wheel
28 Fixed wheel
29 Shift device
30 Main transmission shaft
31 Shift device
32 Planetary gearset
33 Planetary gear carrier
34 Sun gear
35 Ring gear
36 Transmission output shaft
37 Shift device
38 Housing
39 , 39 ′ Fixed wheel
40 , 40 ′ Loose wheel
41 , 41 ′ Fixed wheel
42 Rotor
43 Friction means
44 Armature
45 Friction means
46 Friction means
47 Energizing magnet
48 Ball ramp device
49 Rotor
50 Friction means
51 Armature
52 Friction means
53 Friction means
54 Energizing magnet
55 Ball ramp device
56 Rotor
57 Friction means
58 Armature
59 Friction means
60 Friction means
61 Energizing magnet
62 Ball ramp device
i k1 Splitter group gear constant
i k2 Splitter group gear constant
i 1 Main transmission gear
i 2 Main transmission gear
i 3 Main transmission gear
i R Main transmission reverse gear
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A multi-group transmission of a motor vehicle which includes at least two transmission groups arranged in a drivetrain and a way for supporting traction force during gearshifts such that traction-force gearshifts are maintained with improved shifting comfort at comparatively low cost, little design effort and compact installation space demands. At least one electromagnetic clutch is a change-under-load unit by which, bypassing the force flow of at least one main group made as a gear-change transmission, an active connection can be formed between a driveshaft and a main transmission shaft or a transmission output shaft. During a gearshift operation, an active connection is temporarily made between a driveshaft and a main transmission shaft or a transmission output shaft by way of at least one electromagnetic clutch designed as a change-under-load unit.
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FIELD OF THE INVENTION
This invention relates to a method of manufacturing molded paper pulp articles and, more particularly, to a method of manufacturing molded paper pulp articles having improved strength, surface characteristics and greater physical properties.
BACKGROUND OF THE INVENTION
With the general public becoming more environmentally aware and the cost of energy sources increasing, recycling of various products has been steadily gaining favor with various industries. Certain products, such as glass and plastic containers, lend themselves to recycling because of their ability to maintain their physical integrity and their mechanical properties during their use. However, the initial cost of manufacturing these types of containers is high due to the cost of the raw materials and the complicated manufacturing processes necessary for forming them.
Vast quantities of paper products are consumed daily in modern society. However, due to the perishability of these paper products and the limited use that can be made of these paper products upon reclamation, extensive utilization of reclaimed paper products has not yet been realized. Although various processes are currently available for utilizing recycled paper in the form of pulp, molded products produced by these processes are limited in the complexity of their form and structure and do not offer satisfactory surface characteristics and physical properties.
U.S. Pat. No. 1 324 935 discloses a process for forming hollow articles, such as bottles, jars, cases, boxes and similar containers, tubes and like structures, from fibrous material held in suspension. In this reference, a fibrous material or pulp held in suspension in a liquid is deposited on a forming mold and then preliminarily dried before entering into a pressing step where the pulp is formed into a finished article. However, the process of this patent is limited to the production of simple, uncomplicated articles.
U.S. Pat. No. 2 023 200 shows a method for making molded pulp containers having smooth internal and external surfaces and optionally providing ribs either in the inner or outer surfaces of the container. The process of this reference also involves the separation of paper or wood pulp out of a solution and onto a forming mold and the preliminary drying of the pulp to a water content of between 45 to 55 percent by weight before a final compression state. Although the articles produced by the process disclosed in this reference can have crude detailing, such as ribs formed thereon, the provision of more sophisticated detailing, such as threads on the articles, is not possible.
U.S. Pat. No. 2 369 488 discloses a method of manufacturing hollow articles, such as a textile winding core or cone, out of paper pulp which have a core whose outer surface is of sufficient strength to withstand a thread being wound therearound. The paper pulp is mixed with a binder and, optionally, other additives before being deposited on a rotating former to form an embryo cone. The embryo cone is then subjected to a preliminary compacting step to reduce the water content thereof and then to compacting, densifying and shaping operations. Although this reference discloses the manufacture of a hollow article out of paper pulp which is capable of supporting a thread wound on the surface thereof, it is necessary that a binder and, optionally, other additives be added to the paper pulp in order to provide a paper article having the physical properties necessary for the desired purposes.
U.S. Pat. No. 2 986 490 discloses a method for making molded pup articles in which wet molded articles having a moisture content varying from about 10 percent to 75 percent are subjected to a drying and finishing operation between a set of complemental heated pressing dies. However, this method is incapable of producing molded paper products having the improved physical characteristics of the present invention.
U.S. Pat. No. 4 491 502 discloses a method of making a molded paper container, such as a dish or tray, from a paperboard sheet in which a formed sheet is dried to a water content in the range of from about 50 to about 100 percent by weight and then subjected to pressing and drying in a matched metal die set. Although the molded paperboard product of this method is said to have improved strength characteristics, the process of this patent is incapable of producing paper articles having complex configurations.
Therefore, an important object of the present invention is to provide a method capable of producing a molded paper pulp article having an improved surface appearance and superior mechanical and physical properties.
A further object is to provide a relatively simple and inexpensive method for forming a molded paper pulp article having improved surface characteristics, improved mechanical properties and which can be formed into complex structures and recycled.
SUMMARY OF THE INVENTION
The objects and purposes of the invention, including those set forth above, are met according to the invention by providing a method which includes the steps of forming a slurry of paper pulp in water, inserting a foranimous mold into the slurry, pulling a vacuum on the foranimous mold so that a layer of wet paper pulp is deposited thereon, removing the foranimous mold with the deposited layer of wet paper pulp from the slurry, separating the deposited layer of wet paper pulp from the foranimous mold and compressing the layer of wet paper pulp having a solids content of from 5 to 20 percent by weight in such a manner that the wet paper pulp is shaped in the form of the molded paper article and the water content thereof is reduced.
The objects and purposes of this invention are also met by providing a process for manufacturing a molded paper article which includes the steps of preparing a slurry of paper pulp in water, inserting a foranimous mold into the slurry, pulling a vacuum on the foranimous mold so that a layer of wet paper pulp is deposited thereon, removing the foranimous mold with the deposit layer of wet paper pulp from the slurry, optionally conducting a premolding step, optionally conducting a predrying step, separating the deposited layer of wet paper pulp from the foranimous mold, compressing the layer of wet paper pulp having a solids content of from 5 to 20 weight percent in such a manner that the wet paper pulp is shaped into the form of the molded paper article and the water content thereof is reduced and drying the wet paper pulp article to form the product molded paper article.
The objects and purposes of the invention are also met by providing a molded paper article having improved surface appearance characteristics, superior mechanical and physical properties and which can be provided in a complex form.
BRIEF DESCRIPTION OF THE DRAWINGS
An embodiment of the inventive method and article will be described in detail hereinafter with reference to the accompanying drawings, in which:
FIG. 1 is a diagram illustrating the process steps of a first embodiment of the present invention;
FIG. 2 is a diagram illustrating the process steps of a second process according to the present invention;
FIG. 3 is a sectional view of a female pressing die which can be used in the present invention;
FIG. 4 is an illustration of a male pressing member which can be used in the present invention; and
FIG. 5 is a partial sectional view showing the compression of pulp between the male pressing member and female pressing die shown in FIGS. 3 and 4.
FIG. 6 is an exploded view of a molded paper article of the present invention.
FIG. 7 is an exploded view showing the interengagement between a split female pressing die, the male pressing member and a retaining ring.
DETAILED DESCRIPTION
Referring to FIG. 1, the process of the present invention begins with the formation of a slurry 1 made up of paper pulp and water. The source of the paper pulp is not particularly limited and may be blank newsprint, inked or de-inked newsprint, unbleached soft wood kraft or any other commercially available type of paper stock, including paper mill sludge or any combination of fiber sources. The solids content in the slurry 1 is typically in the range of from 0.1 percent to about 3 percent by weight solids. A solids content of 0.6 percent by weight is particularly preferred in the present invention. The temperature of the slurry is not critical and it is preferably provided at ambient temperatures. However, it must be kept in mind that the colder the temperature of the slurry, the more difficult it will be to deposit the pulp on the forming mold 2 in the subsequent step because of the increased viscosity of the slurry 1.
A forming mold 2 is then inserted into the slurry 1 and a vacuum applied to the forming mold. The forming mold 2 is of the same general configuration as the finished product molded paper pulp article and foranimous in order that the paper pulp will deposit upon the surface thereof from the slurry 1 due to the application of the vacuum. The amount of vacuum to be used to cause the deposition of the paper pulp onto the forming mold 2 will depend on process considerations such as the temperature of the water in the slurry 1, the type of paper pulp provided in the slurry 1 and the product article being produced and is readily determined by one of ordinary skill in the art. At a slurry content of about 0.6 percent by weight solids and a temperature of 85° F., a vacuum applied to the forming mold 2 of 21 inches mercury has been found to be satisfactory. During production, it is best that a slurry 1 of a fixed consistency is used so that the amount of pulp deposited on the forming mold 2 can be readily determined according to the volume of liquid separated from the slurry 1.
After a layer of wet paper pulp 7 has built upon the forming mold 2 at the desired thickness, the forming mold 2 is removed from the slurry 1 and transferred to a female pressing die 3 having a cavity 6 formed therein. The cavity 6 is also provided in a similar configuration of the finished product molded paper article to be produced. The forming mold 2 is lowered into the cavity 6 and the layer of wet paper pulp 7 transferred to the walls of the cavity 6 from the forming mold 2 by the application of a positive air pressure to the forming mold 2. At this stage of the presently claimed process, the layer of wet paper pulp contains from about 5 to about 20 percent by weight solids. In order to aid in the removal of the finished product molded paper article from the female pressing die cavity 6, the female pressing die can be made of separable halves, as illustrated in FIG. 7, in order to facilitate the release of items with negative release angles, sharp curves or abrupt changes in surface orientation. The separable halves are joined together during the pressing step and separated from each other to release the finished product molded paper article.
As shown in FIG. 2, optionally, a premolding step can be performed before the layer of wet paper pulp 7 is delivered to the female pressing die cavity 6. In the premolding step, the vacuum that is applied to the forming mold 2 during the deposition of the layer of wet paper pulp 7 on the forming mold 2 from the slurry 1 is continued after the forming mold 2 is removed from the slurry 1. This continuous application of vacuum can increase the solids content of the layer of wet paper pulp from about 5 to 7 percent solids to about 12 to 15 percent solids. By the continuous application of vacuum to the forming mold, the layer of wet paper pulp 7 is caused to more closely pack to the forming mold 2 and approximate the shape thereof.
As is also illustrated in FIG. 2, in addition to or in place of the premolding step, a predrying step can be performed before the introduction of the layer of wet paper pulp 7 into the female pressing die cavity 6. The predrying step involves the introduction of a warm gas, such as air, into contact with the layer of wet paper pulp 7 while it is still adhered to the forming mold 2. In the present invention, the solids content of the wet paper pulp layer 7 can be raised up to 20 percent by weight solids if desired. The warm gas can be introduced into contact with the internal surfaces of the layer of wet paper pulp 7 either through the connection for supplying the vacuum to the forming mold 2 or directed at the outer surfaces of the layer of wet paper pulp 7 from an external heating source (not shown). After the premolding and/or predrying steps, the layer of wet paper 7 pulp is then transferred to the female pressing die cavity 6 as discussed above.
As shown in FIG. 1, the layer of wet paper pulp 7 is transferred into the cavity 6 in a manner such that the walls thereof are in substantial alignment with the walls of the cavity 6. That is, the layer of wet paper pulp 7 is deposited into the cavity of the female pressing die 6 in such a manner that the layer of wet paper pulp contacts with the walls of the cavity 6 along the length thereof. At this stage of the inventive process, the solids content of the layer of wet paper pulp 7 is approximately from 5 to 20 percent by weight solids, more preferably 10 to 15 percent by weight solids.
After the layer of wet paper pulp 7 has been deposited in place onto the walls of the female die cavity 6, a male pressing member 8 is inserted into the cavity 6 in such a manner that the layer of wet paper pulp is confined and compressed between the walls of the female pressing die cavity 6 and the male pressing member 8. The male pressing member 8 can be operated by any conventional source, such as pneumatic or hydraulic pressure, and is extendible into and retractable from the female pressing die cavity 6. The male pressing member 8 is provided in the form of the finished product molded paper article and by application of pressure to the layer of wet paper pulp 7 from the male pressing die 8, the layer of wet paper pulp 7 is molded into the shape of the product molded paper article while being constrained in the female pressing die cavity 6. Due to the low solids content of the layer of wet paper pulp 7, the layer 7 readily conforms to the shape of the die cavity 6 and the pressing member 8.
During this pressing step, the solids content of the layer of wet paper pulp 7 can be increased up to 55 percent by weight solids. In order to aid in the removal of water from the layer of wet paper pulp 7, the male pressing member 8 and the female pressing die 6 may be perforated and connected with a source of vacuum in order to more easily transport the water away from the layer of wet paper pulp 7.
It has also been discovered that the placing of a wire screen between the surface of the wet paper pulp layer 7 and the surface of the male pressing member 8 and/or the female pressing die 6 can, in some applications, greatly increase the rate of water removal from the wet paper pulp layer 7. Although this phenomena is not completely understood, it is believed that the wire screen maintains the fibers of the wet paper pulp layer 7 in order and prevents them from blocking the drainage paths in the wet paper pulp layer 7. The mesh size and the overall size of the wire mesh is not critical and can be readily determined depending on the process conditions.
After the layer of wet paper pulp 7 has been molded into the desired configuration, it can then be sent to an oven for final drying. The layer of wet paper pulp 7 is preferably dried while still being confined between the female pressing die cavity 6 and the male pressing member 8 in order to avoid warpage in the molded paper article. In a preferred embodiment of the present invention, the female pressing die 3 and the male pressing member 8 are heated and the layer of wet paper pulp 7 is pressed, dried and vacuumed simultaneously. When the pressing and drying steps are conducted simultaneously, the final solids content of the molded paper article is raised to about 75 to 90 percent by weight solids.
As discussed above, the process of the present invention can be used to prepare molded paper articles having a surface appearance and detailing far superior to those articles produced by conventional processes. As illustrated in FIG. 6, the process of the presently claimed invention is capable of producing a paper container 11 of sufficient strength and detailing that a thread 12 can be provided on an upper portion 13 that is distinct and strong enough for a threaded cap (not shown) to be removably secured thereto.
For the preparation of the threaded container upper portion 13, the female pressing die 3 is provided in the form illustrated in FIG. 4. The female pressing die cavity 6 is provided in two portions; a frustum-shaped upper portion 16 and a cylindrically shaped lower portion 17. Grooves 18 are provided in the walls of the female pressing die cavity cylindrically shaped lower portion 17 and are used to provide the threads 12 in the container upper portion 13. In the female pressing die 3 illustrated in FIG. 4, a retaining ring 21 is provided in a slot 22 formed in a lower support member 32 thereof. A central opening 23 is provided in the retaining ring 21 and, as illustrated in FIG. 5, functions to center the male pressing member 8 in the female pressing die cavity 6 during the compression of the layer of wet paper pulp 7. In place of the retaining ring 21, an opening can be provided at the bottom of the female pressing die 3 to center the male pressing member 8.
The male pressing member 8 used in producing the threaded container upper portion 13 is illustrated in FIG. 4. This male pressing member 8 comprises a frustum-shaped upper portion 26 and a cylindrically shaped lower portion 27. Additionally, a bevelled intermediate portion 28 of the male pressing member is provided just above and adjacent to the cylindrical portion 27. With the inclination of the bevelled intermediate portion 28, the layer of wet paper pulp 7 adjacent to the grooves 18 in the female pressing die 3 is pressed more firmly into contact with the grooves 18 during the compression of the layer of wet paper pulp 7 between the male pressing member 8 and the female pressing die 3 as illustrated in FIG. 5. With the low solids content of from 5 to 20 weight percent in the wet paper pulp layer 7, the layer 7 is fluid enough to assume the exact dimensions and shape of the grooves 18 and thereby provide a molded paper article having clearly defined threads.
After the compressing and drying stages, the threaded container upper portion 13 is provided. The container bottom 28 can be produced in a similar fashion using suitable male and female pressing die members and the container body 31 formed by rolling a sheet of paper into a cylinder of the desired shape. The container upper portion 13, the container body 31 and the container bottom 28 are then adhered to each other by a suitable adhesive to produce the threaded paper container 11.
As discussed above, the present invention can be used to provide molded paper articles of any desired configuration. That is, many articles made of plastic that are currently vacuum-formed or injection-molded can be made from paper using the process of the present invention.
The present invention will be further illustrated by the following examples and comparative examples.
EXAMPLE 1
A fiber slurry was prepared made up of 0.6 percent by weight solids. The solids consisted of 25 percent by weight unbleached soft wood kraft and 75 percent by weight newsprint blank. The slurry was agitated in order to assure the uniform distribution of the paper pulp in the water and the slurry temperature was maintained at 85° F. A forming mold was inserted into the slurry and a vacuum of 21 inches mercury was pulled thereon for 1 minute and 45 seconds in order to deposit a layer of wet paper pulp made up of 7 percent by weight solids on the forming mold. The forming mold with the layer of wet paper pulp adhering thereto was then transferred to a female pressing die and the layer of wet paper pulp transferred from the forming mold to the cavity of the female pressing die through the application of a positive pressure to the forming mold. A male pressing member was then inserted into the die cavity and the layer of wet paper pulp, at an initial solids content of 7 percent by weight, was compressed between the die cavity and the male pressing member. The layer of wet paper pulp was pressed to a solids content of 60 percent by weight and then transferred to an oven for final drying. The finished product molded paper article had an unblemished smooth surface and clearly defined threads provided thereon.
EXAMPLE 2
The process of Example 1 was repeated under identical conditions except that a premolding step was performed to increase the solids content of the wet paper pulp layer to 14 percent by weight before the introduction of the wet paper pulp layer into the die cavity. The finished product paper article also had an unblemished smooth surface and clearly defined threads provided thereon.
EXAMPLE 3
The process of Example 2 was repeated except that a predrying step was performed in addition to the premolding step to increase the solids content of the layer of wet paper pulp to 18 percent by weight before its introduction into the die cavity. The finished product paper article had a smooth unblemished surface and clearly defined threads provided thereon.
COMPARATIVE EXAMPLE 1
The process of Example 3 was repeated except that the layer of wet paper pulp was predried to a solids content of 21 percent by weight before its introduction into the die cavity. The finished product paper article had a rough surface with cracks provided therein and the thread detailing was irregular.
COMPARATIVE EXAMPLE 2
The process of Example 3 was repeated except that the layer of wet paper pulp was predried to a solids content of 24 percent by weight before its introduction into the cavity of the female pressing die. The surface appearance of the finished product molded article was very rough with numerous cracks and uneven portions provided therein and the thread detailing was very poor.
Certain articles may be transferred to a male member and pressed by the female member. This is determined by the geometry of the product to be produced.
Although particular preferred embodiments of the present invention have been disclosed in detail for illustrative purposes, it should be recognized that variations or modifications of the disclosed invention, including variation of process steps, lie within the scope of the present invention.
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A method of manufacturing a molded paper pulp article from a fiber slurry involves the vacuum deposition of a layer of wet paper pulp onto a forming mold, the separation of the wet layer of paper pulp from the forming mold and the pressing and shaping of the layer of wet paper pulp at a solids content of from about 5 to 20 percent solids. A finished product molded paper article is prepared having improved surface appearance and detailing and improved mechanical and physical properties.
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FIELD OF THE INVENTION
[0001] This invention relates to food formulations and particularly the reduction of calories without concomitant loss of mouth feel, flavor and texture.
BACKGROUND OF THE INVENTION
[0002] A low or reduced calorie product, such as chips, crackers, cookies, cakes, muffins, brownies, breakfast cereals, pasta, and the like, of a good taste has been the elusive dream of formulators for many years.
[0003] Despite the obvious desirability of these products, technological limitations have prevented food manufacturers from bringing such products to market. These limitations manifest themselves in unacceptable taste or texture, or negative effects on digestion. It is the object of this invention to delineate the existing limitations in the current art, and provide a method by which to overcome the limitations of the current art, and create acceptable products with significant calorie reduction. This reduction is defined as in excess of 30% of the standard product (i.e. below about 3.25 calories per gram on a dry weight basis, as will be explained herein).
[0004] One of the easiest paths to caloric reduction is achieved by retaining elevated levels of moisture in the final product. For example, standard white bread often exhibits a caloric value of a mere 2.6 calories per gram, simply due to its high moisture content, which approaches forty percent. Other products such as muffins (again close to 40% moisture), sponge cakes (30% moisture), and doughnuts (35% moisture) continue to bear out this trend. However, this represents a false caloric savings to the consumer, and is no more effective than drinking additional water with the product. Without providing a greater degree of satiation, the consumer will simply be hungry sooner, and will end up consuming the same or greater number of calories eventually.
[0005] Since moisture levels for baked goods such as cookies, muffins and cakes can vary dramatically between categories, and even between individual formulations within the same category, it is impossible to evaluate the true caloric reduction by looking at the published, FDA-mandated, caloric values of the finished product, since they are based solely on the calories per gram on a non-dry weight basis. Rather, the most appropriate measure to determine caloric reduction is by examining the calories per gram on a dry weight basis. This value can be obtained by dividing the total number of calories of the constituent ingredients, by the total weight in grams of the constituent ingredients less the total weight in grams of the moisture of the constituent ingredients. The term “calorie” in the context of this invention is understood to refer to the kilocalorie unit of energy, also known as the large or food calorie, which is equal to 4.186 kilojoules or one thousand thermal energy calories, and is the energy necessary to raise the temperature of one kilogram of water by one degree Celsius (1.8 degrees Fahrenheit).
[0006] One inherent difficulty in creating a low-calorie product is that there are very few raw ingredients with which to work. All common ingredients used in baking manufacture have a relatively high caloric value, on a per-gram basis. For instance, flour, sugar, and starch are all carbohydrates, and, as such, each contains approximately four calories per gram. Any proteins will also provide four calories per gram, while fats and oils provide nine calories per gram. Therefore, in a basic formulation, even if the amount of fat is greatly reduced or even entirely removed, there will still be approximately 110 calories for a 28 gram (1 ounce) serving (28×4=112), on a dry weight basis.
[0007] There is much prior art embodied in many patents, dating back to the 1950's, which have focused on creating a large variety of low-calorie products. Although a plethora of raw ingredients have been suggested, which could, under the proper conditions, possibly produce a truly low calorie product, when it comes to actual practice and specific examples, the limitations of the use of the ingredients become apparent. In all these patents, which were attempting to create lower-calorie baked goods, such as muffins, doughnuts, cakes, cookies, and the like, the examples presented consistently only offered products with a resultant calorie count on a dry weight basis of between 3.27 and 5.57 calories per gram. Below is an exemplification collection of the patents, the example number within the patent, type of flavored baked good used in the example, and the total calories on a dry weight basis for that example. The highest and lowest values are noted in bold type.
TABLE 1 Patent Number Example Number Type of flavored baked goods Calories on a dry weight basis 2,802,741 2 Cake 4.29 2,865,757 1 Cookies 4.47 2,865,757 2 Cookies (2) 4.45 2,952,548 2 Cookie 4.62 3,023,104 1 Honey doughnuts 3.36 3,023,104 2 Peanut Butter Cookie 4.26 3,579,548 15a Cake 3.86 4,109,025 16 Biscuits (3) 3.86 4,109,025 4 Biscuits (2) 3.85 4,109,025 5 Biscuits 3.85 4,219,580 10 Chocolate cookies 3.65 4,219,580 12 Chocolate cake 2 3.57 4,219,580 13 Cake 2 3.44 4,219,580 14 Vanilla cookies 4.64 4,219,580 16 Cake 3 3.76 4,219,580 2 Cake 3.79 4,219,580 4 Chocolate Cake 3.92 4,225,628 1 Yellow layer cake 4.69 4,247,568 26 Cake 4.79 4,247,568 31 Lincoln biscuit 4.74 4,275,088 1 Yellow layer cake 4.17 4,275,088 3 Yellow layer cake (2) 4.13 4,351,852 1 (B) Cake 1 4.36 4,351,852 2 Cake 2 4.26 4,351,852 5 Devil's Food Cake 3.89 4,351,852 6 Yellow cake 4.00 4,424,237 8 Cake 4.09 4,431,681 1 Cake 3.28 4,431,681 2 Cake (2) 3.89 4,431,681 3 Cake (3) 3.92 4,451,489 2 Cake 3.74 4,526,794 4 Orange cake 3.87 4,526,799 1 Cake 3.82 4,526,799 2 Cake 2 3.76 4,526,799 3 Cake 3 3.69 4,774,099 2 Brownie 4.83 4,871,571 2 Cookie 3.77 4,950,140 1 PB Cookie 5.04 4,968,694 8 Biscuit 4.17 5,051,271 2-1 Sugar cookie 5.01 5,051,271 2-2 Sugar cookie (2) 5.12 5,051,271 5 Brownies 4.88 5,051,271 6 Sugar cookie (3) 4.61 5,073,387 6 Brownie 3.27 5,106,644 IV-A White cake 4.40 5,106,644 IV-B White cake (2) 4.38 5,106,644 IV-C White cake (3) 4.43 5,106,644 VI Sugar cookies 4.76 5,106,644 VII-A Rolled biscuits 4.63 5,106,644 VII-B Rolled biscuits (2) 4.57 5,108,764 1 Fermented crackers 3.98 5,108,764 2 Unfermented crackers 3.85 5,133,984 1-B Loaf cake 3.63 5,133,984 11 Cake 3.93 5,133,984 12 Cake 2 5.00 5,133,984 13 Cake 3 3.87 5,133,984 8 Oatmeal cookie 3.64 5,169,671 13-A American pastry 4.02 5,169,671 15 Doughnut 3.93 5,169,671 23-C Sponge cake 3.98 5,194,282 2 Chocolate cake 4.28 5,194,282 6 Yellow cake 4.05 5,281,584 1-6 Cookie 3.98 5,308,639 16 Sugar cookie 4.37 5,308,639 24 Chocolate Chip Cookie 5.24 5,466,479 11 Chocolate chip cookies 3.51 5,466,479 12 Oatmeal Cookies 3.28 5,466,479 13 Blueberry muffins 3.51 5,472,732 29 (Food example 22) Donut 4.20 5,472,732 31 (Food example 24) Butter cookie 4.04 5,472,732 32 (Food example 25) Pound cake 4.26 5,472,732 33 (Food example 26) Sponge cake 3.61 5,472,732 34 (Food example 27) Apple Pie 5.57 5,514,404 1 Fermented cracker 4.01 5,514,404 2 Unfermented cracker 4.30 5,593,503 6 Oatmeal cookie 4.90 5,593,503 7 Crackers 4.25 5,593,503 9 Yellow cake 5.37 5,766,662 11H Brownie 3.29 5,804,243 1 Donut 4.12 5,902,410 10 Yellow cake 5.37 5,902,410 9 Oatmeal cookie 4.89 5,906,852 2 Cookies 4.52 5,906,852 3 Wafers 3.78 5,906,852 3 Chocolate chip cookies 4.73 5,906,852 3 Chewy Chocolate Chip Cookies 4.31 5,906,852 3 Sandwich Cookies 3.90 5,976,598 3 Cookies 4.64 5,976,598 5 Cookies (2) 4.52 6,030,654 11 Cake 4.43 6,030,654 4 Cookie 4.14 6,280,526 14 Cookie 4.56 6,299,924 11 Muffin 3.92 6,299,924 12A Yellow cake 3.83 6,613,373 9 Cookies 4.49 6,627,242 1 Pizza crust 4.21
SUMMARY OF THE INVENTION
[0008] It is an object of the present invention to overcome the limitations of the existing state of the art by developing a process and ingredients by which one can produce a food product with acceptable mouth-feel, having a nutritive value between about 1 and 3.25 calories per gram, on a dry weight basis.
[0009] In order to understand the scope of the present invention it is important to initially understand that there are many ingredients used in low calorie formulations, which do not add increased bulk. These include gums, artificial sweeteners, and emulsifiers. There are however only a limited number of ingredients that can provide the low calorie bulk necessary for satiation. These ingredients fall into three categories:
Polyols (sugar alcohols) Cellulose and related fibers Enzyme-resistant starches
[0013] The advantage of these ingredients is that they have a range of very low caloric values, with the lowest caloric category being the cellulose fibers, which can be as low as 0.1 calories per gram. However, despite their low caloric value, these ingredients provide satiation, and are therefore useful to help restrict caloric intake and promote weight loss. There are numerous studies that indicate that fiber produces both a satiation effect and a gastric fullness effect.
[0014] The limitation of these ingredients however is that their recommended use level in standard baking formulations is relatively low. The reason for the low recommended levels is that when these ingredients are increased to higher levels, in standard formulations, they result in imperfections in flavor or texture.
[0015] In addition, some ingredients provide another concern, in that even if they could be tolerated in the product formulation at high levels from a texture perspective, they must be restricted because of negative digestive effects. In the polyol category, for example, each polyol has recommended acceptable use levels, as dictated by the FDA, above for which a warning label must be included, suggesting that the product may have laxative effects. In addition, certain ingredients which the FDA has allowed high levels of usage have been shown to produce flatulence and other undesirable effects even at low levels.
[0016] For example, polydextrose has been shown to cause flatulence at levels of 10 grams per day, even though the FDA has determined that a laxative effect will not be felt until 90 grams per day are consumed.
[0017] The second category, cellulose fiber, is composed of alpha-cellulose, hemicellulose, lignin, and other such naturally indigestible plant material. Only insoluble fibers are considered non-caloric by the US Food and Drug Administration (FDA). Cellulose fibers impart a grainy and piece-like texture in the final product. When highly processed, they produce less graininess, but at the expense of increasing siltiness. In all forms, they produce an unacceptable mouth-feel when used at high levels in the final product. In addition, the high water absorption of the cellulose creates many additional problems in the formulation.
[0018] The third category, enzyme resistant starch, is that fraction of starch which resists digestive enzymes, and so is not digested in the small intestine. Although not exactly quantifiable due to its heterogeneous nature, some is determined as dietary fiber by the official Association of Official Agricultural Chemists (AOAC) method. Resistant starches have been categorized into four classes:
[0019] RS_I. Physically inaccessible starches found in seeds and legumes.
[0020] RS-II. Starch consumed as granular, non-gelatinized starch that is found in flour and potatoes, for example.
[0021] RS-III. Inaccessible starch formed by retrogradation caused by heating or shear. Examples would be starch in bread or RTE cereals.
[0022] RS-IV. Chemically modified starch, such as through cross-linking, substitution, or the addition of side-chains.
[0023] The prior art is however replete with the use of resistant starch. It has been postulated to add as much resistant starch as possible into baked goods but only a maximum Percentage of the Final Food Product which is Resistant to Digestion has been successfully demonstrated of 12.2%—that is 12.2% of the finished product was resistant to digestion as determined the “AOAC Method 991.43”, a measure of what percentage of the starch is digested by digestive enzymes under conditions which mimic the human body. Much higher levels of the Percentage of the Final Food Product which is Resistant to Digestion, have been generally suggested but without actual substantiation.
[0024] Table 2 lists prior art experiments collected from numerous patents with their calculations of the Percentage of the Flour-Component which is Resistant to digestion, and the Final Food Product which is Resistant to Digestion. Also listed here are examples from the current patent which are included here to determine the acceptable range of functionality of the various resistant starches:
TABLE 2 Percentage Percentage Percentage of the Percentage of the of the Flour- of the Final Starch Flour- Component Food which is component which is Product Resistant which was Resistant which is Resistant Experiment Patent to Replaced to Resistant to Starch Product Number digestion with Starch digestion digestion Type type 6,830,767 40.00% 2.20% 0.88% Unknown 2 Chips 6,830,767 40.00% 3.40% 1.36% Unknown 2 Chips 6,613,373 32.00% 50.00% 16.00% 8.48% 3 Cookies 6,613,373 47.00% 50.00% 23.50% 12.46% 3 Cookies 6,613,373 34.00% 50.00% 17.00% 9.01% 2 Cookies 6,613,373 46.00% 50.00% 23.00% 12.19% 2 Cookies 6,613,373 28.00% 50.00% 14.00% 7.42% 3 Cookies 6,613,373 43.00% 50.00% 21.50% 11.40% 3 Cookies 6,451,367 20.00% 48.27% 9.65% 8.40% 2 Cereal 6,451,367 20.00% 49.60% 9.92% 8.61% 2 Cereal 6,451,367 20.00% 11.76% 2.35% 1.68% 2 Cereal 6,451,367 20.00% 17.07% 3.41% 2.73% 2 Cereal 6,451,367 20.00% 5.00% 1.00% 0.60% 2 Bread 6,451,367 20.00% 10.00% 2.00% 1.20% 2 Bread 6,451,367 20.00% 15.00% 3.00% 1.80% 2 Bread 6,451,367 20.00% 20.00% 4.00% 2.40% 2 Bread 6,451,367 20.00% 25.00% 5.00% 3.00% 2 Bread 6,451,367 20.00% 24.00% 4.80% Unknown 2 Noodles 6,299,907 70.00% 25.00% 17.50% 8.11% 4 Cookies 6,299,907 31.00% 25.00% 7.75% 3.59% 4 Cookies 5,902,410 60.00% 14.00% 8.40% 3.49% 3 Cookies 5,902,410 60.00% 4.50% 2.70% 0.53% 3 Cake 5,776,887 40.00% 26.50% 10.60% 5.36% 2 Granola Bar 5,776,887 40.00% 20.40% 8.16% 2.80% 2 Cookies 5,776,887 40.00% 26.80% 10.72% 4.40% 2 Snack Bar 5,593,503 40.00% 14.00% 5.60% 2.33% 3 Cookies 5,593,503 40.00% 4.50% 1.80% 0.35% 3 Cake 5,593,503 40.00% 16.45% 6.58% 4.10% 3 Crackers 5,593,503 40.00% 16.66% 6.66% 6.00% 3 Cereal
[0025] Once levels near 20% were reached, the prior art was not able to achieve a product with acceptable organoleptic properties. Alternatively, in a low calorie formulation, where the amount of fat is by necessity limited (since fat contains 9 calories per gram, as opposed to the 4 calories per gram of starch or protein), the amount of resistant starch that can be tolerated from a functional and organoleptic standpoint is far lower. It is possible that high levels of fat are able to mask the negative organoleptic properties of the resistant starch. In the prior art and current state of the art the amount of resistant starch employed is relatively small. In addition, Kraft/Nabisco, the leading baked-goods manufacturer in the world, indicated in its U.S. Pat. No. 6,613,373 that the best achievable results for flour replacement have been found with resistant starch type III. However with respect to resistant starch types III and IV, Kraft/Nabisco propounded that they are not as suitable for use as a flour replacement and characterized them as having low melting points, which do not survive a baking process, and do not exhibit good baking functionality. For example, granular starches in the presence of excess water melt at a temperature of about 80 degree C. to about 100 degree C., which is generally below baking temperatures for cookies and crackers. Kraft/Nabisco further found that the digestibility of starch may be reduced by cross-linking or the presence of various substituents such as hydroxypropyl groups. However, the chemical or thermal modification of the starch, which results in a type IV resistant starch, often affects the baking characteristics of the starch. In addition, chemically or thermally modified starches may exhibit undesirable flavors or colors when used in substantial amounts in baked goods. In contrast the type III resistant starch was found by Kraft/Nabisco to be thermally very stable, which is highly advantageous for producing reduced-calorie baked goods.
[0026] In accordance with the present invention, despite the teachings of the prior art it has been experimentally discovered that resistant starch types II and IV actually produce a far superior product to RS III in formulations which follow.
[0027] Generally the present invention comprises food products having in the range of about 1 to 3.25 calories per gram, on a dry weight basis, and comprising resistant starch with a maintained granular structure (preferably with a chemical modification). Starch can be chemically modified to achieved resistancy using any of a vast array of reactions, each with their own optimum temperature, pH, and other reaction conditions. In general, however, the actual reaction (or reactions) fall into two broad categories: the addition or substitution of chemical side-chains onto the starch molecule. Cross-linking can be viewed a subset of the former category, in which the added “side-chain” is another starch molecule. The plethora of possible modifications available for actual use is severely limited (though not a limitation of the present invention) by the FDA's Code of Federal Regulations, Title 21, Volume 3, Section 172.892 “Food starch-modified.”, which allows only a small number of chemical compounds to be used, and at restricted usage levels as well. The most likely chemical approved modifications which can be used, alone or in combination, are then: modification by oxidation, etherification, or esterification; the addition of acetyl or phosphate groups (acetylation or phosphorylation, respectively); or the cross-linking of starch molecules by adipic or phosphate bonds. In particular the resistant starch is a type II resistant starch, and wherein the total dietary fiber arising from the resistant starch constitutes 14-20% of the final food product by weight. Alternatively the resistant starch is a type IV resistant starch, and wherein the total dietary fiber arising from the resistant starch constitutes 14-60% of the final food product by weight.
[0028] The food products containing a type II resistant starch, preferably have the resistant fraction of the flour component of the product constitutes 25-30% of the flour component by weight. Similarly the food products containing a type IV resistant starch, preferably have the resistant fraction of the flour component of the product constituting 25-80% of the flour component by weight.
DETAILED DESCRIPTION OF THE INVENTION
[0029] It has been experimentally determined that the amount of resistant starch that can be added to a product varies greatly depending on the type (RS-III, RS-II, or RS-IV) of the resistant starch being utilized. In extensive experiments it was found that:
[0030] When RS-III was used, then when the Percentage of the Final Food Product which is Resistant to Digestion (“PFFPRD”) was above around 11%, creation of a product acceptable in organoleptic evaluation was unable to be made. Somewhat acceptable results were obtained at around 7% PFFPRD.
[0031] When RS-II was used, then when the PFFPRD was above around 20% creation of a product acceptable in organoleptic evaluation was unable to be made. Somewhat acceptable results were obtained at around 14% PFFPRD.
[0032] Surprisingly when RS-IV was used, then even when the PFFPRD was as high as 60% a product acceptable in organoleptic evaluation was readily obtained.
[0033] Another way at looking at this is seeing the Percentage of the Flour-Component which is Resistant (“PFCR”) to digestion as compared to the total flour component (column D). This percentage is stated in a different way in the prior art patents in Table 2, which typically give the Percentage of the Starch which is Resistant to digestion (second column) and Percentage of the Flour-component which was Replaced with Starch (third column). These two factors were taken and multiplied to arrive at the Percentage of the Flour-component which is Resistant to digestion (fourth column). In all the experiments cited in the existing patent literature, the PFCR was at most 23.5%.
[0034] In further extensive experiments it was found that
[0035] When RS-III was used, then when the PFCR was 30%, creating a product acceptable in organoleptic evaluation was not possible. Somewhat acceptable results were obtained at 15% PFCR.
[0036] When RS-II was used, then when the PFCR was 60% creating a product acceptable in organoleptic evaluation was not possible. Somewhat acceptable results were obtained at 30% PFCR.
[0037] When RS-IV was used, then even when PFCR was 80%, creation of a product acceptable in organoleptic evaluation was readily possible.
[0038] The rationale behind this discovery seems to be that since RS-III's retrogradation destroys its granular structure:
[0039] a) RS-III has a higher level of water absorption which makes it difficult to form into a dough, with textural issues when creating a dry product and not allowing the granules to fully swell; and
[0040] b) the particles of RS-III are irregular and amorphous, with no definite size or shape, resulting in a grainy texture in finished products
[0041] In contrast, RS-II maintains more of the granular structure, and therefore performs better in formulations. But since its granular structure is unprotected, it is often broken down to an extent in processing, resulting in similar negative effects to those observed in RS-III.
[0042] RS-IV has cross-links which provide a protective barrier not only against digestive enzymes (amylase), but also of the granular structure. This makes it the most workable and acceptable form for the products claimed in this patent.
[0043] Consequently, in accordance with the present invention and included there are all products utilizing RS-IV with a PFFRD from 14-60%, and/or a PFCR from 25-80%. Additionally, all products utilizing RS-II with a PFFRD from 14-20% and/or a PFCR from 25-30% are within the scope of the present invention.
EXPERIMENTAL EXAMPLES
[0044] The resistant starches which were used for these experiments fit into three of the resistant starch categories described above, namely types II, III, and IV. FiberSym 70 and FiberSym 80 are type IV resistant starches derived from wheat and potato starches, with 70% and 80% resistant starch content, respectively, and are supplied by MGP Ingredients, Inc. GemStar R70 is also a type IV resistant starch derived from wheat starch with 70% resistant starch content. It is manufactured by Manildra Group USA using an undisclosed process, which the manufacturer claims is not identical to that employed in the FiberSym starches. Novelose 260 is a type 11 resistant starch with 60% resistant starch, and Novelose 330 is a type III resistant starch with 30% resistant starch. Both of the Novelose starches are derived from corn starch, and are supplied by National Starch and Chemical Company. ActiStar 11700 is a type III resistant starch derived from tapioca starch (maltodextrin), with 50% resistant starch content, and is supplied by Cargill Inc. Other non-resistant starches used as controls in the experiments include unmodified potato and corn starches.
[0045] Unmodified potato and corn starches exhibit low water binding capacity, of about 91% and 95% their weight in water, respectively. These starches also leach significant quantities of amylose, and to a higher degree in corn starch than in potato.
[0046] The chemical treatment undergone by FiberSym 70 and FiberSym 80 to become partially resistant to digestion allows the granular structure of the starch to remain intact, except for some minor shrinkage, resulting in the maintenance of a low water binding capacity, of about 70% and 80% their weight in water, for FiberSym 70 and FiberSym 80 respectively. Additionally, the processing reduces the amount of amylose leakage from the granules. The GemStar R70 performs similarly to the FiberSym.
[0047] Novelose 260 (RS type II) is considered a “natural” resistant starch, and its granular structure is unaffected during the processing. Its water binding capacity is somewhat elevated, however, since it is able to bind 115% of its weight. By contrast, in Novelose 330 (RS type III) the entire starch, even the enzyme-susceptible component, is altered during processing through thermal retrogradation, and the entire granular structure is lost. Its water binding capacity increases to 200% of its weight. ActiStar 11700 performs similar to the Novelose 330.
[0048] Olean is an indigestible oil (sucrose polyester) supplied by the Procter & Gamble Company, and approved by the FDA for use in fried snack products, such as the crisp experiments described below.
[0049] I. Cookies
[0050] These experiments were conducted by combining and blending the dry ingredients thoroughly, in the order given below. The wet ingredients were then combined in the order given below and added to the dry ingredients. Water was added until it formed an acceptable batter. In cases where too much water was added, additional starch was added to compensate, as recorded below. The dough was then formed into 10 flattened circular cookies 1.5-inches in diameter (similar to standard “Nilla” wafers), placed onto a greased cookie sheet, and baked at 375 Fahrenheit until lightly browned. The exact baking time is recorded below.
[0051] Some experiments employed quantities of standard unbleached all-purpose wheat flour in addition to the starch. Those experiments, and the quantities of flour used, are indicated in the Flour Quantity column. All material units are in grams and times are in minutes.
[0052] Base ingredients:
Starch (see below) (see below for quantity) Crisco 2.5 Sugar 5 Corn Syrup 5.5 Condensed Milk 5 Vanilla (McCormick) 1 Salt 0.1 Whole Egg 4 Gluten 4 Baking Powder 0.3 Xanthan Gum 0.1
[0053]
Experiment
Starch
Starch
Flour
Water
Bake
Number
Type
Quantity
Quantity
Quantity
Time
Notes
1
Unmodified
27
8
8, 12
Good, slightly tougher
Corn Starch
texture
2
Unmodified
30
2.5
8
Good
Potato Starch
3
FiberSym 70
25
2.5
8
Good
(RS-IV)
4
FiberSym 80
25
2.5
8
Good
(RS-IV)
5
Novelose 260
25
12
8, 14
(High moisture)
(RS-II)
Starchy initially, turned
wet and mushy the next
day
6
Novelose 260
25
5
8, 12
(Low moisture)
(RS-II)
Starchy, chalky
7
Novelose 260
25
2.5
NA
Unable to form dough
(RS-II)
8
Novelose 260
12.5
12.5
3
8
A bit moist, maybe some
(RS-II)
starchiness, but
nominally acceptable
9
Novelose 330
25
14
8,
Dense, chewy, nearly
(RS-III)
12,
inedible; too chalky,
14
awful
10
Novelose 330
25
2.5
NA
Unable to form dough
(RS-III)
11
Novelose 330
12.5
12.5
8.5
8, 10
Also moist, slight degree
(RS-III)
of graininess and
starchiness, but edible;
not as light as the type
IV cookies
Baked some for another
2 minutes, which helped
reduce moistness
12
ActiStar
25
2.5
8
Awful, grainy, sticks to
11700
teeth
(RS-III)
13
GemStar R70
25
2.5
8
Slightly starchy
(RS-IV)
A bit dense, odd odor,
but nominally acceptable
[0054] Summary: Using the FiberSym 80 product, which contains the highest percentage of resistant starch, and provides a very acceptable product, the final product provides 2.66 calories per gram on a dry weight basis, well within the range of 1 to 3.25 calories per gram of the present invention.
[0055] II. Chocolate Cake
[0056] These experiments were conducted by combining and blending the dry ingredients thoroughly, in the order given below. The wet ingredients were then combined in the order given below and added to the dry ingredients. Water was added until it formed an acceptable batter. The amount of water is variable, and is recorded below. The batter was then poured into a greased loaf pan, and baked at 350 degrees Fahrenheit for at least 15 minutes.
[0057] Base ingredients:
Starch (see below) 26 Sugar 10 Ghirardelli chocolate 5 Baking Powder 0.7 Nutrasweet 0.5 Xanthan Gum 0.3 Baking Soda 0.2 Condensed Milk 5 Vanilla Extract 1 Whole Eggs 20
[0058]
Experiment
Number
Water
Starch Type
Notes
1
20
FiberSym 80
Batter was runny
(RS-IV)
Final product was good and cake-like
2
20
FiberSym 70
Batter was runny
(RS-IV)
OK, but not as good as the FS-80
3
20
Novelose 260
(Low moisture)
(RS-II)
Batter was sticky
Final product was wet and gummy after 15, so
put half back in for another 10 minutes
Neither version (baked for 15 or 25) was very
good
4
35
Novelose 260
(High moisture)
(RS-II)
Batter was runny
Baked for 25 minutes total, in attempt to dry it
out to an acceptable texture
Final product was gummish, brownie-like
5
35
Novelose 330
Batter was too dry with 20 g water, so upped to
(RS-III)
35. Batter at that point was sticky, similar to the
Novelose 260.
Was wet and gummy after 15, so put back in for
another 10 minutes
Bad, grainy, starchy, nearly inedible; worse than
the Novelose 260, even.
6
20
Unmodified
Good, perhaps a bit tough
Corn Starch
7
20
Unmodified
Too rubbery, elastic
Potato Starch
[0059] Summary: Using the FiberSym 80 product, which contains the highest percentage of resistant starch, and provides a very acceptable product, the final product provides 2.39 calories per gram on a dry weight basis, within the range of 1 to 3.25 calories per gram of the present invention.
[0060] Crisps 1
[0061] These experiments were conducted by combining the starch and salt with 3 g of Vital Wheat Gluten and 15 g of water. Additional gluten and water were added in 1 g and 2 g increments (respectively) until the dough attained an appropriate machineable consistency. The dough was then rolled through a hand-operated double roller to achieve a uniform thickness, cut into strips, baked for 12 minutes at 375 degrees Fahrenheit, and fried in Olean for 1 minute at 375 Fahrenheit.
[0062] Base ingredients:
Starch (see below) 25 Gluten (initial) 3 Water (initial) 15 Salt 1
[0063]
Experiment
Added
Added
Number
gluten
water
Starch type
Notes
1
4
Unmodified
Very crunchy,
Corn
a bit sticky on teeth
Starch
2
0
Unmodified
Very crunchy
Potato Starch
3
10
Novelose 260
Stuck to teeth
(RS-II)
4
3
22
Novelose 330
Burnt, gritty
(RS-III)
5
4
FiberSym 70
Brittle, crumby,
(RS-IV)
a little starchy
6
4
FiberSym 80
Very crunchy, tiny bit
(RS-IV)
starchy, but doesn't
stick to palate
[0064] IV. Crisps 2
[0065] These experiments were conducted by combining the starch and salt with 3 g of Vital Wheat Gluten and 15 g of water. Additional gluten and water were added in 1 g and 2 g increments (respectively) until the dough attained an appropriate machineable consistency. The dough was then rolled through a hand-operated double roller to achieve a uniform thickness, cut into strips, baked for 10 minutes at 375 degrees Fahrenheit, and fried in Olean for 30 seconds at 375 Fahrenheit.
[0066] Base ingredients:
Starch (see below) 25 Gluten (initial) 3 Water (initial) 15 Salt 1
[0067]
Experiment
Added
Added
Number
gluten
water
Starch type
Notes
1
4
Unmodified
Good, crunchy, but
Corn Starch
tough
2
0
Unmodified
Excellent. Very
Potato Starch
crispy, a little hard
3
10
Novelose 260
Good. A little softer
(RS-II)
and starchier. Some
aftertaste.
4
3
20
Novelose 330
Awful, inedible
(RS-III)
5
4
FiberSym 70
Brittle, crumby, a
(RS-IV)
little starchy, silty,
tough to chew
6
2
FiberSym 80
Excellent, very crispy
(RS-IV)
[0068] Summary: Using the FiberSym 80 product, which contains the highest percentage of resistant starch, provides a very acceptable product, the product, prior to frying in Olean, provides 1.15 calories per gram on a dry weight basis, within the range of 1 to 3.25 calories per gram of the present invention. Since Olean contributes no calories, but some weight, the final product would provide even fewer calories. The actual number is unknown, due to the difficulties inherent in estimating Olean uptake, but it is estimated to be at least as low as 1 calorie per gram.
[0069] V. Standard Pasta
[0070] All of the ingredients were combined and kneaded for 5 minutes. The dough was then formed into a ball and allowed to rest for 5 minutes. It was then rolled through a hand-operated double roller to a uniform thickness, cut into strips, and hung to dry for 8 hours. Finally the pasta was boiled in water for 5-10 minutes, until al dente.
Starch (see below for starch 21 type) Gluten 6 Salt 0.3 Whey Protein Concentrate 1
[0071]
Experiment
Number
Starch type
Water
Notes
1
Novelose
20
Refused to cook and get limp
260
Starchy, grainy; unacceptable
(RS-II)
2
Novelose
30
Starchy, grainy, chewy, leaves
330
mouth kind of dry; unacceptable
(RS-III)
3
FiberSym
14.5
Very good, strongly reminiscent of
70
real pasta
(RS-IV)
4
FiberSym
15
Good, though slightly softer than
80
FiberSym 70 version; acceptable
(RS-IV)
[0072] Several successful attempts were then made to salvage the Novelose 260 version.
Gluten 6 Salt 0.3 Whey Protein Concentrate 1
[0073]
Novelose
Experiment
260
Wheat
Guar
Wa-
Number
(RS-II)
Fiber
Gum
Oil
ter
Notes
5
19
2
20
Sticky, starchy,
chewy,
unacceptable
6
11
10
30
Too fibrous
7
11
10
0.3
2
23
Too fibrous,
though
harder
8
16
5
23
Too fibrous,
though
harder
[0074] VI. Egg Noodles
[0075] All of the ingredients were combined and kneaded for 5 minutes. Water was added as demanded by the consistency of the dough. The dough was then formed into a ball and allowed to rest for 5 minutes. It was then rolled through a hand-operated double roller to a uniform thickness, cut into strips, and left to dry in the air for 10 minutes. Finally the pasta was boiled in water for 5-10 minutes, until al dente.
Starch (see below for starch 21 type) Gluten 4 Whole Eggs 10
[0076]
Experiment
Xanthan
Number
Starch Type
Gum
Water
Notes
1
FiberSym 70
5
Starchy, not enough
(RS-IV)
resistance to bite-through
2
FiberSym 70
0.2
5
Gummy
(RS-IV)
3
FiberSym 80
5
Cooked very fast
(RS-IV)
Not enough resistance to
bite-through or body
4
Novelose
10
Starchy, grainy
260
(RS-II)
5
Novelose
0.2
10
Starchy, grainy
260
(RS-II)
6
Novelose
0.2
7.5
Starchy, grainy
260
(RS-II)
7
Novelose
0.2
20
Starchy, grainy
330
(RS-III)
[0077] VII. Crisps 3
[0078] These experiments were conducted by combining the FiberSym 80 and salt with 3 g of Vital Wheat Gluten and 15g of water. Additional gluten and water were added in 1 g increments until the dough attained an appropriate machineable consistency. The dough was then rolled through a hand-operated double roller to achieve a uniform thickness, cut into strips, baked for 10 minutes at 375 degrees Fahrenheit, and fried in Olean for 30 seconds at 375 Fahrenheit.
FiberSym 80 25 Gluten (initial) 3 Water (initial) 15 Salt 1
[0079]
Experiment
Added
Wheat
Whole
Added
Number
Water
Fiber
Egg
Gluten
Notes
1
2
Good
2
10
3
1
Good. Crispier,
tougher to
chew
3
5
3
5
1
Good. Soft, broke
up very
easily in mouth in a
positive fashion
[0080] These experiments were conducted by combining the all of the ingredients except for the Potato Flakes (when present in the experiment) and an amount of water equal to the weight of the Potato Flakes called for in the experiment (i.e., 5 g of water for 5 g of flakes, 10 g of water for 10 g of flakes). The dough was then rolled through a hand-operated double roller to achieve a uniform thickness. At this point the potato flakes were lightly combined with the corresponding amount of water and worked into the dough. Additional water was added in 0.5 g increments until the dough attained an appropriate machineable consistency. The dough was then cut into strips, baked for the specified number of minutes at 375 degrees Fahrenheit, and fried in Olean for 30 seconds at 375 Fahrenheit.
[0081] Base ingredients:
Gluten 2 Salt 0.5
[0082]
Exper-
Bake
iment
FiberSym
Potato
Total
Time (in
Number
80
Flakes
Shortening
Water
minutes)
Notes
4
25
0
0.5
16.5
5
Good
5
20
5
1
18
5
Better
6
15
10
1
20
4
Best
[0083] VIII Flavored Pasta
[0084] The most successful version of the STANDARD PASTA was adapted with flavoring, using the same procedures as above. All of the ingredients were combined and kneaded for 5 minutes. The dough was then formed into a ball and allowed to rest for 5 minutes. It was then rolled through a hand-operated double roller to a uniform thickness, cut into strips, and hung to dry for 8 hours. Finally the pasta was boiled in water for 5-10 minutes, until al dente.
Experiment Number Ingredient 1 2 3 FiberSym 70 21 23 22 Gluten 6 6.4 6.5 Salt 0.5 0.5 0.5 Whey Protein Concentrate 1 1 1.5 Tomato Paste 7 7 Spinach 8 Water 12 13 10.5 Notes Too soft Good Good
[0085] IX. Cheese Crackers
[0086] The dough in this experiment was rolled through a hand-operated double roller to achieve a uniform thickness, cut into strips, baked for 15 minutes at 325 degrees Fahrenheit, turned over, and baked for an additional 3 minutes again at 325 degrees Fahrenheit.
FiberSym 80 21 Gluten 4 Salt 0.2 Paprika 0.3 WCB 3.5 Crisco 1.8 EMC Cheddar 0.5 Water 10
[0087] X. Instant Noodles
[0088] All of the ingredients were combined and kneaded for 5 minutes. Water was added as demanded by the consistency of the dough. The dough was then formed into a ball and allowed to rest for 5 minutes. It was then rolled through a hand-operated double roller to a uniform thickness and cut into thin strips. At this point, the experiment was optionally boiled in water for 2.5 minutes (indicated in chart). All experiments were then deep-fried in vegetable oil at 375 Fahrenheit for 1.5 minutes. Finally, the noodles were placed in Styrofoam cup which was then filled with boiling water, covered, and allowed to sit for 5 minutes.
[0089] Base ingredients:
FiberSym 70 21 Salt 0.3
[0090]
Experiment
Guar
Number
Gluten
WPC
Gum
Water
Boiled?
Notes
1
4
1
14.5
No
Bit through to easily, not much
resistance, soft and quick-
dissolving
2
6
1
14.5
No
Bit through to easily, not much
resistance, soft and quick-
dissolving
3
6
1
14.5
Yes
Acceptable, but a little too soft
4
6
1
0.3
15
No
A little too hard
5
6
1
0.3
15
Yes
Still a little too hard
6
6
1
0.15
14.5
No
Acceptable
7
6
1
0.15
14.5
Yes
Acceptable, but a little too soft
8
6
0.15
14.5
No
Acceptable
9
6
0.15
14.5
Yes
Acceptable, slightly rubbery
[0091] It is understood that the above examples are illustrative of the present invention and that changes may be made may be made in ingredients, formulations, processing and the like without departing from the scope of the present invention as defined in the following claims
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A food product having in the range of about 1 to 3.25 calories per gram, on a dry weight basis, and comprising resistant starch with a maintained granular structure, preferably, with a chemically modification to obtain the maintained granular structure. With a type II resistant starch, the total dietary fiber within the food product arising from the resistant starch comprises 14-20% of the final food product by weight. With a type IV resistant starch, the total dietary fiber within the food product arising from the resistant starch constitutes 14-60% of the final food product by weight. The food product may be cookies, cakes, crisps, instant noodles, cheese crackers, pasta, and egg noodles.
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FIELD OF THE INVENTION
[0001] This application is a continuation in part, claiming priority upon U.S. Ser. No. 09/599,693. The invention relates to coating compositions for use with metallic substrates and more particularly to automotive refinish coating compositions intended for use on metallic substrates, and especially to two component polyurethane primers which can be sanded and recoated and are intended for use on steel substrates.
BACKGROUND OF THE INVENTION
[0002] As used herein, “automotive refinish” refers to compositions and processes used in the repair of a damaged automotive finish, usually an OEM provided finish. Refinish operations may involve the repair of one or more outer coating layers, the repair or replacement of entire automotive body components, or a combination of both. The terms “refinish coating” or “repair coating” may be used interchangeably.
[0003] Automotive refinishers must be prepared to paint a wide variety of materials. Examples of commonly encountered materials are one or more previously applied coatings, plastic substrates such as RIM, SMC and the like, and metal substrates such as aluminum, galvanized steel, and cold rolled steel. Bare metal and plastic substrates are often exposed as a result of the removal of the previously applied coating layers containing and/or surrounding the defect area. However, it is often difficult to obtain adequate adhesion of refinish coatings applied directly to exposed bare substrates.
[0004] Among the many factors influencing the degree of refinish coating/substrate adhesion are the type of exposed substrate, the presence or absence of adhesion promoting pretreatments and/or primers, the size of the exposed area to be repaired, and whether previously applied “anchoring” coating layers surround the exposed repair area.
[0005] For example, refinish adhesion is particularly challenging when the exposed substrate is a bare metal such as galvanized iron or steel, aluminum or cold rolled steel. It is especially hard to obtain adequate refinish adhesion to galvanized iron. “Galvanized iron or steel” as used herein refers to iron or steel coated with zinc. “Steel” as used herein refers to alloys of iron with carbon or metals such as manganese, nickel, copper, chromium, molybdenum, vanadium, tungsten and cobalt.
[0006] Refinish operations have traditionally used adhesion pretreatments to overcome the adhesion problems associated with the coating of bare metal substrates. Pretreatment as used herein may refer to either mechanical or chemical alterations of the bare metal substrate. Mechanical alterations used to obtain improved adhesion include sanding, scuffing, and the like. Chemical alterations include treatment of the substrate with compositions such as chromic acid conversion coatings, acid etch primers and the like.
[0007] Although such pretreatments have obtained improved refinish adhesion, they are undesirable for a number of reasons. Most importantly, pretreatments are inefficient and expensive to apply in terms of material, time, and/or labor costs. Some chemical pretreatments also present industrial hygiene and disposal issues. Finally, the use of some pretreatments such as acid etch primers may contribute to water sensitivity and/or coating failure under test conditions of extreme humidity.
[0008] Accordingly, it is highly desirable to eliminate the need for substrate pretreatment as regards the refinish coating of bare metal substrates.
[0009] In addition, adhesion to bare metal substrates is improved when the defect area to be repaired is relatively small and is surrounded by previously applied coating layers. Such previously applied coating layers act as an ‘adhesion anchor’ to the refinish coating. However, many refinish repairs are of a size such that they lack any surrounding adhesion anchors. Moreover, such anchoring adhesion may be completely absent when replacement body parts are painted with a refinish coating.
[0010] Finally, improvements in refinish adhesion to bare exposed metal substrates must not be obtained at the expense of traditional refinish coating properties. Such properties include sandability, recoatability, corrosion resistance, durability, ambient or low temperature cure, application parameters such as pot life, sprayability, and clean up, and appearance. Performance properties such as sandability, recoatability and corrosion resistance are particularly important for coating compositions intended for use as primers over steel substrates.
[0011] However, it has been difficult for the prior art to obtain the proper balance with regard to sandability, recoatability, corrosion resistance, and metal adhesion requirements.
[0012] Failure to provide adequate corrosion resistance or salt spray resistance typically manifests as “scribe creep”. “Scribe creep” refers to the degree of corrosion and/or loss of adhesion which occurs along and underneath film adjacent to a scribe made in a cured film after the scribed film has been placed in a salt spray test apparatus. The scribe generally extends down through the film to the underlying metal substrate. As used herein, both ‘corrosion resistance’ and ‘salt spray resistance’ refer to the ability of a cured film to stop the progression of corrosion and/or loss of adhesion along a scribe line placed in a salt spray test apparatus for a specified time. Cured films that fail to provide adequate salt spray resistance are vulnerable to large scale film damage and/or loss of adhesion as a result of small or initially minor chips, cuts and scratches to the film and subsequent exposure to outdoor weathering elements.
[0013] Although urethane coatings have been known to be useful as refinish primers, they have not achieved the desired balance of properties.
[0014] In particular, for polyurethane films to provide desirable salt spray resistance, they have typically relied upon the use of corrosion protection components containing heavy metal pigments such as strontium chromate, lead silica chromate, and the like. Unfortunately, sanding such a film produces dust that is environmentally disfavored due to the presence of the heavy metal containing pigments. Since sanding is a necessity for automotive refinish primers, this disadvantage can render the coating unusable in most commercial refinish application facilities. Accordingly, it would be advantageous to provide a coating which can provide adequate salt spray resistance but which is substantially free of any heavy metal containing pigments.
[0015] Aluminum pigments have traditionally been used to provide a desirable metallic or lustrous appearance. For example, the 1977 Federation Series on Coatings Technology teaches that aluminum pigment containing paints have no specific anti-corrosive effect, such as is afforded by rust-inhibitive pigments traditionally used in commercially acceptable metal primers. Indeed, it is further taught that strontium chromate should be used in combination with aluminum pigments to provide aluminum containing paints having an anti-corrosive effect.
[0016] Aluminum pigments, especially leafing aluminums, are known to produce an apparently continuous film of aluminum metal.
[0017] Barrier pigments, especially platy or platelet pigments have been known to provide anticorrosive effects.
[0018] However, leafing aluminums and barrier pigments have traditionally been somewhat disfavored due to recoatability and/or sanding performance issues. Moreover, the anticorrosive effect of the coating post sanding can be impaired due to the removal of the barrier or leafing layer. As a result, the use of aluminum pigments in primers is to some extent disfavored.
[0019] The prior art has thus failed to provide a coating composition intended for use as a direct to metal primer which has commercially acceptable performance properties with regard to salt spray resistance, sandability, recoatability and adhesion to metal substrates, especially iron and/or steel.
[0020] Accordingly, it is an object of the invention to provide a curable coating composition that can be applied directly to a metal substrate and provides a commercially acceptable level of salt spray resistance.
[0021] It is a further object of the invention to provide a curable coating composition which has commercially acceptable performance properties with regard to direct to metal adhesion and salt spray resistance and further can be sanded without the production of environmentally disfavored dust.
[0022] It is a further object of the invention to provide a curable coating composition which has commercially acceptable performance properties with regard to direct to metal adhesion, salt spray resistance, sandability, and further can be recoated with a second application of the curable coating composition of the invention or another curable coating composition.
[0023] Finally, it is an object of the invention to provide a curable coating composition which has commercially acceptable performance properties with regard to direct to metal adhesion, salt spray resistance, sandability, and recoatability, especially a curable coating composition having a film forming component selected from the group consisting of polyurethane systems and epoxy/amine systems.
SUMMARY OF THE INVENTION
[0024] It has been found that these and other objects of the invention have been achieved with the use of a curable coating composition comprising a film-forming component selected from the group consisting of polyurethane systems and epoxy/amine systems, and a corrosion protection component consisting of aluminum selected from the group consisting of nonleafing aluminum pigments and present in an amount effective to prevent corrosion of the substrate, wherein a cured film of the coating applied to a metallic substrate has a pass rating after 480 hours in salt spray per ASTM B117, and is both sandable and recoatable.
[0025] In a preferred embodiment of the invention, the aluminum pigment will be a lamellar shaped aluminum pigment and will be present in an amount of from 0.011 to 0.051 P/B.
[0026] In a particularly preferred embodiment of the invention, the film forming component of the invention will be a polyurethane based coating system comprising a film forming polymer which is an active hydrogen containing group polymer and an isocyanate functional crosslinking agent.
[0027] In a most preferred embodiment of the invention, the polyurethane film forming component will further comprise a composition comprising (I) an effective amount of a first compound having an acid number of from 70 to 120 mg KOH/g, a hydroxyl number of from 200 to 400 mg KOH/g, a number average molecular weight of from 300 to 700, and which is the reaction product of (a) at least one difunctional carboxylic acid, (b) at least one trifunctional polyol, (c) at least one chain stopper, and (d) phosphoric acid, and (I) an effective amount of a second compound comprising a carboxy phosphate ester having the formula:
[0028] wherein R is an C5-C40 aliphatic group in which one or more aliphatic carbon atoms are substituted with lateral or terminal —COOR1 groups, wherein R1 is H, metal, ammonium, C1-C6 alkyl, or C6-C10 aryl, M is hydrogen, metal or ammonium and x is a number from 0 to 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] The methods of the invention utilize two-component coating compositions. As used herein, the term “two-component” refers to the number of solutions and/or dispersions which are mixed together to provide a curable coating composition. Up until the point of mixing, neither of the individual components alone provides a curable coating composition.
[0030] Once mixed, the resulting curable coating composition is applied to a substrate as quickly as possible. Typically, “as quickly as possible” means immediately after the mixing of the separate components or within eight (8) hours from the time the separate components are mixed, preferably less than one (1) hour after mixing. In a typical two-component application process the components are mixed together either (i) at the nozzle of a sprayer by the joining of two separate carrier lines at the nozzle or (ii) immediately upstream of the nozzle of a sprayer and then delivered to the nozzle via a single carrier line. Once at the nozzle, the mixture is immediately atomized into a mist which is directed at a substrate which is being coated with a film of the mixture of the two-components.
[0031] Unlike one-component compositions, two-component compositions will generally cure in the absence of elevated temperatures. The individual components (I) and (II) will react with each other upon admixture to provide a crosslinked product, most often at ambient temperatures, or more particularly at temperatures of from 15 to 60° C. and most preferably from 24 to 60° C.
[0032] The coating compositions of the invention comprise a corrosion protection component that consists essentially of, and more preferably consists of, one or more aluminum pigments. Although the composition may contain other filler and/or extender pigments such as talc, barrites, silicas and the like, such are not generally considered to substantially contribute to the salt spray resistance of cured films made from the coating compositions of the invention.
[0033] Aluminum pigments suitable for use in the instantly claimed compositions are those aluminum pigments defined as nonleafing aluminum pigments. Although the prior art has taught that the leafing aluminum pigments may be superior in regards to possible anti corrosive effects due to the formation of a barrier-like layer, it has been found that the use of nonleafing aluminum pigments is advantageous in the coating composition of the invention.
[0034] Leafing aluminum pigments have a hydrophobic nature which causes the pigments to float on the surface of water. When placed in a coating, the flakes of leafing aluminum pigments will orientate at or near the surface of the cured film. The flakes are normally oriented in a parallel overlapping fashion and provide a continuous metallic sheath.
[0035] In contrast, nonleafing aluminum pigments are distributed evenly throughout the entire cured film. This distribution is generally attributed to the lubricants used during the aluminum pigment manufacturing process. Typically used lubricants are unsaturated fatty acids such as oleic acid.
[0036] Suitable nonleafing aluminum pigments will have flake thicknesses of from 0.1 μm to 2.0 μm and diameters of from 0.5 μm to 200 μm.
[0037] Acid-resistant grades of nonleafing aluminum pigments are particularly preferred.
[0038] In general, the corrosion protection component of the invention will be present in an amount of from 0.011 to 0.051, more preferably 0.015 to 0.045, and most preferably from 0.025 to 0.040, all being based on P/B, i.e., the % by weight based on the total nonvolatile of the film-forming component, i.e., the total nonvolatile weight of the film-forming polymer and the crosslinking agent.
[0039] Coating compositions of the invention will generally have a pass rating for 480 hour salt spray tests per ASTM B117, incorporated herein by reference. A pass rating is scribe creep of less than 3 mils along the edge of the scribe. More preferably, the coating compositions of the invention will have no more than 2 mils of adhesion loss along the scribe and most preferably will have scribe creep of from 0.5 to 1.5 mils. The coating compositions of the invention will also be free of blistering and rust spots upon completion of salt spray tests per ASTM B117.
[0040] The two-component coating composition typically comprises a film-forming component that in turn comprises a film-forming polymer or binder and a crosslinking agent. The film-forming polymer is typically in a polymer or binder component (I), while the crosslinking agent is typically in a hardener component (II).
[0041] Coating compositions of the invention may comprise any of the film-forming components used in the refinish coatings industry. Such coating compositions may rely on air dry lacquer film formation, film formation via chemical crosslinking, or a combination thereof Thermosetting films produced by chemical crosslinking are most preferred.
[0042] Thermosetting coatings of the invention will comprise at least one film-forming polymer and at least one crosslinking agent. The film-forming polymer will comprise one or more functional groups reactive with one or more functional groups on the crosslinking agent. Examples of functional group combinations useful for the production of crosslinked coatings include, but are not limited to, active-hydrogen and isocyanate, epoxide and carboxylic acid, hydroxyl/carboxylic acid and/or urea-formaldehyde/melamine-formaldehyde, epoxide and amine, and the like.
[0043] Although the film-forming polymer may contain any functional group reactive with the functional group present on the crosslinking agent, preferably the functional group present on the film-forming polymer is at least one functional group selected from the group consisting of hydroxyl, amine, carboxylic acid, epoxy and mixtures thereof. Especially preferred functional groups for use on the film-forming polymer are hydroxyl groups and amine groups, with hydroxyl groups being most preferred.
[0044] Examples of suitable film-forming polymers are acrylic polymers, polyurethane polymers, polyesters, alkyds, polyamides, epoxy group containing polymers, and the like.
[0045] Particularly preferred film-forming polymers will be difunctional, generally having an average functionality of about two to eight, preferably about two to four. These compounds generally have a number average molecular weight of from about 400 to about 10,000, preferably from 400 to about 8,000. However, it is also possible to use low molecular weight compounds having molecular weights below 400. The only requirement is that the compounds used as film-forming polymers not be volatile under the heating conditions, if any, used to cure the compositions.
[0046] More preferred compounds containing reactive hydrogen groups are the known polyester polyols, polyether polyols, polyhydroxyl polyacrylates, polycarbonates containing hydroxyl groups, and mixtures thereof In addition to these preferred polyhydroxyl compounds, it is also possible to use polyhydroxy polyacetals, polyhydroxy polyester amides, polythioether containing terminal hydroxyl groups or sulphydryl groups or at least difunctional compounds containing amino groups, thiol groups or carboxy groups. Mixtures of the compounds containing reactive hydrogen groups may also be used.
[0047] In a most preferred embodiment of the invention, the film-forming polymer reactable with the crosslinking agent is an acrylic resin, which may be a polymer or oligomer. The acrylic polymer or oligomer preferably has a number average molecular weight of 500 to 1,000,000, and more preferably of 1000 to 20,000. Acrylic polymers and oligomers are well-known in the art, and can be prepared from monomers such as methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and the like. The active hydrogen functional group, e.g., hydroxyl, can be incorporated into the ester portion of the acrylic monomer. For example, hydroxy-functional acrylic monomers that can be used to form such resins include hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, and the like. Amino-functional acrylic monomers would include t-butylaminoethyl methacrylate and t-butylamino-ethylacrylate. Other acrylic monomers having active hydrogen functional groups in the ester portion of the monomer are also within the skill of the art.
[0048] Modified acrylics can also be used. Such acrylics may be polyester-modified acrylics or polyurethane-modified acrylics, as is well known in the art. Polyester-modified acrylics modified with e-caprolactone are described in U.S. Pat. No. 4,546,046 of Etzell et al, the disclosure of which is incorporated herein by reference. Polyurethane-modified acrylics are also well known in the art. They are described, for example, in U.S. Pat. No. 4,584,354, the disclosure of which is incorporated herein by reference.
[0049] Polyesters having active hydrogen groups such as hydroxyl groups can also be used as the film-forming polymer in the composition according to the invention. Such polyesters are well-known in the art, and may be prepared by the polyesterification of organic polycarboxylic acids (e.g., phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid) or their anhydrides with organic polyols containing primary or secondary hydroxyl groups (e.g., ethylene glycol, butylene glycol, neopentyl glycol).
[0050] Polyurethanes having active hydrogen functional groups are also well known in the art. They are prepared by a chain extension reaction of a polyisocyanate (e.g., hexamethylene diisocyanate, isophorone diisocyanate, MDI, etc.) and a polyol (e.g., 1,6-hexanediol, 1,4-butanediol, neopentyl glycol, trimethylol propane). They can be provided with active hydrogen functional groups by capping the polyurethane chain with an excess of diol, polyamine, amino alcohol, or the like.
[0051] Although polymeric or oligomeric active hydrogen components are often preferred, lower molecular weight non-polymeric active hydrogen components may also be used in some applications, for example aliphatic polyols (e.g., 1,6-hexane diol), hydroxylamines (e.g., monobutanolamine), and the like.
[0052] Examples of suitable crosslinking agents include those compounds having one or more functional groups reactive with the functional groups of the film-forming polymer. Examples of suitable crosslinking agents include isocyanate functional compounds and aminoplast resins, epoxy functional compounds, acid functional compounds and the like. Most preferred crosslinkers for use in the coating compositions of the invention are isocyanate functional compounds.
[0053] Suitable isocyanate functional compounds include polyisocyanates that are aliphatic, including cycloaliphatic polyisocyanates, or aromatic. Useful aliphatic polyisocyanates include aliphatic diisocyanates such as ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,6-diisocyanatohexane, 1,4-butylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate (HDI), 1,4-methylene bis-(cyclohexylisocyanate) and isophorone diisocyanate. Useful aromatic diisocyanates include the various isomers of toluene diisocyanate, meta-xylenediioscyanate and para-xylenediisocyanate, also 4-chloro-1,3-phenylene diisocyanate, 1,5-tetrahydro-naphthalene diisocyanate, 4,4′-dibenzyl diisocyanate and 1,2,4-benzene triisocyanate can be used. In addition, the various isomers of alpha.,.alpha.,.alpha.′,.alpha.′-tetramethyl xylene diisocyanate can be used..
[0054] In a most preferred embodiment, the crosslinking agent will comprise one or more components selected from the group consisting of hexamethylene diisocyanate (HDI), the isocyanurates of HDI, the biurets of HDI, and mixtures thereof, with the isocyanurates and biurets of HDI being particularly preferred.
[0055] Suitable isocyanate functional compounds may be unblocked, in which case the coating composition should be utilized as a two component system, i.e., the reactive components combined shortly before application, or they may be blocked. Any known blocking agents, such as alcohols or oximes, may be used.
[0056] In a most preferred embodiment of the coating compositions of the invention, the coating composition will be a two-component system with the reactive film forming polymer and the crosslinking agent combined shortly before application. In such an embodiment, the most preferred coating composition of the invention comprising the mixture of compounds (I) and (II) will be preferably incorporated with the film-forming polymer containing component.
[0057] Hardener component (II) may also comprise one or more solvents. In a preferred embodiment, component (II) will include one or more solvents. Suitable solvents and/or diluents include aromatics, napthas, acetates, ethers, esters, ketones, ether esters and mixtures thereof.
[0058] Additives, such as catalysts, pigments, dyes, leveling agents, and the like may be added as required to the coating compositions of the invention.
[0059] In a most preferred embodiment of the invention, the coating compositions of the invention will further comprise an adhesion enhancing composition comprising a mixture of a first compound (I) and a second compound (II), wherein compound (I) and compound (II) cannot be the same. It has unexpectedly been found that the combination of compounds (I) and (II) provides an improvement in refinish adhesion, i.e., the adhesion of a refinish coating to a bare exposed metal substrate, which is better than that obtained with the use of either compound (I) or compound (II) alone.
[0060] Compound (I) is a low molecular weight polyester compound having both acid and hydroxyl functionality. It will generally have a number average molecular weight in the range of from 150 to 3000, preferably from 300 to 1000, and most preferably from 400 to 600. Compound (I) will generally have a polydispersity of from 1.00 to 2.00, with a polydispersity of 1.50 being most preferred.
[0061] Suitable compounds (I) will also have an acid number in the range of from 70 to 120 mg KOH/g, preferably from 70 to 100 mg KOH/g, and most preferably from 70 to 80 mg KOH/g.
[0062] In addition, suitable compounds (I) will have a hydroxyl number in the range of from 200 to 400 mg KOH/g, more preferably from 300 to 400 mg KOH/g and most preferably from 330 to 360 mg KOH/g.
[0063] Compound (I) generally comprises the reaction product of the reaction of (a) at least one difunctional carboxylic acid, (b) at least one trifunctional polyol, (c) at least one chain stopper, and (d) phosphoric acid.
[0064] Examples of suitable difunctional carboxylic acids (a) include adipic acid, azeleic acid, fumaric acid, phthalic acid, sebacic acid, maleic acid, succinic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer fatty acids, itaconic acid, glutaric acid, cyclohexanedicarboxylic acid, and mixtures thereof. Preferred difunctional carboxylic acids (a) are adipic acid and azeleic acid. Adipic acid is most preferred for use as difunctional carboxylic acid (a).
[0065] The at least one trifunctional polyol (b) may be branched or unbranched, but branched trifunctional polyols are preferred. Examples of suitable trifunctional polyols (b) are trimethylolpropane, trimethylol ethane, glycerin, 1,2,4-butanetriol, and mixtures thereof. Preferred trifunctional polyols (b) are trimethylolpropane and trimethylol ethane, with trimethylolpropane being a most preferred trifunctional polyol (b).
[0066] The at least one chain stopper will generally be a carboxylic acid that is different from the at least one difunctional carboxylic acid (a). Monocarboxylic acids are preferred. Suitable carboxylic acids (c) will preferably contain one or more aromatic structures and will preferably contain some branched alkyl groups. Examples of suitable carboxylic acids (c) include para-t-butyl benzoic acid, benzoic acid, salicylic acid, 2-ethylhexanoic acid, pelargonic acid, isononanoic acid, C 18 fatty acids, stearic acid, lauric acid, palmitic acid, and mixtures thereof. Preferred carboxylic acids (c) include para-t-butyl benzoic acid, benzoic acid, and 2-ethylhexanoic acid, with para-t-butyl benzoic acid being most preferred.
[0067] Phosphoric acid (d) should be added to the reaction mixture in an amount of from 0.03 to 0.20, preferably from 0.05 to 0.15, and most preferably from 0.07 to 0.10. It will be appreciated that while phosphoric acid is most preferred, phosphate esters such as butyl or phenyl acid phosphate and the like are suitable for use as component (d) in the preparation of compound (I).
[0068] Polymerization of the reactants may occur at typical esterification conditions, i.e., 200-230° C. reaction temperature while continuously removing water as a reaction by-product. Solvents that facilitate the removal of water from the reaction system (those that form an azeotrope) such as xylenes, may be used.
[0069] Reactants (a), (b), (c) and (d) will generally be used in a molar ratio of 4.2:4.9:0.01:0.0005 to 5.1:5.6:0.7:0.005, preferably from 4.4:5.0:0.02:0.0008 to 5.0:5.5:0.6:0.003, and most preferably from 4.8:5.2:0.02:0.0009 to 4.9:5.4:0.06:0.002.
[0070] A commercially available and most preferred example of compound (I) is Borchigen HMP, commercially available from the Wolff Walsrode division of the Bayer Corporation of Burr Ridge, Ill., U.S.A.
[0071] Compound (II) comprises a carboxy phosphate ester having the formula:
[0072] wherein M is hydrogen, metal or ammonium, x is a number from 0 to 3, and R is a saturated or unsaturated C 5 -C 40 aliphatic group in which one or more of the aliphatic carbon atoms can be substituted or replaced with a halogen atom (such as fluorine or chlorine), a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a C 6 -C 10 aromatic hydrocarbon group, preferably phenyl or naphthyl, or a C 6 -C 10 aromatic hydrocarbon group that is substituted with one or more (preferably 1 to 3) C 1 -C 6 alkyl groups or —COOR 1 groups wherein R 1 is H, metal, ammonium, C 1 -C 6 alkyl, or C 6 -C 10 aryl, or mixtures thereof
[0073] In preferred compounds (II), R will contain one or more C 6 -C 10 aromatic hydrocarbon groups, and most preferably, one or more C 6 -C 10 aromatic hydrocarbon groups which contain one or more, preferably at least two, —COOR 1 groups wherein R 1 is H, metal, ammonium, C 1 -C 6 alkyl, or C 6 -C 10 aryl.
[0074] In a most preferred compound (II), R will contain at least one C 6 -C 10 aromatic hydrocarbon group and at least two —COOR 1 groups wherein R 1 is H, metal, ammonium, C 1 -C 6 alkyl, or C 6 -C 10 aryl. R 1 will most preferably be a C 1 -C 6 alkyl or a C 6 -C 10 aryl group.
[0075] The —COOR 1 groups may be lateral or terminal. It will be appreciated that when R 1 is H, compound (II) will comprise one or more free carboxylic acid groups. Similarly, when R 1 is a metal or ammonium ion, compound (II) will have one or more carboxylic acid salt groups. Finally, when R 1 is a C 1 -C 6 alkyl or a C 6 -C 10 aryl, compound (II) will comprise one or more ester groups.
[0076] It will be appreciated that suitable compounds (II) can and most preferably will comprise mixtures of compounds having the formula:
[0077] wherein R, M, x, and R 1 are as described above. However, in a most preferred embodiment, such a mixture will contain one or more molecules having the above structure wherein x is 1 or 2, preferably 1, R has at least one C 6 -C 10 aromatic hydrocarbon group substituted with at least one, preferably two, —COOR 1 groups wherein R 1 is H or a C 1 -C 6 alkyl or C 6 -C 10 aryl, most preferably a C 1 -C 6 alkyl, and M is H.
[0078] Compound (II) will generally have a number average molecular weight in the range of from 600 to 1200, preferably from 700 to 900, and most preferably from 750 to 850. Compound (II) will generally have a polydispersity of from 1.00 to 2.00, with a polydispersity of 1.00 to 1.50 being preferred and a polydispersity of 1.15 to 1.35 being most preferred.
[0079] Suitable compounds (II) will also have an acid number in the range of from 50 to 200 mg KOH/g, preferably from 100 to 180 mg KOH/g, and most preferably from 120 to 160 mg KOH/g. In addition, suitable compounds (II) will have a hydroxyl number in the range of from 100 to 250 mg KOH/g, preferably from 120 to 230 mg KOH/g, and most preferably from 150 to 200 mg KOH/g.
[0080] Suitable compounds (II) generally comprise the reaction product of (a) at least one difunctional polyol, (b) phosphoric acid, and (c) at least one trifunctional carboxylic acid.
[0081] Examples of suitable difunctional polyols (a) include neopentanediol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hydrogenated bisphenol A, 1,6-hexanediol, hydroxypivalylhydroxypivalate, cyclohexanedimethanol, 1,4-butanediol, 2-ethyl-1,3-hexandiol, 2,2,4-trimethyl-1,3-pentandiol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,3-propanediol, and mixtures thereof. Preferred difunctional polyols (a) are neopentane diol and 2-ethyl-2-butyl-1,3-propanediol, with neopentane diol being most preferred.
[0082] The at least one trifunctional carboxylic acid (c) may be aromatic or aliphatic in nature, but aromatic containing structures are most preferred. Examples of suitable trifunctional carboxylic acids are trimellitic acid, 1,3,5-benzenetricarboxylic acid, citric acid, and mixtures thereof. Preferred trifunctional carboxylic acids are 1,3,5-benzenetricarboxylic acid and trimellitic acid, with trimellitic acid being most preferred.
[0083] Phosphoric acid (c) is as described above with respect to (I(d)).
[0084] Polymerization of the reactants (a), (b), and (c) may occur at typical esterification conditions, i.e., 200-230° C. reaction temperature while continuously removing water as a reaction by-product. Solvents that facilitate the removal of water from the reaction system (those that form an azeotrope) such as xylenes, may be used. The reaction can also be subsequently admixed with suitable solvents.
[0085] Reactants (a), (b), and (c) will generally be used in a ratio of 6.3:3.0:0.05 to 7.9:4.0:0.15, preferably from 6.7:3.2:0.07 to 7.6:3.8:0.12, and most preferably from 6.9:3.3:0.09 to 7.3:3.5:0.11.
[0086] A commercially available and most preferred example of compound (II) is LUBRIZOL™ 2063, available from the Lubrizol Corp of Wickliffe, Ohio.
[0087] Compound (I) will typically comprise from 50 to 80% by weight of the mixture of compound (I) and compound (II), preferably from 60 to 75% by weight, and most preferably from 65 to 70% by weight, based on the total weight of the mixture of compound (I) and compound (II). Compound (II) will comprise from 20 to 50% by weight of the mixture of compound (I) and compound (II), preferably from 25 to 40% by weight, and most preferably from 30 to 35% by weight, based on the total weight of the mixture of compound (I) and compound (II).
[0088] The composition comprising the mixture of compound (I) and compound (II) will typically be present in a coating composition in an amount of from 0.10 to 1.00% by weight, preferably from 0.10 to 0.30%, and most preferably from 0.15 to 0.25% by weight, based on the total nonvolatile weight of the coating composition.
[0089] The mixture of compound (I) and compound (II) may incorporated into finished coating compositions by conventional mixing techniques using mixing equipment such as a mechanical mixer, a cowles blade, and the like. Although the additives may be added during the manufacturing process or subsequently to a finished coating, those skilled in the art will appreciate that in a most preferred embodiment, the additives will be added post grind during the manufacturing process. Although the mixture of compound (I) and compound (II) may be used in single or two component systems, use in two-component systems is preferred, particularly where the mixture of compounds (I) and (II) is placed in the resin component of a two component system.
[0090] Finally, although a variety of packaging options are suitable for containing the coating compositions of the invention, it is most preferred that coating compositions containing the mixture of compounds (I) and (II) be packaged in epoxy or phenolic lined cans. Packaging in such containers has been found to ensure the retention of optimum adhesion characteristics.
[0091] The mixture of compound (I) and compound (II) when used in coating compositions provides improved adhesion of the coating composition to bare untreated metal substrates, including aluminum and galvanized steel substrates.
[0092] The coating compositions of the invention may be stored as such for prolonged periods at room temperature without gel formation or undesirable changes. They may be diluted as required to a suitable concentration and applied by conventional methods, for example, spraying or spread coating, and cured by exposure to ambient temperatures of from 70 to 75° F. for a period of from 1 to 3 hours, preferably from 1.5 to 2 hours. However, sandable films of the coating compositions of the invention comprising mixtures of compounds (I) and (II) may also be obtained upon exposure of the applied coating to temperatures in the range of from at least 120° F., more preferably up to 140° F., for periods of from 30 to 50 minutes, preferably from 30 to 40 minutes.
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The invention provides a coating composition for use with metallic substrates that provides a unique balance of required properties. In particular, the coating composition of the invention simultaneously provides desirable levels of adhesion to metal, sandability without the production of harmful dust, corrosion resistance, and recoatability. The coating composition of the invention comprises a polyurethane or epoxy/amine film-forming component, and a corrosion protection component consisting of aluminum selected from the group consisting of nonleafing aluminum pigments, the corrosion protection component being present in the composition in an amount effective to prevent corrosion of the substrate. A cured film of the coating applied to a steel substrate has a pass rating after 480 hours in salt spray per ASTM B117.
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FIELD OF THE INVENTION
The present invention relates generally to an open-end spinning frame having a plurality of rotor-type spinning stations in alignment with each other, and relates more particularly to a novel debris disposal arrangement associated with the spinning stations.
BACKGROUND OF THE INVENTION
Open-end spinning frames of this type are known and typically have at each spinning station a spinning rotor supported on a supporting disk seat for rotation in a rotor housing on which a vacuum is applied. Each spinning station includes a pivoted cover on which is disposed a sliver opening device having a rotating opening cylinder for delivering opened fibers into the rotor and a fiber conduit plate for closing the front of the rotor housing. Each spinning station has a debris discharge opening in the pivoted rotor housing cover which communicates with a debris disposal arrangement extending along the spinning frame.
One such representative spinning frame is described, for example, in the manual "AUTOCORO" of the W. Schlafhorst AG & Co. As shown on page 1.3.20, an endless moving debris conveying belt extends the length of the machine underneath the sliver opening devices of the spinning units of the rotor spinning frame for receiving debris discharged through the debris discharge openings of the pivoted rotor housing covers and for conveying such debris to transfer stations disposed at the end of the machine, into which the belts are emptied.
Alternatively, it is also known to provide pneumatic debris aspirating devices in the area of the sliver opening devices in place of such mechanical debris disposal arrangements. For example, German Patent Publication DE 21 12 170 A1 describes a rotor spinning device in which a sliver fed between a draw-in roller and a feed trough is opened into individual fibers by means of an opening cylinder. In the course of this process, debris particles and fibers are also separated to the greatest extent possible. The opening cylinder conveys both components over a fiber guide surface into the area of a debris outlet opening. In the course of this conveyance, the fibers as well as the debris particles are accelerated by the opening cylinder or by the air flow circulating along with opening cylinder to approximately the circumferential speed of the opening cylinder. In the process, the fibers and debris particles have a tendency to leave the circular path tangentially as soon as the compulsory mechanical guidance is interrupted, such as takes place in the area of the debris outlet opening of the opening cylinder housing.
A debris collection chamber is disposed immediately below the debris outlet opening and is connected to a central aspirating device of the spinning frame through a connecting conduit.
A comparable open-end spinning device, slightly modified in the area of the debris outlet opening, is described in German Patent Publication DE 28 56 028 C2. In this case, the debris outlet opening is also designed as an aspirating opening for an air flow directed into the opening cylinder housing to prevent spinnable fibers from being released from the opening cylinder along with debris particles. This air flow is directed onto the opening cylinder to act in the nature of a pneumatic guide to keep the opened fibers on the opening cylinder as a result of their relatively large specific surface in relation to their low mass. However, the debris particles, because of their size and mass, have a clearly higher kinetic energy which overcomes this air flow, causing the debris particles to be propelled away tangentially. Subsequently, the debris particles are entrained by a further air flow and are removed through an aspirating opening. A debris chamber is disposed directly adjoining the debris outlet opening of the opening cylinder housing, which is divided into a debris separating zone and a debris removal zone by means of an air guide wall disposed at a short distance from the debris outlet opening.
Another open-end rotor spinning device with a debris chamber disposed underneath the opening cylinder is known from German Patent Publication DE 43 10 810 A1, which has two separate air flow systems with their own respective aspirating openings. An air flow system acting in the bottom area of the debris chamber disposes of the debris particles combed out by the opening cylinder, while a second, oppositely acting air flow system terminates in a suction flow rotating along with the opening cylinder. The particular disposition of the aspirating opening results in an essentially definite separation of the two flow systems.
Furthermore, the later published German Patent Publication DE 43 34 483 describes an open-end spinning device which has an opening cylinder housing disposed in the pivoted cover element of the spinning unit to be pivotable along with the cover element. The opening cylinder housing has a debris outlet opening with an associated pneumatically chargeable debris reception element disposed at a spacing opposite the opening, resulting in a free space between the debris outlet opening and the debris reception element which communicates with the ambient air. The debris reception element is releasably fastened on the cover element seated on a pivot shaft and is tilted downward around the pivot shaft together with the cover element when the spinning device is opened.
Debris removal at the opening cylinder housings of a rotor spinning frame represents an important element in achieving the objective of faultless processing of fiber materials. Even though the technology of the debris removal devices appears to be relatively simple, these devices are nevertheless very difficult and react sensitively to changes. Even small modifications in the area of the debris outlet openings can disadvantageously change the flow conditions and thereby have a considerable effect on the spinning result which can be achieved.
SUMMARY OF THE INVENTION
Based on the known open-end spinning devices described above, it is an object of the present invention to provide an improved pneumatic debris removal arrangement and, in particular, not provide a debris removal arrangement which can be universally employed.
Briefly summarized, the present invention is adapted to essentially any open-end spinning frame comprising a plurality of aligned spinning stations and a common debris disposal conduit extending along the spinning stations, wherein each spinning station has a spinning rotor drivenly rotated within a rotor housing, a sliver opening device having an opening cylinder rotating in an opening cylinder housing formed with a debris outlet opening, and a pivotable cover having a fiber conduit plate movable with the cover into and out of covering relation to the rotor housing. According to the present invention, each spinning station is equipped with a support rail to which a debris disposal means is mounted in a disposition which is below the debris outlet opening in the open cylinder housing for receiving debris therefrom and which is out of the pivoting path of movement of the cover so as not to interfere with movement of the cover. Basically, the debris disposal means comprises a debris pickup funnel disposed at a spacing from the debris outlet opening of the opening cylinder housing and a connector conduit connecting the debris pickup funnel to the common debris disposal conduit.
The basic design of the pneumatic debris aspirating arrangement of the present invention has the advantage, among other things, that retrofitted installation of the device is possible in rotor spinning frames of the type originally designed for mechanical debris disposal without structural changes in the spinning stations being necessary. Thus, the present debris disposal arrangement makes it possible to equip a rotor spinning machine selectively with either a mechanical or a pneumatic debris disposal installation, and to change the selection later if desired. For example, an existing mechanical debris disposal system can be replaced without problems by the pneumatic debris aspirating device in accordance with the present invention.
In particular, the design of the debris aspirating device in accordance with the present invention, as well as the manner of its installation on the spinning units, assure that none of the functions of the spinning units, especially the opening of the covers for cleaning or other maintenance of the spinning stations, are interfered with in any way.
In a preferred embodiment, the pneumatic debris aspirating device, which is disposed underneath the pivot housings of the rotor spinning units, essentially consists of a debris pickup funnel connected directly or indirectly via a rear aspiration connector to a debris disposal conduit which is charged with a vacuum and extends over the length of the machine. The debris pickup funnel preferably has a transversely extending connecting strip with bores, by means of which the pickup cone can be fixed in place on the support rail disposed on the spinning units. If required, the guide conduit elements of a mechanical debris disposal installation are also fastened on these support rails.
In an advantageous embodiment, the debris pickup funnels may be embodied as asymmetrical injection- molded parts, preferably made of plastic. On the one hand, a component designed in this way can easily be adapted to the structural realities of existing open-end spinning frames, and on the other hand such injection-molded parts can be economically produced, which is also advantageous in view of the great number of spinning stations.
Preferably, the rear aspirating connector of the debris pickup funnel is extended rearward closely underneath the support rail of the rotor spinning units and is connected by a flexible line, for example a spiral hose, to the vacuum-charged debris conduit.
According to a further aspect of the invention, the debris disposal conduit may be embodied as a suction rail extending longitudinally along the full length of the machine, for example underneath a conduit utilized for electrical energy supply. Preferably, the debris disposal conduit is connected at the end of the machine to an aspiration system which is part of the spinning mill and which has, among other things, a filter arrangement and a vacuum source.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a frame unit of an open-end rotor spinning frame with an integrated debris collecting conduit, for assemblage with one or more additional frame units to form a completed open-end spinning frame, and including a schematic representation of an aspirating device forming part of the spinning mill to which the debris collecting conduit is connected;
FIG. 2 is a perspective view of a rotor spinning unit with a debris pickup cone underneath the open cylinder housing, in accordance with the present invention;
FIG. 3 is a vertical cross-sectional view of the rotor spinning unit of FIG. 2, illustrating the pneumatic debris aspirating device in accordance with the present invention; and
FIG. 4 is a top view of a debris pickup cone of FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 depicts an intermediate frame unit 2 of an open-end rotor spinning frame i which is typically assembled end-to-end with additional intermediate frame units 2 (up to twelve intermediate units in total), and a drive frame unit (not shown) at one end of the intermediate units 2 and an end frame unit (also not shown) at the opposite end of the intermediate units 2. As shown, each one of these intermediate units 2 has twenty-four spinning stations 3 (twelve on each side). Each respective spinning station 3 has one open-end rotor spinning unit 4 and a yarn winding unit 5.
As further represented in FIG. 1, each intermediate unit 2 has an aspirating conduit 6 by means of which a common vacuum source is applied to the rotor housings 20 (FIG. 2) of the rotor spinning units 4. An electrical supply conduit 7 and a debris collecting conduit 8 are disposed underneath the aspirating conduit 6. The debris collecting conduit 8 is embodied as a suction rail of the same length as the machine and is connected to an aspirating device 9, typically part of the spinning mill in which the spinning frame is disposed, which basically comprises, among other things, a suction source 10, a filter element 11 and a debris disposal unit 12. Each spinning station 3 also is equipped with a pneumatic debris aspiration device, indicated only schematically at 13 in FIG. 1, the pneumatic debris aspirating devices 13 of the rotor spinning units 4 being individually connected to the debris collection conduit 8 as indicated schematically by broken lines in FIG. 1.
The rotor spinning units 4 are represented in more detail in FIGS. 2 and 3. As is known, each spinning unit 4 includes a spinning rotor 17 mounted to one end of a rotor shaft 16 which is rotatably seated on a set of supporting disks 15, with the opposite end of the shaft 16 supported in an axial bearing 18 against axial forces acting on the rotor. The spinning rotor 17 is driven via a tangential belt 19 to rotate at a high speed in the rotor housing 20. The rotor housing 20 is connected via a connecting line 21 to the aspirating conduit 6.
The rotor housing 20 is closed at its forward side by a fiber conduit plate 22, which is fastened on a cover assembly 23 pivotably mounted to the spinning unit 4. A yarn draw-off nozzle 25 is disposed centrally in an extension 24 of the fiber conduit plate 22. In addition, the cover assembly 23 includes a sliver opening device 27 supported within the cover assembly 23 and a two-part fiber guide conduit 26 which extends from the sliver opening device 27 and terminates in the plate extension 24 to connect the opening device 27 with the interior of the spinning rotor 17. The cover 23 is affixed to a pivot shaft 29 and is normally secured in covering relation over the spinning rotor 17 and the rotor housing 20 by a latch 28, which upon release permits pivoting movement of the cover 23 in the direction S into a first cleaning position or a second maintenance position.
The sliver opening device 27 essentially consists of a sliver draw-in trough 33 opening outwardly through the cover 23 in facing relation to a sliver feed condenser 35, a driven sliver draw-in cylinder 32 disposed within the cover, and a driven opening cylinder 31 rotating inside a sliver opening housing 30 within the cover 23 adjacent the draw-in cylinder 32. The sliver 34 is fed into the sliver opening device 27 via the condenser 35. The housing 30 surrounding the opening cylinder 31 is partially open to define a downwardly oriented debris outlet opening 36.
Each rotor spinning unit 4 is equipped with a pneumatic debris aspirating device 13 fixed in place on a support rail 37 of the spinning unit 4 at a distance below the opening cylinder housing 30. Each debris aspirating device 13 has an asymmetrically formed debris pickup funnel 38 opening upwardly toward the debris outlet opening 36 of the associated opening cylinder housing 30 and is connected via a rear aspirating conduit 39 to the vacuum-charged debris conduit 8 of the rotor spinning frame 1.
As can be seen from FIG. 4 in particular, the debris pickup funnel 38 comprises an asymmetrical receptacle portion defining an upwardly opening debris receiving opening, and the receptacle is asymmetrically tapered inwardly and rearwardly into a rear connecting portion. The receptacle portion of the debris pickup funnel also has a connecting strip 40 formed with fastening bores 41 by which the debris pickup funnel 38 can be fastened on the support rail 37 of the associated rotor spinning units 4.
In the installed state of the pneumatic debris aspirating device, a freely accessible space is created between the downward debris outlet opening 36 of the opening cylinder housing 30 and the upward opening of the debris pickup funnel 38, which permits air to be aspirated without interruption into opening cylinder housing 30 and, in particular, without being negatively affected in any way by the suction force being applied into the aspirating connector 39.
It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof.
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A pneumatic debris aspirating device adapted to be retrofitted on open-end spinning frames originally designed for a mechanical debris disposal installation utilizes an asymmetrical debris pickup funnel which can be connected via a connector conduit to a source of suction which is part of the spinning mill. The debris aspirating device is embodied and disposed such that opening of a cover to each rotor spinning unit is not hampered.
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The present application is a continuation of application Ser. No. 568,403, filed Jan. 5, 1984, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method and apparatus for imparting a simple contour to a workpiece and, more particularly, to a method and apparatus for shot peening a wing skin to form a simple contour which matches the chordwire curvature of an aircraft wing.
2. Description of the Prior Art
The application of simple curvatures to aircraft skins by shot peen forming is not new. It has been done with air nozzle peening for many years as exemplified by U.S. Pat. No. 2,701,408; and by centrifugal shot throwing wheels as exemplified by U.S. Pat. No. 3,705,510. However, the use of shot peening in a metal part as taught by these and other state of the art patents encourages the formation of simple and compound contours. In the typical peening process, a flat piece of metal is peened to form a predetermined shaped contour which approximates the chordwise curvature of a desired aircraft wing. Because the shot consists of spherical elements, their striking of the treated metal part causes the application of compressive stresses to the metal part along axes in all directions, thereby resulting in the curving or contouring of the part in all directions. This peen shaping is known as hemispheric shaping and is desirable for some applications. Accordingly, a compound contour is imparted to the metal skin, namely the skin develops a spanwise curvature in addition to the more desirable chordwise curvature. U.S. Pat. No. 4,329,862 is exemplary of a complicated method for utilizing and propagating compound contours throughout a flat metal sheet to more closely approximate the exact shape of an aircraft wing. However, devising a system which controls and encourages both chordwise and spanwise curvature is extremely complicated and requires extensive trial and error testing to develop appropriate banks of information which can be later programmed into a computer to control the shot peening equipment. It is, therefore, highly desirable to have a method which easily treats the workpiece and develops only chordwise curvature. In response thereto and in applications where it is necessary to inhibit or prevent compound contour formation, pre-stressing or clamping the metal part in an over-curved condition during peening can be an effective preventive method. Further, some metal parts are provided with longitudinal stiffeners which discourage compound curvature by supplying increased strength to the metal part for withstanding the multi-directional compressive forces of the peening process. Additionally, after compound contours have been formed in the peened metal part, subsequent touch-up peening can also be utilized. Touch up peening is substantially a trial-and-error method employed to correct localized compound contouring by peening various locations on the part in an attempt to reverse some of the undesirable growth and compound curvature which had been previously imparted thereto as described above. Unfortunately, such methods of correction are cumbersome and time consuming and extremely expensive, especially when the costs of the additional touch up peening are included.
SUMMARY OF THE INVENTION
The present inventive method and apparatus overcomes the aforementioned problems and effectively minimizes the formation of compound contours in metal having no integral longitudinal stiffeners and further minimizes the amount of touch-up peening which may subsequently be required.
Accordingly, it is a primary objective of the present invention to provide a new method and apparatus for imparting a simple contour to a workpiece and to simultaneously minimize the formation of compound contouring therein.
In accordance with an aspect of the present invention, an improved method for imparting a simple contour to a workpiece is disclosed and includes passing a flat sheet of metal through shot peening equipment, with the equipment shot peening the metal only on one side thereof with the peening being of variable predetermined intensity and specifically applied spanwise to, and in the direction of, the movement of the metal sheet. After completing the application of a single strip of peening to the metal, the orientation of the shot peening equipment and the metal sheet are modified in such a manner as to allow subsequent shot peening to be done in narrow spanwise strips applied in the direction of movement of the workpiece along chord percentage lines of the metal part.
The apparatus of the present invention provides a treatment chamber which has a conveyor means for moving a workpiece therethrough. The conveyor means has a transport means and a rail means. A workpiece affixing means is also provided thereon and includes adjusting means for positioning the workpiece relative to the rail means. One or more shot throwing means further provided in the treatment chamber and is movable and rotatable about an axis and is positioned to one side of the workpiece. Finally, a control system is employed and is electrically connected to the shot throwing means to regulate the flow and direction of the discharged shot and is further connected to the adjusting means to direct and position the workpiece in order to receive the discharged shot in spanwise extending strips.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, advantages and characterizing features of the present invention will become clearly apparent from the ensuing detailed description of an illustrative embodiment thereof, taken together with the accompanying drawings wherein like reference numerals denote like parts throughout the various views and in which:
FIG. 1 is a side elevational view of the shot peening apparatus according to the teachings of the present invention;
FIG. 2 is a perspective view of a flat piece of metal showing an array of spanwise narrow strips of where the shot peening is typically applied; and
FIG. 3 is a schematic of the regulating process utilized by the control system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now in detail to FIGS. 1 through 3, there is disclosed a novel method and apparatus according to the teachings of the present invention having a treatment chamber 10 with a conveyor means 12, or monorail system, extending therethrough. The conveyor means 12 includes a rail means 14 which includes rails 16 extending outwardly from the treatment chamber 10 and supported by any well known support structure (not shown). A transport means 18, which typically includes a tractor 20, provides movement along the rail means 14. A first hoist 22 and a second hoist 24 are rigidly connected via tie bars 26 to the tractor 20 and are each provided with wheels 28 which ride along rail means 14 and further enable ease of movement of the transport means 18 along the conveyor means 12. The first hoist 22 is preferably at least one ton electric chain hoist having a one horsepower motor for the lowering or raising of a chain 30 extending therefrom. The adjusting means, or second hoist 24 is also preferably a one ton electric chain hoist having a one horsepower motor for the lowering or raising of chain 32 which can be programmed to lengthen or shorten the chain 32 to any length thereby pivoting lead beam 36 about pivot point 60. The preferred maximum programmed length for the chain 32 is approximately three feet, but other longer lengths can easily be used with the present invention and are therefore believed to be within the scope of the present invention.
A load beam 36 is provided and is attached to the chains 30, 32 in a manner well known in the art. A flat sheet of metal, or workpiece 38, which is to be treated to become a wing skin, is attached to the underside of the load beam 36 in such a manner by any rigid means as is well known in the art as to be suspended from the rail means 14 via the adjusting means which includes hoists 22, 24, chains 30, 32 and load beam 36. Upon activation of the tractor 20, this entire assembly can be easily transported through treatment chamber 10.
A shot throwing means 40, or blast unit, which is a centrifugal shot throwing wheel, is further provided at a predetermined spaced relationship to the workpiece 38 within treatment chamber 10. In order to carry out the present method and apparatus, a single blast wheel 40 is provided to discharge shot at one side 42 of the flat sheet of metal 38. Side 42, after treatment, will become the convex side of the wing. However, in a preferred embodiment of the present apparatus, an oppositely disposed blast unit (see FIG. 1) is also provided and is utilized in the event that subsequent touch up peening is required. It is important to note that the actual details of the internal workings of the blast units are well known and beyond the scope of the present invention. Shot feeding means and supply apparatus (not shown), including supporting structure, are also provided to supply and receive shot to and from the blast as is also well known in the art. A parameter of importance to the shot throwing means 40, however, is that the shot pattern of discharge must be extremely narrow and is typically a function of the width, curvature, thickness and surface roughness of the metal sheet. The shot throwing means 40 is further provided with an actuator 44 which can be hydraulic or electric and, when activated, causes the shot throwing means 40 to be rotated through a range of predetermined angles about an axis. A vertical support means 46 which supports and allows vertical movement of the shot throwing means 40 is also positioned within treatment chamber 10.
As is more clearly shown in FIG. 3, a programmable control system 48 is provided and is informationally and electronically connected to the transport means 18, the adjusting means 24 and the shot throwing means 40. It is of prime importance to the present invention that in order to maximize the amount of simple contour formation and simultaneously minimize compound contour formation, the discharged shot must be applied to the workpiece 38 in narrow, spanwise strips 50 (see FIG. 2), with the shot throwing means 40 aligned to apply the shot along the direction of movement and the common chord percentage lines of the workpiece 38. Accordingly, the orientation of the discharged shot relative to the workpiece 38 must be highly controlled and regulated by control system 48. More particularly, the adjusting means 24 must operate in synchronization with the shot throwing means 40 in order to allow strips 50 to be formed along predetermined spanwise locations. In order to program the apparatus, via the control system 48, two data bases 52, 54 are generated and fed into the control system 48. Data base 52 consists of the positions of the common chord percentage lines of the workpiece 38. The chord distance is defined as the distance between the leading edge 56 and the trailing edge 58 of the workpiece 38. The values for the common chord percentage lines are defined as the constant percentage of chord distances calculated over the span of the wing. These values, hence, are based on the length of workpiece 38 and the varying chord distances and are easily calculatable values. Data base 54 is generated by measuring the overall dimensions and thickness of the workpiece 38 along its span.
The control system 48 uses the values generated in the data bases 52, 54 to synchronize and control various elements in the treatment chamber 10. The speed of the workpiece 38 is controlled by electronically connecting the tractor 20 thereto. The intensity of the discharged shot is controlled by varying the revolutions per minute of the wheel contained within the shot throwing means 40. The intensity is varied to compensate for the varying thickness and the desired contour of the workpiece 38. The control system 48 utilizes the adjusting means 24 which can raise and/or lower chain 32 and can also either move or rotate the shot throwing means 40 by engaging the vertical support means 46, or the hydraulic actuator 44. Typically, after a particular strip 50 has been shot peened, the control system 48 can then orient the different elements to allow spanwise peening along any given strip 50 on workpiece 38. In this manner, selective portions or entire strips 50 can be treated as desired or programmed. At the present time, it is generally believed that the best results in propagating simple contours occur by shot peening the center of the workpiece 38 and working the method outwardly toward the leading edge 56 and trailing edge 58.
In operation, a workpiece 38 is attached to the load beam 36 and the tractor 20 is activated to transport the workpiece 38 into treatment chamber 10. Data bases 52, 54 have previously been generated by calculating the percentage chord lines and measuring the overall dimensions, including the thickness, of the workpiece 38. The programmable control system 48 is engaged and simultaneously regulates the speed of the tractor 20, the angular and vertical position of the shot throwing means 40, as well as the intensity of the shot to be discharged therefrom. The tractor 20 moves the affixing means and transport means 18 along conveyor means 12 with the workpiece 38 suspended therebelow. The control system 18 longitudinally orients the shot throwing means 40 so that the shot is discharged in a narrow spanwise strip 50 along the direction of travel and on the common chord percentage lines of workpiece 38. After treatment of a strip 50 has been completed, the control system 48 utilizes the adjusting means 24 to either raise or lower chain 32. The angular and vertical orientation of the blast unit 40 is likewise adjusted with the workpiece 38 again passing the blast unit 40, thereby allowing treatment of a second narrow strip 50 on the surface of the workpiece 38. The particular adjustments of the adjusting means 24 and blast unit 40 are dependent upon the location of the second and subsequent strips 50 on the workpiece 38.
In summary of the overall operation of the present invention, a flat sheet of metal, or workpiece 38, is passed through shot peening equipment, with shot peening occurring on a single side thereof and with the peening occurring with variably controlled intensity in the direction of movement of the workpiece 38. The positioning of workpiece 38 is regulated by a control system 46 which monitors the spatial relationship between workpiece 38 and shot throwing means 40 assuring that the peening occurs in narrow spanwise strips 50 along common chord percentage lines.
From the foregoing, it is apparent that the objects of the present invention have been fully accomplished. As a result of the present invention, a new and improved method and apparatus for imparting a simple contour to a workpiece has been disclosed. A preferred embodiment of the principles of this invention having been described and illustrated, it is to be realized that the same are not limited to the particular method and apparatus shown in the drawings, and that modifications thereof are contemplated and can be made without departing from the spirit and scope of this invention as defined in the appended claims.
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An improved method and apparatus is provided for imparting a simple contour to an aircraft skin. A treatment chamber having a conveyor with a workpiece attached thereto and a shot peening blast unit positioned therein is provided. The workpiece is conveyed past the blast unit for peening treatment. A control system is provided for orienting the workpiece and blast unit so that the peening is done only in narrow spanwise strips and only on common chord percentage lines of the workpiece. This method and apparatus thereby creates chordwise simple curvature to the workpiece while minimizing compound curvature effects.
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PRIORITY CLAIM
[0001] This application claims the benefit of prior U.S. provisional application Ser. No. 61/407,761 filed Oct. 28, 2010, the contents of which are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] This application relates to slicing devices, particularly including devices for slicing fruits and vegetables.
BACKGROUND OF THE INVENTION
[0003] Devices for cutting apples into sections have been available for many years. In a typical device, several radial blades are supported by a central hub blade and an outer frame. As the device is pushed downward over an apple, the central hub blade cuts the core into a central cylinder while the radial blades divide the remaining apple into several wedge-shaped sections.
[0004] Unfortunately, the current devices can be difficult to use because they do not readily push all the way through an apple or other food item. The skin of an apple, for example, may provide resistance against a complete cut. This leads to users pushing against the final bit of apple with their fingers, risking a cut or injury as the fingers come into contact with the blade.
SUMMARY OF THE INVENTION
[0005] A preferred example of the invention includes a slicer and a pusher, in which the slicer has a peripheral frame and internal cutting blades. The pusher is configured to be used to push at least partially sliced food items through the gaps between cutting blades.
[0006] In a preferred version of the invention, the device is configured to cut fruits into wedges and therefore the cutting blades are arranged in a radial fashion with substantially wedge-shaped gaps between blades.
[0007] In other versions of the invention, the blades may be arranged in a grid fashion, creating square, rectangular, or other shaped openings. In either case, for the sake of simplicity, the device will be referred to as an apple wedger.
[0008] In some examples the pusher is hingedly attached to the slicer so that it can swing away from or toward the slicer in a pivotal fashion. When pivoted toward the slicer, raised projections on the pusher are urged into the openings between blades to push through any food items remaining in those openings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Preferred and alternative examples of the present invention are described in detail below with reference to the following drawings:
[0010] FIG. 1 is a perspective view of a preferred apple wedger, shown with a slicer and a pusher in a closed position.
[0011] FIG. 2 is a perspective view of the apple wedger of FIG. 1 , shown with the pusher in an open position.
[0012] FIG. 3 is a perspective view of the apple wedger of FIG. 1 , shown with the pusher in an intermediate position.
[0013] FIG. 4 is a perspective view of the apple wedger of FIG. 1 , shown with the pusher in an intermediate position, nearly in the closed position.
[0014] FIG. 5 is an exploded view of the apple wedger of FIG. 1 .
[0015] FIG. 6 is a bottom perspective view of the apple wedger of FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] A preferred version of the apple slicer and wedger is shown in the Figures as described below. As illustrated, the wedger includes a slicer 10 and a pusher 100 pivotally secured to the slicer.
[0017] The slicer includes a peripheral frame 20 that is preferably formed in a ring or circular shape. In some alternate versions, the frame may be square or have a different shape other than circular. In a preferred example, the frame is rigid and formed from plastic, stainless steel, or other materials of sufficient strength to withstand the force imparted by urging the blades through an apple.
[0018] The blade portion of the slicer includes a central ring blade 30 and several radial blades 40 spanning the distance between the ring blade and the frame. Because the ring blade is located substantially at the center of the frame, each of the radial blades is substantially identical and divides the annular space between the frame and ring blade into equal wedge-shaped sections. In a preferred version the ring blade and radial blades are formed from stainless steel and welded or otherwise permanently secured to one another.
[0019] As best seen in the top perspective view, each of the blades 40 includes a sharpened lower edge 41 . Likewise, the central ring blade includes a sharpened lower edge.
[0020] The frame may optionally include a pair of handles 50 , 52 to aid in pushing the blades downward against an apple or other fruit. In the version as illustrated, the handles are diametrically opposite one another and oriented with distal ends that are raised above the plane of the blades and the rest of the frame, extending generally away from the sharpened edge of the blades. In other versions handles may be formed as a peripheral flange and need not be above the plane of the blades. Still further, in some versions the handle may include a soft grip which, for example, may be in the form of a resilient material over-molded onto a more rigid handle foundation.
[0021] The pusher 100 is configured for pivotal attachment to the slicer, preferably being attached at a hinge located along an edge of each of the pusher and slicer. Thus, in the preferred example the pusher and slicer each include complementary loops positioned and configured to receive a pin 70 that serves as an axis of rotation. As shown, the slicer 10 preferably includes a single loop 60 that is positioned between a pair of loops 110 , 112 formed on the perimeter of the pusher. The loops are each configured with a central bore to receive the pin, thereby allowing the pusher and slicer to pivot about the pin with respect to one another. In alternate version of the invention, a variety of other configurations may be used to enable the pusher to pivot with respect to the slicer.
[0022] In the illustrated version, the hinge is formed at an upper end of the frame 20 , and therefore the loops 110 , 112 are positioned above the bottom of the pusher. In this configuration, the pin 70 forming the pivot axis is positioned at or above the top surface of the raised projections of the pusher. This positioning of the pivot axis allows a fuller rotation of the pusher before it contacts the food at the bottom of the slicer, thereby providing a more even force against the food rather than a force initially applied at the side adjacent the hinge.
[0023] In yet other versions, the pusher and slicer are not pivotally attached to one another, and in such versions the loops and pin are not used. The pivotal attachment is preferred, however, for ease of use and to retain the two components together for easy storage. Most preferably, each of the pusher and the slicer has a substantially circular perimeter, with the pusher and slicer being pivotally attached to one another at a location on the perimeter.
[0024] The pusher 100 is shaped with a perimeter that generally matches that of the slicer. Thus, most preferably the pusher is circular and includes an upwardly extending peripheral flange 120 . In a version in which the perimeter of the blade is square or otherwise shaped, preferably the pusher has a corresponding perimeter. The frame 20 of the slicer 10 preferably is also formed with an outer sidewall that includes a complementary channel or other surface that is sized and configured to receive the flange when the pusher is pivoted to a position in which the pusher is closed snugly against the slicer. Thus, the outer perimeter of the slicer is seated just within the flange of the pusher when the two components are pivoted together.
[0025] In the version as illustrated, rather than a complementary channel formed along a lower edge of the frame, the outer sidewall of the frame 20 includes an upper portion 23 and a lower portion 22 , with the lower portion being recessed radially inward with respect to the upper portion. Accordingly, the diameter of the upper portion is somewhat larger than the lower portion, with a shoulder 21 defined at the transition between the upper and lower portions. The diameter of the outer surface of the lower portion of the frame is sized to snugly receive the inner surface of the peripheral flange 120 of the pusher when the pusher is pivotally rotated into a position closely adjacent the slicer.
[0026] The pusher further includes an interior floor portion that is generally planar, transitioning to several raised projections sized and positioned to fit in the spaces between the blades. The projections are raised in an upward direction that extends toward the slicer when the pusher is rotated into a closed position adjacent the slicer.
[0027] In the version as shown, there are eight radial blades 40 that define eight wedge-shaped spaces between the blades. Likewise, the pusher includes eight raised projections 140 that are positioned to fit between a respective one of the wedge-shaped spaces. In other versions, the device includes a greater or lesser number of blades and therefore a greater or lesser number of projections so that a projection is positioned between each pair of blades.
[0028] The projections 140 as shown in the preferred version have a height that is greatest adjacent the center of the pusher and somewhat rounded and tapered to a lower height toward the ends of the projections that are radially outward from the center. This greater height at the middle provides for a stronger pushing force at the center, where the greatest force may be required. In other versions, the height of the projections may be substantially the same across the entire top surface of the projection.
[0029] A central hub projection 130 is provided at the center of the pusher, positioned and shaped to fit within the ring blade 30 . Thus, the hub projection is generally cylindrical in shape, though with slightly rounded corners to more readily fit within the ring blade and to provide for greater tolerance as the pusher rotates into contact with the slicer.
[0030] In the version as shown, the device is configured as an apple wedger that removes a core of an apple while slicing the remainder of the apple into wedge-shaped pieces. Accordingly, the pusher is configured with a central hub and eight wedge-shaped projections (when viewed from the top or bottom), each of the wedge-shaped projections being arranged circumferentially about the central hub.
[0031] In alternate versions, a greater or lesser number of wedge-shaped projections may be used. Likewise, the slicer and pusher may be formed without a central ring blade and corresponding hub, thereby forming a slicer that does not simultaneously separate the core from the fruit. In such a version, the blades 40 are simply joined substantially at the center of the slicer to form a plurality of wedges.
[0032] In yet other versions, the slicer includes a plurality of blades arranged perpendicularly to form a grid of squares which may be used to cut a potato into French fries or other such shapes. As still another version, the slicer may include a plurality of blades oriented parallel to one another to create slices, but without the orthogonal blades forming a grid as noted above, or with only a single blade perpendicular to the group of parallel blades in order to provide structural support. In the preferred implementation of each of the preferred versions the pusher includes projections sized and oriented to fit between the spaces separating the blades.
[0033] At a location diametrically opposite the hinge joining the pusher and slicer, the pusher includes a radial lip 150 sufficiently large to be engaged by a thumb or finger in order to separate the pusher from the slicer. The slicer and pusher may each further include a tongue and groove or other such complementary surfaces to retain the pusher against the slicer for storage (in the position as shown in FIG. 1 ), thereby requiring a small separation force to detach the tongue from the groove to rotate the pusher pivotally away from the slicer. The tongue and groove feature is provided on the inner face of the flange 120 and outer face of the sidewall of the frame 20 , positioned at complementary locations.
[0034] In the version as shown, the shoulder between the upper and lower portions of the peripheral sidewall of the frame 20 includes an upwardly scalloped edge 24 to accommodate the tongue and groove feature. Likewise, the lip 50 is positioned at a raised location along the outer flange 120 of the pusher.
[0035] In use, the slicer is placed against an apple or other food item. In the case of an apple, the slicer is preferably positioned such that the central ring blade is coaxial with an axis extending through the core of the apple from the stem to the blossom. The slicer is pushed downward against the apple, thereby separating the apple into wedges and forming a central cylinder segment that contains the majority of the core. In this initial operation of the slicer, the pusher is pivoted away from the slicer, preferably at an obtuse angle, so that it does not interfere with the slicing action. This orientation of the pusher with respect to the slicer is shown in FIG. 2 , in which the pusher has been pivoted away from the slicer through an arc of more than 180 degrees with respect to its initial position as illustrated in FIG. 1 . Most preferably, the pusher may be rotated about 225 degrees away from its resting or storage position in FIG. 1 in order to facilitate slicing. A suitable configuration, however, is one in which the pusher can simply be rotated away from the slicer sufficiently to allow the slicer to be pressed fully downward onto a horizontal surface while the pusher is rotated laterally away from the slicer. Such a rotation would be about 180 degrees, and perhaps slightly more or less depending on the position and configuration of the hinge. In the illustrated example, the hinges are positioned on the upper end of the frame and therefore a rotation of the pusher of less than 180 degrees will effectively move the pusher out of the area defined by an arc of 180 degrees with respect to the slicer. Thus, a rotation of “about” 180 degrees should be understood to include a somewhat smaller path of rotation as long as it allows the slicer to be pressed onto a horizontal surface with the pusher attached.
[0036] As noted above, the initial slicing is performed with the pusher rotated away from the slicer. Thus, the initial slicing is done by pressing the slicer downward against a food item and toward a countertop or cutting board while the pusher is rotated away.
[0037] At the termination of the slicing action, a portion of the meat and skin of the apple may not be fully sliced. In such a case, the pusher is rotated toward a closed position, adjacent the slicer. The path of rotation is shown in FIGS. 3 and 4 , which illustrate intermediate positions of the pusher as it is progressively pivoted toward the slicer. As the pusher is rotated toward a fully closed position (as in FIG. 1 ), the raised projections of the pusher are urged into the spaces between the blades, thereby pushing any remaining bits of apple further through the spaces defined between the blades. Once the pusher is fully rotated to a closed position adjacent the slicer, the apple will be fully sliced by the blades and pushed into a position fully separated from the blades.
[0038] In some versions, the slicer may include a receptacle attached to the slicer and positioned to receive sliced bits as they are pushed upward and through the blades. Ideally, the receptacle is removably attached to the frame of the slicer, to allow the slices to be accessed readily after slicing. This version is intended to be used in a fashion as described above, first pressing the slicer through the food item and against a cutting board or countertop, then swinging the pusher around to push the remaining bits through the blades.
[0039] 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. 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.
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An apple wedger for cutting fruits or vegetables into wedges or other desired shapes includes a slicer and a pusher, in which the slicer has a peripheral frame and internal cutting blades. The pusher is configured to be used to push at least partially sliced food items through the gaps between cutting blades. In some versions, the pusher is pivotally attached to the slicer.
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RELATED APPLICATIONS
This patent arises from a continuation of U.S. patent application Ser. No. 09/883,546, filed Jun. 18, 2001, the entirety of which is hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to audience measurement and, more particularly, to method and apparatus to count audience members.
BACKGROUND
It is customary in the field of audience research to employ a measurement apparatus with each program receiver within each of a plurality of statistically selected locations in order to determine tuning data. Program receivers include television receivers, radio receivers, computers, and/or other devices capable of being tuned to programs that are distributed over the air, over cable systems, by way of satellites, etc. Tuning data, for example, includes the identity of the channel or station to which the program receiver is tuned and/or the identity of the program to which the program receiver is tuned.
It is further customary to provide a manual input 20 device that can be used by those audience members who are actually in an audience of a receiver to indicate their identities to the measurement apparatus. This manual input is frequently provided in the form of a Peoplemeter which not only allows each audience member to manually enter a corresponding audience member identification but also provides a visual status indicator for showing which of the audience members have indicated that they are currently in the receiver's audience. For example, this visual status indicator may comprise a plurality of selectively illuminated light emitting diodes disposed on a box placed adjacent to a receiver and within the field of view of the audience members.
The manual input device alternatively may be a battery-powered remote control or other remote device that includes a keypad and an infra-red pulse transmitter which permit an audience member to manually enter the member's identity and to transmit that identity by way of infra-red pulses to the measurement apparatus or other data collector. The measurement apparatus or other data collector also provides a visual status indication as discussed above. An exemplary remote control of this type is disclosed by Kiewit in U.S. Pat. No. 4,876,736. Still other alternative devices which collect manually entered audience member identification data and which use the receiver to indicate the currently recorded audience status are known.
The tuning data from the measurement apparatus and the audience member identities from the manual input device are commonly time stamped with the times of each tuning event and/or of each change in audience composition. The time stamped tuning and audience member records are then stored in a store and forward unit within the statistically selected location for subsequent forwarding to a data collection central office, such as on a daily or other basis.
Because audience members forget from time to time to enter their identities, it is known to prompt the audience members to manually enter their identities. 15 However, it is well known in audience measurement that systems relying on prompting signals sent to cooperating audience members must be concerned about the frequency of those prompting signals. If a cooperating individual perceives the prompting signals as being so frequent as to be annoying, he or she may stop cooperating. On the other hand, if the prompting is too infrequent, the cooperating individual may forget to enter data at appropriate times.
McKenna et al., in U.S. Pat. No. 4,816,904, discloses an arrangement in which a prompting message is displayed on a television screen overlaid on viewer selected programming by mixing the prompting message with the video signal being sent to the display. However, McKenna et al. do not teach how to effectively regulate the prompting frequency.
Therefore, the present invention is directed to the use of tuning and/or audience response data in an 10 adaptive prompting algorithm to select the frequency with which prompting occurs.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features and advantages of the present invention will become more apparent from a detailed consideration of the invention when taken in conjunction with the drawings in which:
FIG. 1 is a schematic diagram of an audience measurement system in accordance with an exemplary 20 embodiment the present invention;
FIG. 2 is a schematic diagram of an audience measurement apparatus of the audience measurement system shown in FIG. 1 ;
FIG. 3 is a schematic diagram of a data storage I 5 and forwarding unit of the audience measurement system shown in FIG. 1 ;
FIGS. 4A and 4B form a flow chart of a prompting program that may be used in connection with the audience measurement system of FIG. 1 ; and,
FIGS. 5-8 are tables of exemplary data useful in the explanation of the operation of the audience measurement system of FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1 , an audience measurement system 10 is provided at a statistically selected location 12 in which known audience members are present. The statistically selected location 12 , for example, may be a household. The audience measurement system 10 includes a portable remote control device 14 which controls a receiver 16 . The receiver 16 , for example, may be a television receiver as shown in FIG. 1 , although the receiver 16 could instead be a radio, a computer, or any other receiver that is capable of being tuned to programs distributed over the air, over cable, by way of satellite, or by way of other communication methodology to the statistically selected location 12 .
The portable remote control device 14 may have a user interface such as a keypad which includes buttons to allow an audience member to enter channel numbers, to change channels up and down, to increase and decrease volume, to mute the receiver 16 , and to turn the receiver 16 on and off. Thus, the portable remote control device 14 can be used from a remote position 18 in order to change the channel, volume level, and so on of the receiver 16 .
The keypad of the portable remote control device may also permit audience members to identify themselves when they are in the audience of the receiver 16 . The names and appropriate demographic information of each of the audience members may be associated with a corresponding one of the buttons of the keypad and may be suitably stored in an appropriate memory. Accordingly, when an audience member presses a button for identification purposes, the time and date of the press, the appropriate identification, and the appropriate demographic information may be stored with the corresponding tuning data.
The audience measurement system 10 is arranged to log data on audience membership (hereinafter “audience member identification data”). The audience measurement system 10 may be arranged to also log tuning data regarding the programs and/or channels to which the receiver 16 is tuned. Periodically, the logged data is transmitted over a network 20 to a data collection central office 22 . The network 20 may be any mechanism for conveying the logged data to the data collection central office 22 . For example, the network 20 may be a public switched telephone network, as is conventional practice in the audience measurement art.
The portable remote control device 14 may be used to enter member identification data into a measurement apparatus 24 which is installed adjacent to the receiver 16 . The measurement apparatus 24 may also be arranged to acquire tuning data from the receiver 16 in any conventional manner in addition to the audience member identification data acquired from the portable remote control device 14 . Additionally or alternatively, the audience member identification data may be entered by devices other than the portable remote control device 14 . For example, a Peoplemeter may be used to enter member identification data into the measurement apparatus 24 as discussed above. Additionally or alternatively, the audience member identification data may be entered by use of switches mounted directly on the measurement apparatus 24 , or the audience member identification data may be entered into the measurement apparatus 24 by use of an electronic program guide (EPG). If an EPG is used, the EPG may also be used to enter tuning data into the measurement apparatus 24 . The acquired tuning and audience member identification data can be communicated to the data collection central office 22 by a variety of techniques known to those skilled in the art.
The audience measurement system 10 includes a data storage and forwarding unit 26 which collects the tuning and audience member identification data from the measurement apparatus 24 and which stores the tuning and audience member identification data until a scheduled forwarding time when the tuning and audience member identification data are forwarded to the data collection central office 22 . The data storage and forwarding unit 26 may also store and forward tuning and audience member identification data collected from a measurement apparatus, similar to the measurement apparatus 24 , associated with each of the other receivers (not shown) located in the statistically selected location 12 . The audience measurement system 10 , the measurement apparatus 24 , and/or the data storage and forwarding unit 26 may be referred to herein as an audience meter.
The measurement apparatus 24 can comprise logic and a memory so that the current tuning data can be acquired and determined by the measurement apparatus 24 based upon channel selection inputs from the portable remote control device 14 .
Alternatively or additionally, the measurement apparatus 24 may receive a signal replica from a signal detector 34 . For example, this signal detector 34 may be in the form of a video signal source detector such as that disclosed by Chan, in U.S. Pat. No. 5,889,548. This video signal source detector may be positioned as taught in the Chan application to acquire a replica of a video signal from an input to a CRT of the receiver 16 .
Alternatively or additionally, the signal detector 34 may be in the form of a microphone which acquires a replica of an audio output from a speaker of the receiver 16 . Accordingly, the signal detector 34 is arranged to non-intrusively acquire from the receiver 16 a replica of the video and/or audio signal processed by the receiver 16 .
The signal replica acquired by the signal detector 34 can then be processed by the measurement apparatus 24 according to a variety of tuning measurement methodologies. For example, (i) an ancillary video and/or audio code (such as a source identification (SID) code) identifying the tuned program or channel can be read from the signal replica, if present, (ii) video and/or audio feature signatures characteristic of the tuned program can be extracted from the signal replica and compared to reference signatures in order to identify the program or channel, and/or (iii) the signal replica can be correlated with a contemporary reference signal obtained by a reference scanning tuner controlled by the measurement apparatus 24 in order to identify the program or channel.
As a further alternative, the signal detector 34 may be arranged to detect the local oscillator frequency of the receiver 16 . This local oscillator frequency indicates the channel to which the receiver 16 is tuned, as is known in the audience measurement art.
Moreover, whether or not the signal detector 34 is employed, the measurement apparatus 24 may receive an ON/OFF input from an ON/OFF sensor 36 . The ON/OFF sensor 36 , for example, may be an inductive sensor which determines that the receiver 16 is on by detecting the inductive signals emanating from the receiver 16 . In the case where the receiver 16 is a television receiver, the ON/OFF sensor 36 may be an inductive sensor which, as is well known, determines that the receiver 16 is on by detecting the horizontal retrace frequency of the CRT of the receiver 16 . Alternatively, the ON/OFF sensor 36 may have a photodetector probe positioned in relation to the screen display of the receiver 16 so that changing light levels or the amount of light emanating from the screen display can be used to indicate when the receiver 16 is on or off. Alternatively, the ON/OFF sensor 36 can be any other type of sensor suitably arranged to determine the on/off status of the receiver 16 .
In controlling the receiver 16 , the portable remote control device 14 preferably operates in the manner of a conventional universal remote control capable of controlling two or more tuner appliances, such as a television receiver, a VCR, and/or a cable converter. Such a universal remote control conventionally uses several different code sets so that it can operate in multiple user-selected modes. One or more of these modes can be used to transmit a tuning or other command (e.g., a fast forward command sent to a VCR) to the currently active tuner (e.g., the tuner of receiver 16 or of a set-top cable converter or of a VCR) controlling the receiver 16 . In addition, one of the modes of the portable remote control device 14 is also used to transmit audience member identification data to the measurement apparatus 24 .
Optionally, the keypad of the portable remote control device 14 may be provided with dedicated buttons associated with each of the audience members. Accordingly, these dedicated buttons may be used by the audience members exclusively for member identification.
The measurement apparatus 24 as shown in FIG. 2 includes a microprocessor 52 suitably connected to a transceiver 54 , the signal detector 34 , a ROM 56 , a RAM 58 , the ON/OFF sensor 36 , and an interface 60 . The transceiver 54 , coupled to the microprocessor 52 executing a program stored in the ROM 56 , is used to receive tuning status and/or audience member identification data from the portable remote control device 14 . The tuning status data, along with the current audience member identification data and a time stamp, are temporarily saved in the RAM 58 . Optionally or alternatively, the measurement apparatus 24 may also respond to the signal detector 34 , as discussed above, in order to identify the tuned program from codes, signatures, or correlations, or to determine the tuned channel such as by detecting the local oscillator frequency of the receiver 16 . This information can be temporarily stored in the RAM 58 . The measurement apparatus 24 additionally may be arranged to determine the ON/OFF status of the receiver 16 from the ON/OFF sensor 36 . The ON/OFF status of the receiver 16 is used as discussed below in the prompting of audience members to enter their identifications by use of the portable remote control device 14 (or otherwise) in accordance with a prompting program described below. As discussed above, the measurement apparatus 24 transmits the ON/OFF, tuning, and audience member identification data to the data storage and forwarding unit 26 by means of the interface 60 .
Accordingly, the measurement apparatus 24 through execution by the microprocessor 52 of a program stored in the ROM 56 acquires and/or determines tuning data associated with the tuning of the receiver 16 and temporarily stores this tuning data in the RAM 58 . The measurement apparatus 24 also acquires and/or determines the ON/OFF status of the receiver 16 and temporarily stores this status in the RAM 58 . Moreover, the measurement apparatus 24 receives audience member identification data and temporarily stores this data in the RAM 58 . The measurement apparatus 24 through use of the interface 60 communicates any or all of this data to the data storage and forwarding unit 26 . For example, the measurement apparatus 24 may communicate this data to the data storage and forwarding unit 26 immediately upon acquisition.
As shown in FIG. 3 , the data storage and forwarding unit 26 includes a microprocessor 82 suitably coupled to an interface 84 , a ROM 86 , a RAM 88 , and an interface 90 . The interface 84 and the interface 60 support communications between the measurement apparatus 24 and the data storage and forwarding unit 26 , and the interface 90 supports communication between the data storage and forwarding unit 26 and the data collection central office 22 as discussed above.
The ROM 86 stores a program 100 represented by the flow chart shown in FIGS. 4A and 4B in order to collect and forward tuning and audience member identification data from each measurement apparatus 24 associated with a corresponding receiver 16 in the statistically selected location 12 and to provide prompting instructions to audience members through the appropriate measurement apparatus 24 so as prompt the audience members to identify themselves. The prompting management implemented by the 15 program 100 relies on audience participation history of each possible audience member, by receiver and by source identification (SID) class. A SID is an ancillary code that is inserted into programs so as to identify the programs or their sources.
Other technologies, such as navigation characteristics, may provide valuable information for prompt management. Navigation characteristics indicate the manner in which certain audience members tune the receiver 16 . For example, one of the audience members may channel surf. Thus, any time that channel surfing is detected, the probability that the channel surfing audience member is in the audience may be increased. The program 100 is particularly useful where the measurement apparatus 24 cannot clearly detect channel changes.
An instance of the program 100 as shown in FIGS. 4A and 4B may be provided at the data storage and forwarding unit 26 for each of the receivers at the statistically selected location 12 . Alternatively, the program 100 as shown in FIGS. 4A and 4B may be arranged to execute at the data storage and forwarding unit 26 and to accommodate all of the receivers at the statistically selected location 12 . As a further alternative, an instance of the program 100 may be provided at the measurement apparatus 24 associated with each of the receivers at the statistically selected location 12 .
As shown in FIG. 4A , when the program 100 receives data indicating that the receiver 16 has been turned on, the program 100 at a block 102 acquires tuning data related to the receiver 16 and stores that data in the RAM 88 . At a block 104 , the program 100 instructs the appropriate measurement apparatus 24 to immediately prompt the audience members in the audience of the receiver 16 to identify themselves. This prompting may be effected by on-screen displays on the receiver 16 , by a visible display provided by the measurement apparatus 24 or the portable remote control device 14 , by an audible message provided by the measurement apparatus 24 or the portable remote control device 14 , etc.
The responsive audience member identification data is received at a block 106 . In the case where the audience member identification data is provided by the portable remote control device 14 and the program 100 is executing at the data storage and forwarding unit 26 , this audience member identification data is received through use of the transceiver 54 and is communicated to the data storage and forwarding unit 26 by the measurement apparatus 24 . Alternatively, the measurement apparatus 24 may be provided with input keys, switches, and the like in which case the measurement apparatus 24 receives the audience member identification data directly and communicates to the data storage and forwarding unit 26 . The program 100 at a block 108 stores the audience member identification data in the RAM 58 or the RAM 88 , as appropriate, and, at a block 110 , also updates the SID class tables as appropriate.
These tables are used by the data storage and forwarding unit 26 to maintain a running accumulator of audience composition. The running accumulator is a count of the number of times each audience member logs onto each of the receivers 16 in the statistically selected location 12 and is maintained by time period and by class of SID code.
The table of FIG. 5 illustrates a single month's accumulation of data for a single household for all SID classes. As the table of FIG. 5 indicates, days are broken into day parts. The table is further broken into the various audience members present in the statistically selected location 12 , and the table further breaks down each audience member by receiver. As shown in FIG. 5 , the audience members are indicated by their sex and age, and the receivers are indicated by their location (such as bedroom, living room, and kitchen). However, instead of sex and age, other identifiers such as names may be used to identify the audience members, which may be particularly useful where multiple members having the same sex and roughly the same age are present at the statistically selected location 12 . Moreover, receiver location identities other that bedroom, living room, and kitchen may be assigned to the receivers used in the statistically selected location 12 , which may be particularly useful where there are multiple rooms of the same room type in the statistically selected location 12 .
The exemplary data provided in the table of FIG. 5 indicates, for example, that the 35-49 year old female audience member used the receiver in the bedroom eighteen 10 times to receive programs at 6:00 AM during the month covered by the table of FIG. 5 , that the 35-49 year old female audience member used the receiver in the bedroom nineteen times to receive programs at 6:30 AM during the month covered by the table of FIG. 5 , that the 35-49 year old female audience member used the receiver in the bedroom twenty-two times to receive programs at 7:00 AM during the month covered by the table of FIG. 5 , that the 35-49 year old female audience member used the receiver in the bedroom twenty-one times to receive programs at 7:30 AM during the month covered by the table of FIG. 5 , and so on. The table holds similar data for the other audience members at the statistically selected location 12 and for other day parts.
The tuning occasions section of the table stores data related to how many times during each day part each receiver 16 at the statistically selected location 12 was used, regardless of the number of audience members in the audience of that receiver during that time and month. Thus, for example, the 35-49 year old female audience member used the receiver in the bedroom eighteen times to receive programs at 6:00 AM during the month covered by the table of FIG. 5 , and the 35-49 year old male audience member used the receiver in the bedroom one time to receive a program at 6:00 AM during the month covered by the table of FIG. 5 . However, there were only eighteen tuning occasions during which the receiver in the bedroom was used at 6:00 AM for the relevant month, because the 35-49 year old female audience member and the 35-49 year old male audience member used the receiver in the bedroom at 6:00 AM on the same day during the month covered by the table of FIG. 5 .
As another example, the 35-49 year old female audience member used the receiver in the living room eight times to receive programs at 6:00 PM during the month covered by the table of FIG. 5 , the 35-49 year old male audience member used the receiver in the living room one time to receive a program at 6:00 PM during the month covered by the table of FIG. 5 , and the 12-17 year old female audience member used the receiver in the living room fourteen times to receive programs at 6:00 PM during the month covered by the table of FIG. 5 . However, there were only fifteen times that the receiver in the living room was on with someone in the audience during the 6:00 PM day part for the relevant month, because on several occasions there were more than one audience members in the audience of the living receiver during that day part. Thus, there were only fifteen tuning occasions during which the receiver in the living room was used at the 6:00 PM day part for the relevant month.
The counts section of the table stores data related to the sum of the data by receiver and day part for the relevant month. Thus, for example, the 35-49 year old female audience member used the receiver in the bedroom eighteen times to receive programs at 6:00 AM during the month covered by the table of FIG. 5 , and the 35-49 year old male audience member used the receiver in the bedroom one time to receive a program at 6:00 AM during the month covered by the table of FIG. 5 . Thus, the count for the bedroom receiver is 18+1=19 for the 6:00 AM day part for the relevant month.
As another example, the 35-49 year old female audience member used the receiver in the living room eight times to receive programs at 6:00 PM during the month covered by the table of FIG. 5 , the 35-49 year old male audience member used the receiver in the living room one time to receive a program at 6:00 PM during the month covered by the table of FIG. 5 , and the 12-17 year old female audience member used the receiver in the living room fourteen times to receive programs at 6:00 PM during the month covered by the table of FIG. 5 . Thus, the count for the living room receiver is 8+1+14=23 for the 6:00 PM day part for the relevant month.
The data in the table of FIG. 5 do not show any SID-specific information, but instead represent a marginal layer collapsing over all SID codes. Data collapsing is useful whenever insufficient data has been collected upon which to make predictions about the audience members in the audience of a receiver at a given day part. For example, data collapsing is particularly useful during the first few months of initial data collection because insufficient data is likely to have been collected upon which to make predictions about the audience members in the audience of a receiver at a given day part.
The table shown in FIG. 5 is only exemplary of the way in which the data may be stored. The data alternatively could be stored in an accumulator table for all sets in the household. This accumulator table is incremented each time there is a change in tuning status or audience composition and includes data for every person, time period, set, and SID class. Thus, the accumulator table may simply log each tuning event and each audience composition event in chronological order.
As a further alternative, such an accumulator table may be used to store data as they are accumulated during a month and then transferred to the type of month table shown in FIG. 5 at the end of the relevant month. Other alternatives are also possible.
The tables store the basic information which is evaluated for each receiver prior to a scheduled prompt. These tables maintained by the measurement apparatus 24 or the data storage and forwarding unit 26 preferably includes four separate tables, a table for the current month, a table for the current month—1, a table for the current month—2, and a total of all months up to and including the current month—3. These tables permit a variable weighting of data by recency of behavior which may be used, for example, during data collapsing.
Thus, this recency weighting is accomplished by combining all four month tables on a weighted basis into a 10 master table that is used for each receiver to determine whether or not to deliver the scheduled prompt to the audience at that receiver. For example, if the recency weights are 2.1, 0.3, 0.3, 0.3, then every cell in the four month tables described above would be combined, giving a 15 weight of 2.1 to the data in the current month table and equal weights of 0.3 to the data in the other three tables.
The program 100 at a block 112 determines whether it is time to evaluate the data in the tables discussed above. For example, the block 112 may use an elapsed time timer such that the block 112 determines that it is time to perform its evaluation when the elapsed time timer accumulates an amount of time T. The time T between evaluations may be set to 42 minutes or any other number of minutes which is deemed appropriate. Accordingly, at T after the receiver 16 has initially been turned on, the program 100 at the block 112 initiates an evaluation of the data stored in the tables to determine if prompting should be suppressed. Thus, a prompt will be given after the passage of T unless the evaluation indicates that prompting should be suppressed.
The evaluation is a probability-based heuristic. 10 The tuning and audience composition history at the statistically selected location 12 is mathematically summarized and represented in multidimensional tables of counts. Each time a prompt is scheduled to be delivered, this information is evaluated, and, if the mathematical structure of audience composition in the household is such that the probability of a specific audience composition exceeds a certain threshold value, then the prompt is suppressed.
The heuristic is an algorithm for parsimoniously summarizing and retrieving knowledge stored in the tables. In a densely populated table, the simplest algorithm would search the cell most similar to the current condition, compute straightforward probabilities for each, and, if the probability of a single tuning composition exceeded a certain threshold, the prompt would be suppressed until the next cycle.
The objective is to determine audience composition. Rather than treating this determination as a problem in combinatorics, this determination may be treated as a problem of individual tuning at a receiver, by SID and day part, but including terms that include co-receiving history and current response to an alternate receiver (co-location).
The operation of the heuristic may be illustrated with the sample frequency tables shown in FIGS. 6 , 7 , and 8 . The tables shown in FIGS. 6 and 7 correspond to the frequency tables for two SID classifications, SID 11 and SID 12. These SID classes, for example, divide the programs by program type such as daytime drama, prime time drama, sports which can be further broken down into subtypes such as football, baseball, etc. Accordingly, Each SID may be assigned to one of these classes. The table in FIG. 8 contains a total of the data in the monthly tables (in the example here, the total of the data in the tables of FIGS. 6 and 7 ).
If the block 112 determines that it is time to make an evaluation (e.g., time T has passed since the last prompt decision), a block 114 determines whether the number of persons who have logged in (i.e., identified themselves as being in the audience) equals the number of persons who have been counted in the audience. Counting of persons may be implemented by using electric eyes, proximity, or other sensing to count the audience members as they enter and leave a reception area associated with the receiver 16 . A counter 90 is shown in FIG. 1 for this purpose. The measurement apparatus 24 collects count information from the counter 90 and passes this count information to the data storage and forwarding unit 26 as appropriate. If the block 114 determines that the number of persons who have logged in is not equal to the number of persons who have been counted in the audience, a block 116 permits the prompt to be given to the audience members at the receiver 16 corresponding to the program 100 .
On the other hand, if the block 114 determines that the number of persons who have logged in is equal to the number of persons who have been counted in the audience, a block 118 determines a variable NUMBER as a result of dividing a data value COUNTS by a data value TUOCC. The data value COUNTS is taken from the counts row, at the receiver location, during the day part, and for the SID class corresponding to the current day part and the current SID of the program being received by the receiver corresponding to the program 100 . For example, if the current day part is 6:30 AM if the SID from the program being received by the appropriate receiver is in SID class 11, and if the appropriate receiver is the bedroom receiver, the data value for COUNTS is 20.
The data value TUOCC is taken from the tuning occasions row, at the receiver location, during the day part, and for the SID class corresponding to the current day part and the current SID of the program being received by the receiver corresponding to the program 100 . For example, if the current day part is 6:30 AM, if the SID from the program being received by the appropriate receiver is in SID class 11, and if the appropriate receiver is the bedroom receiver, the data value for TUOCC is 19.
Therefore, the variable NUMBER is determined as 20/19. If either the numerator or denominator which is used to determine the variable NUMBER falls below a predetermined threshold, it may be necessary to collapse each cell in the tables from right to left (SID, and then receiver) until this threshold is reached because there are otherwise insufficient data in the SID tables on which a prediction can be based. Following such data collapsing, the variable NUMBER may be recomputed.
A block 120 determines whether the variable NUMBER exceeds a corresponding threshold. If the variable NUMBER does not exceeds the corresponding threshold, the block 116 permits the prompt to be given to the audience members at the receiver 16 corresponding to the program 100 . On the other hand, if the variable NUMBER exceeds the corresponding threshold, a block 122 rounds NUMBER to the nearest integer and compares the rounded NUMBER to the current persons count. This current persons count may be derived, for example, by summing the number of audience members who have logged into the measurement apparatus 24 at the receiver 16 corresponding to the program 100 . Alternatively, the current persons count may be derived by using the sensing described above to count the audience members as they enter and leave a reception area associated with the receiver 16 . If the rounded NUMBER is different than the current persons count, the block 116 permits the prompt to be given to the audience members at the receiver 16 corresponding to the program 100 .
On the other hand, if the rounded NUMBER is not different than the current persons count, the variable NUMBER is consistent with history as represented by the data in the tables so that the audience members can be further evaluated by the program 100 . Therefore, if the rounded NUMBER is not different than the current persons count, a block 124 sets a variable PREDICTED PERSON equal to the person having the maximum probability of being in the audience of the receiver 16 corresponding to the program 100 . For example, using the tables of FIGS. 6-8 and as described above, the person having the maximum probability of being in the audience of the bedroom receiver at the current time (6:00 AM+T) watching a program in SID class 11 is the 35-49 year old female. Therefore, the variable PREDICTED PERSON is set to the 35-49 year old female.
Also, the block 124 computes the probability that the PREDICTED PERSON (the 35-49 year old female in the example) is in the audience by dividing the number of times the 35-49 year old female tuned into a program having the relevant SID class and during the current day part by the count for that SID class and day part. For example, the probability that the 35-49 year old female is in the audience of the bedroom receiver which is tuned to a program having the SID class 11 at and during the current time (6:00 AM+T) is 19/20 using the table of FIG. 6 . This probability 19/20 may be adjusted by a lead-in adjustment factor F LI . This lead in factor F LI is used to adjust the computed probability when the PREDICTED PERSON was in the audience of the relevant receiver during the immediately preceding day part. This lead in factor F LI may be a predetermined number set to a suitable value greater than one and is multiplied by the computed probability in order to increase the computed probability.
Following the processing at the block 124 , the program 100 at a block 126 determines whether the probability calculated at the block 124 is less than a predetermined threshold. If the probability calculated at the block 124 is less than this predetermined threshold, the block 116 permits the prompt to be given to the audience members at the receiver 16 corresponding to the program 100 . It is noted that there may be insufficient data in the tables at this point during the execution of the program 100 , in which case the data may be collapsed as indicated above. However, if the data is so collapsed, it is likely that the probability calculated at the block 124 is less than a predetermined threshold, so that it is correspondingly likely that a prompt will be permitted.
On the other hand, if the probability calculated at the block 124 is not less than the predetermined threshold, the program 100 at a block 128 determines whether the audience member, who is in the audience of the receiver 16 corresponding to the program 100 and who has entered his or her identification into the corresponding measurement apparatus 24 , is the PREDICTED PERSON. If the audience member, who is in the audience of the receiver 16 corresponding to the program 100 and who has entered his or her identification into the corresponding measurement apparatus 24 , is not the PREDICTED PERSON, the block 116 permits the prompt to be given to the audience members at the receiver 16 corresponding to the program 100 .
On the other hand, if the audience member, who is in the audience of the receiver 16 corresponding to the program 100 and who has entered his or her identification into the corresponding measurement apparatus 24 , is the PREDICTED PERSON, then the program 100 at a block 130 suppresses prompting.
After the block 116 permits the prompt to be given 10 to the audience members at the receiver 16 corresponding to the program 100 , or after the block 130 suppresses prompting, the elapsed time timer used by the block 116 is reset, and the program 100 returns to the block 116 in order to repeat the execution of blocks 112 - 130 at 6:00 AM+2T and at each increment of T thereafter.
At a particular time during the day, the data storage and forwarding unit 26 communicates its stored tuning and audience member identification data to the data collection central office 22 .
Other events may also be used by the block 116 of the program 100 to trigger prompts. Such other events include, for example, a channel change when no audience member is logged in, the passage of a predetermined number of days when a particular household member has not logged in, the passage of a predetermined number of days when a short term visitor has not logged in, no log ins when the receiver 16 is turned on, no log ins of particular household members (such as children) when the receiver 16 is tuned to particular programs (such as children's programming), and the like.
As described above, navigation characteristics may provide valuable information for prompt management. Navigation characteristics indicate the manner in which certain audience members tune the receiver 16 . Thus, in the same way that tuning to individual programs or tuning during specific day parts or on specific sets may be correlated with a particular household member as described above, tuning styles may also be associated with individual household members. Accordingly, when tuning patterns are evaluated, the styles in which people select their programs may also be evaluated.
Tuning styles can be described by a variety of terms depending on which paradigm is being used to conceptualize receiver tuning. Tuning styles can be considered to mean or include “navigational patterns”, “biometric signatures,” or “keystroke dynamics.” These styles can be characterized by some very simple “statistics” or by more complex forms of representing knowledge.
“Statistics” are formally defined by mathematicians as a mathematical projection of a vector or set of data onto a single or simple set of parameters. Thus, statistics are used, in effect, to summarize data. A mean is an example of a statistic which may be used to summarize a set of data. However, in summarizing data, certain knowledge about the data, such as variance, kurtosis, skew, and, of course, the exact value of each data point, is lost. Therefore, the statistics used to summarize the data may or may not be sufficient.
“Sufficiency” in theoretical statistics refers to the ability of a “statistic” to reproduce the required detail of a data distribution. In some households, a simple statistic can “sufficiently” represent tuning style. One such statistic is the average number of stations or programs tuned per time period. For example, if one audience member views “appointment television” (i.e, an audience member tunes to a channel carrying a selected program and stays on that channel throughout most or all of the selected program), the average number of stations “hit” per half hour will be very small. But if another audience member is a “surfer,” the average number of “hits” per half hour will be much, much larger. While summaries of the tuning habits of these audience members may cause knowledge of variance and skew to be lost, the sheer difference between the average velocities (average rate of channel change) of these two audience members is sufficient to distinguish between these audience members. Thus, in this example, the mean rate of_is sufficient to identify the individual.
However, in some households, there may be several members that have the same average rate of channel changing (velocity). In this case, the only way to distinguish these households is to consider channel velocity along with other parameters of tuning which might provide “sufficiency” in order to identify the recent presence of a household member.
For example, for every time period T (e.g., ½ hr), the average number of channels tuned during that half hour may be recorded and stored in the tables of FIGS. 6-8 for every individual logged on to a receiver. However, velocity may not be sufficient to distinguish between people whose “instantaneous rate of change”, often called acceleration, is different. For example, two people may average twenty channel hits per half hour with one of the people methodically surfing by watching every other hit for a minute or two, while the other of the two people surfs through twenty channels, finds an appealing program, and then watches for a half hour. The average velocity is not a sufficient statistic to distinguish these two audience members. However, their acceleration can be used to distinguish between them.
There are several statistics that can represent “acceleration.” An exemplary statistic to represent acceleration is given by the following description. If it assumed that the time period is thirty. minutes, the following ratio may be used to characterize acceleration:
#
of
channels
in
past
30
minutes
#
of
minutes
in
which
channel
was
changed
in
past
30
minutes
For example, if twenty channels were hit in ten separate minutes of tuning, then the acceleration is 20/10 or a modest 2. On the other hand, if twenty channels were hit in two minutes of surfing, then the acceleration is 20/2 or a moderate ten.
In some homes, even “acceleration” may not be sufficient to distinguish between audience members. For example, it may be the case that where an audience member surfs in a program or channel space is the key to distinguishing between two audience members. Therefore, in such households, a learning heuristic can be used to classify the “cluster of channels” that an audience member surfs and to match this surfing cluster to the “clusters of programs” to which an audience member tunes. Accordingly, classification and matching may be done specifically to distinguish between the channel-surfing patterns of two audience members with similar velocity and acceleration histories.
Accordingly, the probability determined at the block 124 can be adjusted up or down by velocity, acceleration, and/or program clustering. Alternatively, any combination of these factors can be included in the program 100 as one or more decision blocks.
Certain parameters used by the program 100 may be downloadable from the data collection central office 22 to the measurement apparatus 24 or the data storage and forwarding unit 26 and stored in the RAM 58 or the RAM 88 . For example, the parameter T may be downloaded.
Certain modifications of the present invention have been discussed above. Other modifications will occur to those practicing in the art of the present invention. For example, it is noted that the portable remote control device 14 may function in several different modes as described above. However, each of these modes may use a separate corresponding remote control.
Also, the present invention as described above relies on the use of certain infrared transceivers. However, it will be appreciated that other signaling modes, such as ultrasonic or spread-spectrum radio, could instead be employed.
In addition, the present invention as described above relies on the use of transceivers. Instead, a separate receiver and transmitter could be used in place of each transceiver.
Moreover, as discussed above, instead of executing the program 100 at the data storage and forwarding unit 26 , the program 100 can be executed at each measurement apparatus 24 within the statistically selected location 12 . In this case, the data storage tables shown in FIGS. 5-8 may be modified by eliminating the receiver category. Also in this case, the storing and forwarding function performed by the data storage and forwarding unit 26 can be performed by the measurement apparatus 24 so that the data storage and forwarding unit 26 can be eliminated.
Furthermore, as described above, the portable remote control device 14 according to the first embodiment 15 of the invention transmits tuning commands which are received by both the controlled tuner and by the measurement apparatus 24 . The controlled tuner responds by effecting the tuning indicated by the tuning command, and the measurement apparatus 24 responds by recording the tuning event. Instead, in accordance with the teachings of U.S. Pat. No. 4,876,736, the portable remote control device 14 may be arranged to transmit tuning commands using codes recognized by the measurement apparatus 24 but not by the tuner of the receiver 16 . Thus, the measurement apparatus 24 records the tuning event, converts the code into a form recognized by the tuner of the receiver 16 , and passes the converted tuning command on to the tuner of the receiver 16 .
Also, a different portable remote control device could be assigned to each person in the household (with additional portable remote control devices provided to visitors). Each person would then carry his or her portable remote control device within the household. The individual's portable remote control device 14 can then be arranged to periodically transit an identification signal to the measurement apparatus 24 either based upon time increments or based upon a command issued by the measurement apparatus 24 .
Moreover, the prompting permitted by the block 116 may have multiple levels. For example, at the lowest level, the initial prompt could be flashed for 10 seconds. If the audience responds appropriately, the program 100 resumes normal execution. If the audience does not respond appropriately within a predetermined amount of time (e.g. 20 seconds), and the prompt is flashed for 20 seconds at a higher flash rate. If the audience responds appropriately, the program 100 resumes normal execution. If the audience still does not respond appropriately, the block 116 may be arranged to provide an audible tone or a voice command. Different and/or additional levels of prompting may be provided.
In addition, it may be deemed desirable for audience members to manually update audience composition without prompting as changes in audience composition occur. Prompting serves mainly as a fail-safe, when sufficient time has elapsed without any unprompted change. Therefore, the elapsed time timer used by the block 116 may be reset at each entry of any audience member identification data whether prompted or not.
As an additional contingency, the interval T between prompts could be lengthened or shortened in order to reinforce timely entry of audience changes. This adjustment of T could be based on the data entry performance of audience members. For example, if a particular audience member typically waits until a prompt appears before reporting an earlier audience change, then the data record will show an improbably high proportion of reported audience changes coinciding with the appearance of the prompt. If this pattern of performance is observed, the program 100 may shorten the interval T between prompts. Shortening the interval T between prompts will tend to reduce any possible lags between the occurrence and reporting of audience changes, as well as to provide a mild negative reinforcement for audience members who fail to report audience changes as they occur.
Alternatively or additionally, it is possible that 10 audience members will report audience changes when they occur and that the intervals T between prompts are shorter than the interval during which no audience change actually occurs. If this pattern is observed, it may be that the prompting interval T is shorter than required for this audience member. In this instance, the program 100 may lengthen the interval T between prompts in order to provide a positive reinforcement. Indeed, different prompting intervals T could be set for various audience members, depending on their previous performance.
Furthermore, the heuristic of the present invention as described above relies upon the representation of tuning history and/or style knowledge in the form of a series of probability tables. Such knowledge, however, can be represented in other forms. For example, as receiver tuning events occur, data relating to these events could be stored in a covariance matrix which could then be evaluated through regression, discriminant, or other parametric techniques which would develop prediction scores for each potential household member. Similarly, non-parametric techniques for representing knowledge, such as weighted digraphs, may be used to represent such knowledge. Conceptually, the heuristic has been described above using the simplest form of knowledge representation. However, an important element of the heuristic is its capacity to manage user prompts or questions regardless of how such tuning histories (knowledge) are represented.
Also, as viewed from the standpoint of a meter, audience members have features: what programs they watch, when they watch, with whom they watch, where they watch, and how they change channels. In some households, one or two of these statistics may suffice to discriminate between audience members. In other households, at certain times of day, many of these statistics may be required. Thus, in a more advanced form of the heuristic described above, aperiodic analysis could be conducted in each household to evaluate the structure, among household members, of each of these features. For example, in a two-person household, one person may surf while the other tunes by appointment. This household would be highly structured with respect to acceleration. In this case, the negentropy, or information content (h 2 ) of acceleration, is very high. In an advanced heuristic, the values of each of these features would be weighted by their information content, that is, their ability to discriminate among audience members.
In addition, specific hardware is described in relation to FIGS. 1 , 2 , and 3 . However, it should be understood that other hardware and/or software arrangements may be used to implement the present invention.
Accordingly, the description of the present invention is to be construed as illustrative only and is for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details may be varied substantially without departing from the spirit of the invention, and the exclusive use of all modifications which are within the scope of the appended claims is reserved.
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Methods and apparatus to count audience members are disclosed. An example method includes identifying a first audience member present at a first time, incrementing a stored first count of a number of times the first audience member is present during a day part corresponding to the first time, incrementing a stored tuning occasion count, identifying a second audience member present at a second time, incrementing a stored second count of a number of times the second audience member is present during the day part, incrementing the stored tuning occasion count, determining a probability that an unidentified audience member is the first audience member based on the first count, the second count, and the tuning occasion count, and counting the first audience member based on a comparison of the probability to a threshold.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of my copending application Ser. No. 330,962, filed Dec. 15, 1981, now allowed and to be issued as U.S. Pat. No. 4,425,728 on Jan. 17, 1984.
BACKGROUND OF THE INVENTION
This invention relates to a street sign adaptor unit and its use in a street sign assembly which is less expensive and more easily installed than street signs using tubular steel posts and the associated hardware used to fix the street sign to the tubular post.
Street signs are well known and in common use with a variety of designs and attachment hardware. For example, Plumbly U.S. Ser. No. 716,098 teaches a street sign assembly in which two pairs of right angularly disposed sign panels are set in back-to-back relation about the tubular adaptor and have upper, lower and intermediate coupling members holding the pairs of sign panels in fixed relation. The machined or stamped parts, threaded connections and tubular post are items which contribute to the cost of this assembly. Further, Ridenour U.S. Pat. No. 1,139,802 shows an additional method of attachment of sign panels to support posts. Finally, Von Gal, Jr., et al. U.S. Pat. No. 3,250,032 teaches the use of conventional fence and highway sign posts of rolled, extruded or pressed steel, iron or aluminum material having projecting, parallel, coplanar side flanges between which a body of trapezoidal cross-section including side walls which converge into a perforate rear wall which is in parallel relation to the side flanges for anchoring and supporting a rotatably adjustable sign in which the rotation mechanism is attached to the upper and lower post sections by trapezoidally cross-sectioned shank and stud portions. However, such conventional fence or sign posts are not adapted to display signs for intersecting streets, e.g., those having sign panels at approximately right angles to each other.
Of further interest is Cooley, U.S. Ser. No. 965,566 which teaches a sign permitting different sign panels to be attached at various angles by means of a post having a slotted head with brackets supporting sign panels attached thereto by fasteners, such as nuts and bolts. Wood, U.S. Pat. No. 1,890,483, teaches a sign having two panels centrally attached on either side to a post and having their ends fastened together. Other patents teaching similar methods of attachment or similar post construction or different adaptation are Beery U.S. Pat. No. 1,220,716; Walsh, U.S. Pat. No. 2,950,787; and Cobb, U.S. Pat. No. 3,138,886.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a street sign adaptor unit for use in the placement of street signs on a perforate metal post of trapezoidal cross-section comprising a lower portion having a trapezoidal cross-section for fitment with the post, the lower portion having means in register with the perforations of the post whereby the unit is attachable to the post and an upper portion having means for attachment of at least one sign panel thereto.
Another embodiment of this invention provides a street sign assembly comprising, in combination, a post having projecting, parallel coplanar side flanges between which there is provided a body of trapezoidal cross-section including side walls converging into a perforate rear wall, said rear wall being in parallel relation to said side flanges; an adaptor unit having a lower portion of a cross-section designed for fitment between the converging side walls of said post and apertures in register with the perforations of said rear wall of said post and an upper portion of a length sufficient for attachment thereto of at least one sign panel; at least one sign panel; and means for securely fastening said adaptor unit and said at least one sign panel to said post.
Another aspect of this invention provides a street sign adaptor unit for use in placement of street signs identifying intersecting streets and adaptable to both perforate metal posts of trapezoidal cross-section and cylindrical hollow metal posts, said adaptor unit comprising a lower portion having a trapezoidal cross-section for fitment within the trapezoidal cross-section of said perforate metal posts or within the top portion of said cylindrical hollow metal posts, said lower portion having means in register with the perforations of said trapezoidal cross-section perforate metal post whereby said unit is attachable to said trapezoidal cross-section perforate post and an upper portion of approximately square cross-section and being greater in area than said lower portion so that at the juncture of the said upper portion and said lower portion said upper portion extends over the largest parallel side of the trapezoidal cross-section of the lower portion forming a shoulder suitable for retaining a wedge used in fixing said adaptor unit in said cylindrical metal post.
DESCRIPTION OF THE DRAWINGS
The present invention is further illustrated in the figures of the drawings in which:
FIG. 1 is a perspective view of the street sign assembly of this invention used with a perforate metal post;
FIGS. 2 and 3 are top and elevational views of the adaptor unit employed in the street sign assembly of FIG. 1;
FIG. 4 is an exploded view of the street sign adaptor unit of this invention used with a cylindrical post;
FIGS. 5 and 6 are cross sections of the adaptor unit taken along section lines 5--5 and 6--6, respectively of FIG. 4.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The street sign assembly of the present invention is a unique adaptation of presently available materials and a response to the needs of municipalities and local governments to provide existing services at lower cost to the public. Street signs must meet rigorous operational criteria of low cost and maintenance, easy installation, resistance to weather and vandalism and high service life and readability. Strangely enough, these factors can all be met even though at first glance they seem highly incompatible. For example, in making a street sign vandal-resistant, one would first think of rugged, expensive metal materials and difficult to remove hardware. However, in contrast, the use of easily replaceable, cheap materials which are easily attached and removed markedly decreases the "challenge" and "trophy value" of a street sign and, hence, decreases the "thrill" of its acquisition or destruction. The present adaptor unit allows the use of standard V-notch, holed, fence posts or high sign posts which are not readily convertible to use at intersecting streets because of their design for one-way attachment. Additionally, such V-notch, holed posts are less expensive and more readily available than tubular iron or steel posts. Further, installation costs are far less than required by the conventional tubular posts. It is therefore surprising that they have not heretofore been employed with the adaptor units of the present novel design or of other designs in street sign applications at intersecting streets.
Referring to FIG. 1, the street sign assembly of this invention is generally indicated by the numeral 10 and includes a first pair of sign panels 12a and 12b and a second pair of sign panels 13a and 13b disposed in back-to-back relation about an adaptor unit 14 with the first pair of sign panels 12a and 12b being attached to the adaptor unit 14 at approximately right angles to the second pair of sign panels 13a and 13b by attaching bolts 24. As shown in FIGS. 2 and 3, adaptor unit 14 has an upper portion 34 which is of square cross-section and a lower portion 30 which is of trapezoidal cross-section (see FIGS. 5 and 6) for better fit into support post 16 (see FIG. 1). Bolt holes 28 and 32 are provided to accommodate attachment of sign panels 12a, 12b, 13a and 13b to the upper portion 34 of adaptor unit 14 and the lower portion 30 of adaptor unit 14 to support post 16.
The support post is of standard, rolled, pressed or extruded metal such as iron, steel or aluminum, as is conventional, and includes side flanges 18 attached to a trapezoidal body 19 with side walls 17 converging to perforate rear wall 20 which is in parallel relation with side flanges 18. The rear wall 20 carries numerous vertically aligned perforations 22.
The sign panels 12a, 12b, 13a and 13b illustrated in FIG. 1 are identical, but need not be. A more detailed illustration of a preferred sign panel 12a as shown in FIG. 1 as having a thin rectangular shape with appropriate fasteners 24 for attachment to the upper section 34 of adaptor unit 14 and fasteners 26 for holding the ends of sign panels 12a and 12b or 13a and 13b together.
The adaptor unit 14 and sign panels 12a, 12b, 13a and 13b can be constructed of metal, wood or plastic materials which are inexpensive, weather-resistant and easily formed. Preferably, the adaptor unit 14 is of wood and the sign panels are of plastic.
As thus far described hereinabove, the adaptor unit 14 is similar to the street sign adaptor unit of my copending application Ser. No. 330,962, filed Dec. 15, 1981. However, higher sign posts are now being used, for example, which are ten (10) feet in height, and which carry traffic control signs as well as street identification signs. Such are illustrated in FIG. 1 which also shows a stop sign 42 (in phantom). In order to have the stop sign 42 firmly attached, the face of lower portion 30 must be not higher than coplanar with the flanges 18 of post 16. This allows flush fitment of the stop sign 42 or other traffic control sign and one or more of the lower bolt holes 28 can be used with bolts 40 and nuts (not shown) to fix the stop sign 42 in place. The shoulder 44 of upper portion 34 of adaptor unit 14 extends out over the stop sign 42. Ordinarily this shoulder would not be necessary and the adaptor unit could be manufactured with a reduced cross-section of upper portion 34. However, by providing the adaptor unit 14 with this unique configuration it is also easily converted to use in standard cylindrical hollow metal posts many of which are already in place.
This added, unique feature of the present invention provides a structure which differs from those known in the prior art and which allows use on both the V-notched perforated metal posts and the hollow cylindrical metal posts. So far as it is known no other street sign adaptor unit can be employed in both uses with metal posts of such different shapes.
As illustrated in FIG. 4 the lower portion 30 of adaptor unit 14 is lowered into the top of hollow metal cylindrical post 46. As this is being done, wedge 48 is placed in interference fit with the front face of lower portion 30 and the inside of the hollow metal cylindrical post 46. The adaptor unit 14 is then hammered home so that shoulder 44 fits over wedge 48, preventing removal of the wedge 48, and just above the top of the post 46. In this position it is firmly wedged into the metal post 46 and the wedge cannot be dislodged for removal of the adaptor unit 14. Then sign panels can be attached in the manner previously described. Through this simple yet unique structural change in the adaptor unit of the present invention the utility of the street sign assembly is widely increased.
Having described the various embodiments of this invention illustratively, those skilled in the art will readily envision various changes and modifications which can be made within the scope and spirit of this invention. Therefore, it is desired that the present invention be limited only by the lawful scope of the following claims.
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A street sign adaptor unit and a street sign assembly for allowing use of standard V-notch perforate or cylindrical metal fence or highway sign posts to be used with standard sign panels for intersecting streets in which the adaptor unit has a varied cross-section to accommodate attachment and fixation with standard fasteners and without expensive conversion apparatus to both types of post and to sign panels.
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BACKGROUND OF THE INVENTION
The present invention relates to integrated circuits for economically communicating between a plurality of peripheral devices and a processor.
Use of MOS (metal-oxide-seminconductor) large-scale integrated (LSI) circuits in electrical devices has contributed to the cost reduction of such devices. In designing such semiconductor chips, the large number of MOSTs (metal oxide-semiconductor-transistors) together with the interconnection patterns of conductor lines therebetween must be optimized to provide the highest component density in order to reduce the required chip area to a minimum. Minimum line widths and spacing between the respective conductors composed of either polycrystalline silicon or aluminum and the MOSTs must be maintained to avoid short circuits and parasitic effects. Yet, the length of the interconnecting lines and their associated capacitances must be minimized not only to reduce chip size, but also to achieve maximum circuit operating speeds. A wide variety of trade-offs, including the necessity to minimize chip size, to increase circuit operating speed, to reduce power consumption, and to achieve acceptable reliability are involved in obtaining an optimum "layout" or arrangement of MOSTs and interconnection patterns therebetween in order to obtain a MOS LSI circuit which is both economical and has acceptable operation characteristics. Often, the technical and commercial success of an electronic product utilizing MOS LSI technology hinges on the ability of the chip designer to achieve an optimum chip topography.
Some of the numerous design constraints faced by the MOS LSI chip designer include specifications for the minimum width and spacing of diffused regions in the silicon, the minimum size required for contact openings in the insulating field oxide, the spacings required between the edges of contact openings to the edge of diffused regions, the minimum widths and spacing of polycrystalline silicon conductors, the fact that such polycrystalline silicon conductors cannot coincide with diffused regions, the minimum widths and spacings between the aluminum conductors, and the constraint that conductors on the same layer of insulating oxide cannot cross over like conductors. The high amount of capacitance associated with diffused regions and the resistances of both diffused regions and the polycrystalline silicon conductors must be carefully considered by the circuit designer and the chip designer in arriving at an optimum chip topography. Accordingly, it is an object of the present invention to provide an integrated circuit communication controller chip for effecting the transfer of data signals between a plurlity of remote peripheral devices and a processor in which the integrated circuit chip has a topography which provides the maximum possible circuit operating speed with the lowest possible chip size and power dissipation. It is a further object of this invention to provide an integrated chip for generating more than one data format for transmission between a processor and a plurality of remote peripheral devices at more than one clock rate. It is still a further object of the present invention to provide an integrated circuit communication controller chip which is very low in cost.
SUMMARY OF THE INVENTION
Briefly described, the invention provides an MOS LSI communication controller integrated chip having optimized chip topography. The chip topography includes two full duplex communication channels and internal data, address, mode, timing and control buses. The integrated circuit chip includes first, second, third and fourth sequentially located edges for forming a rectangle. Input/output circuitry for each communication channel is located along the right edge of the chip and is coupled to the address, data and control buses. Clock control circuits located along the left edge of the chip provide either one of two data clocking frequencies. A clock generator circuit is located in the upper left hand corner of the chip which, together with the input/output circuitry, receives control signals from the processor for generating a plurality of clock signals for use in operating the circuitry. The integrated circuit chip includes storage circuits located along the right edge of the chip in which input and output data is stored under the control of the input/output circuitry. The input/output circuitry and the storage circuits are spaced apart, allowing the buses to be located adjacent circuits to which the buses are connected. Counter circuits coupled to the clock generator circuit provide selected first and second clock rates used in transmitting data between the processor and the peripheral devices.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B, taken together, constitute a block diagram of a communication controller system in which the integrated circuit of the present invention is included;
FIG. 2 is a block diagram illustrating the general location of the major sections of circuitry on the surface of the integrated circuit chip of the present invention;
FIGS. 3A-3F inclusive, taken together, provide a more detailed block diagram of FIG. 2 illustrating the general location of the various sections of circuitry on the surface of the integrated circuit chip of the present invention;
FIG. 4 is a diagram showing how FIGS. 3A-3F inclusive are arranged;
FIG. 5 is a scale reproduction of a photo mask utilized to define the pattern of the source-drain diffused regions in the integrated circuit chip of the present invention;
FIG. 6 is a scale reproduction of a photo mask utilized to define the pattern of the ion implanted depletion regions of the integrated circuit chip of the present invention;
FIG. 7 is a scale reproduction of a photo mask utilized to define the pattern of contacts between the polycrystalline silicon conductors and the diffused regions of the integrated circuit chip of the present invention;
FIG. 8 is a scale reproduction of a photo mask utilized to define the pattern of the polycrystalline silicon layer of the integrated circuit chip of the present invention;
FIG. 9 is a scale reproduction of a photo mask utilized to define all conductor interconnection contacts in the integrated circuit chip of the present invention;
FIG. 10 is a scale reproduction of a photo mask utilized to define the pattern for the metal interconnection layer of the integrated circuit chip of the present invention showing locations of the mounting pads together with the signals associated with the circuit;
FIG. 11 is a scale reproduction of a photo mask utilized to define the pattern for the passivation layer of the integrated circuit chip of the present invention;
FIG. 12 is a scale reproduction of a composite of all the photo masks used in the fabrication of the integrated circuit chip of the present invention; and
FIG. 13 is a diagram illustrating the package and lead configuration of the package in which the integrated circuit of the present invention is ultimately housed.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1A and 1B, there is shown a block diagram of the communication controller circuit generally indicated by the numeral 18 which includes an interface logic unit 20 which interfaces a host processor 21 with a plurality of remote peripheral devices 29 over a pair of communication channels each consisting of four wires 22-28 inclusive. Since each channel is of the same construction, the following description will cover only one channel with like elements in both channels having the same numerical designation.
As shown in FIG. 1A, each channel includes an Output Buffer 30 in which a data character transmitted in parallel over the data bus 32 from the host processor 21 is stored. Under control of signals generated in a Control Logic unit 36, the data character stored in the Output Buffer 30 is transferred in parallel over bus 38 to the Serial Send Register 40 along with the required parity bits. The data character and its associated parity bits is shifted synchronously with the clock signals CLK0 on line 24 out of the Serial Send Register 40 and transmitted by a Data Driver 42 over the send data (SDATA) line 22 to the selected remote peripheral device at one of two clock rates selected by the Control Logic unit 36. At the completion of the transmission of the data character and its associated parity bits in a manner that will be described more fully hereinafter, the Control Logic unit 36 will signal the Bus Interface Logic unit 20 over line 43 enabling the unit 20 to lower the signal INT over line 56 raising an interrupt to the processor 21. The selected clock out signals CLK0 are outputted by a Clock Driver 44 over line 24 to a remote peripheral device.
When a remote peripheral device requests access to the host processor 21, the peripheral device will lower the signal on the receive data (RDATA) line 28 signalling the Control Logic unit 36 of the request. The Control Logic unit 36 will enable a Clock Driver 46 to output one of a plurality of two clock in signals (CLKI) over line 26 enabling the peripheral device to transfer the data character over line 28 through a Data Receiver 48 and into the Serial Receive Register 50. Under the control of signals generated by the Control Logic unit 36, the data character in the Serial Receive Register 50 is loaded in parallel over bus 52 into an Input Buffer 54. At this time, the Control Logic unit 36 will signal the Bus Interface Logic unit 20 of the storing of the data character in the Buffer 54, enabling the Bus Interface Logic unit 20 to lower the signal INT on line 56 raising an interrupt to the processor 21.
The communication format of the data message is provided by the processor over the data bus 32 and lines 58-68 inclusive. The Bus Interface Logic unit 20 will load the Mode Register 70 with a data word signifying that the data format generated will be either an 8-bit word or a 9-bit word, together with one of two clock rates. In an 8-bit word data format, five bits represent the data to be transferred, one bit is an end-of-message flag, while two bits are used for parity checking. In the 9-bit format, eight bits represent the data while one bit represents the "end-of-message" flag. Each of the data formats can be executed at a clock rate of either 48 KHz. or 144 KHz. In addition to the Mode Register 70, the controller 18 includes a Status Register 72 which includes data indicating a character is required to be written to the Output Buffer 30; a character is available to be read from the Input Buffer 54; a parity error was detected during the reception of the 8-bit data character format and a last byte flag was detected during reception. Also included in the controller circuit 18 is a Control Register 75 which provides task definition. Data stored in the Register 75 provides masking of the signal INT, transmitting of the last character and diagnostic selection.
Referring now to FIG. 2, there is shown a block diagram illustrating the general location of the major sections of circuitry on the surface of the integrated circuit chip of the present invention herein generally designed by the numeral 15. The chip includes top 74, bottom 76, left 78 and right side edges 80. The edge assignments are used in explaining the topography of the chip with the realization that a chip may have an orientation other than that shown in the drawing. Located adjacent the left portion of the top edge 74 is a bi-phase Clock Generator 82 for generating the various clock signals used by the controller. Located in the upper central portion of the chip in a horizontal alignment are the Control Register 75, an Interrupt Control circuit 84 which is located in the Control Logic unit 36 (FIG. 1), the Mode Register 70 and the Status Register 72. Stacked along the left edge 78 of the chip is a Sync Counter 86 for selecting the clock rates at which the data is to be transmitted, a Receive Handshake circuit 88 for enabling data to be shifted into the Serial Receive Register 50 from the peripheral device, and a Send Handshake circuit 90 for enabling data received from the host processor 21 (FIG. 1) to be transmitted through the Serial Send Register 40 to the peripheral devices. The circuits 86, 88 and 90 are included in the Control Logic unit 36 associated with channel 1 of the controller 18.
Further included in the stack is a Receive Handshake circuit 92 and a Send Handshake circuit 94 constructed for operation in the same manner as circuits 88 and 90. Circuits 92 and 94 are located in the Control Logic unit 36 (FIG. 1) associated with channel 2. Located adjacent the bottom edge 76 of the chip is an Address Decode circuit 96 located in the Bus Interface Logic unit 20 (FIG. 1) which decodes the address bits transmitted over the A0 line 60, A1 line 62 from the processor 21 and the read/write strobes RD appearing on line 64 and WR on line 66 for use in addressing the peripheral devices for which the data is intended.
Stacked vertically along the right edge 80 of the chip is the Input Buffer unit 54, a Parity Check circuit 98 for checking the parity bit of the data received from the peripheral device, the Serial Receive Register 50, a Parity Generator circuit 100 for generating a parity bit for the data outputted to the peripheral device and the Output buffer 30. The latter-cited circuit elements are associated with channel 1 of the controller circuit 18 with the Parity Check circuit 98 and the Parity Generator circuit 100 located in the Control Logic unit 36 (FIG. 1).
Further located in the stack along the right edge 80 of the chip are similar circuit elements associated with channel 2 of the controller circuit 18. These elements include the Input Buffer unit 54, Parity Check circuit 102, Serial Receive Register 50, Serial Send Register 40, Parity Generator circuit 104 and the Output Buffer unit 30 with circuits 102 and 104 located in the Control Logic unit 36 (FIG. 1) associated with channel 2 of the controller circuit.
Referring now to FIGS. 3A-3F inclusive and as arranged in the manner disclosed in FIG. 4, there is shown a more detailed block diagram of the circuits location disclosed in FIG. 2. Included in the circuitry is an address bus 106 (FIGS. 3A-3F inclusive) extending along the top edge 74 of the chip between the Clock Generator circuit 82 (FIG. 2) and the Register circuits 70-75 inclusive. The address bus 106 also extends along the left 78 and bottom sides 76 of the chip and further extends vertically through the middle of the chip (FIGS. 3B, 3D and 3F). The address bus 106 distributes the decoded address signals from the Address Decode circuit 96 (FIG. 3E) which receives over lines 58-66 inclusive (FIG. 1) the address signals from the processor 21. The circuit decodes the signal and transmits the decoded signals over the bus 106 to the Control Register 75 for writing a control byte of data signalling the last byte of a message being sent to the peripheral device; the Mode Register 70 for selecting the clock rate used to transmit/receive the data and word format; the Receive and Send Handshake circuits 88, 90, 92 and 94 (FIG. 2) inclusive and to the Input and Output Buffers 54 and 30 respectively enabling a data message to be transferred between the host processor 21 and a remote peripheral device in a manner that will be described more fully hereinafter.
Further included in the circuitry is a control bus 108 extending through the middle of the chip and over which control signals stored in the Control Register 75 (FIG. 3A) are distributed to other circuits on this chip for controlling the operation of the controller circuit 18. Located between the control bus 108 and a portion of the address bus 106 is a mode bus 110, and the data bus 32 (FIGS. 3B, 3D and 3F). The mode bus is coupled to the Mode Register 70 (FIG. 3B) which stores data bits selecting the clock rate and word format by which data is transmitted between the communications controller circuit 18 and the remote peripheral devices. In the case of a data character transmission, the data character is transferred over the data bus 32 (FIGS. 1, and 3F) from the processor 21 to the Output Buffer 30 (FIG. 3F). The data character is transferred through the Parity Generator 104, which appends the appropriate parity information to the Serial Send Register 40 for serial transmission to the peripheral device. In the case of a data character originating in the peripheral device, the data character described previously is received in the Serial Receive Register 50 (FIG. 3B) from which it passes through the Parity Check circuit 102 (FIG. 3B) and transferred to the Input Buffer 54 from where it is transferred on the data bus 32 (FIG. 3F) to the processor 21.
Referring now to FIG. 3A, there is shown a diagram of the Sync Counter 86 which includes a 4-bit Sync Counter 114 receiving 1.152 KHz. clock signals over line 115 (FIG. 1) from the processor 21. The Counter 114 is controlled by either of the signals CLK1, CLK2 received over line 120 and 122 respectively from the Mode Register 70 (FIG. 3B) and distributed through the mode bus 110 for selecting the clock rate of 48 KHz. or 144 KHz. respectively. The output bits of the Counter 114 are decoded in Counter Decoder 116 and transmitted to the Frequency Selector 118 which selects the required clock frequency in accordance with the mode signals CLK1 and CLK2 for distribution through a timing bus 124 which extends along the left edge of the chip adjacent the address bus 106.
Located below the Sync Counter 86 on the chip is the Receive Handshake circuit 88 associated with channel 1 of the controller circuit 18 for controlling the storing of the data received from the peripheral device in the Serial Receive Register 50. Since the construction and operation of the Receive Handshake circuit 88 for channel 1 is the same for the Receive Handshake circuit 88 (FIG. 3C) for channel 2, the description of the circuit will be limited to the circuits shown in FIG. 3A, and like numerals will be used in both circuits to designate like elements.
Included in the Receive Handshake circuit 88 (FIG. 3A) is the CLOCK I Generator 126 which receives over timing bus 124 the 48 KHz. or the 144 KHz. clock signals generated by the Sync Counter 86 in the manner described previously. When the RDATA 1 line 28 (FIG. 1) goes low indicating that the peripheral device is ready to send data to the processor, a Receive Control unit 130 comprising a pair of flip-flops enable the CLOCK I Generator 126 to output the clock signals received over bus 128. The output clock signal (CLOCK I) corresponding to either 48 or 144 KHz. is outputted over line 26 (FIGS. 1, 3A and 3B) to the peripheral device, enabling the peripheral device to clock out a data character into the Serial Receive Register 50 (FIG. 3B) over line 28. The Register 50 is controlled by shift in signals SFTI generated by the CLOCK I Generator 126 over line 134. The contents of the Register 50 are transferred by a load signal transmitted over the control bus 108 from the Control Register 74 to the Input Buffer 54.
The CLOCK I output signals from the Generator 126 are also transmitted over line 26 to a Counter 136 which counts the number of CLOCK I transitions outputted by the Generator 126. As previously described, data stored in the Mode Register 70 (FIG. 3B) selects an 8-bit data format (S) for processing or a 9-bit format (F) in which the latter format does not include a parity bit. In accordance with the level of the format data signal S/FI appearing on input line 138 (FIG. 3A and 3B) from the mode bus 110, a Counter Decoder 140 (FIG. 3A) coupled to the output of the CLOCK I Counter 136 will output a stop receive sigal over line 142 of the Counter 136 if the Counter has reached a count equal to the selected format, thus indicating that the data character received from the peripheral device is stored in the Receive Register 50 (FIG. 3). The stop receive signal appearing on line 142 will stop the operation of the Handshake circuit 88.
After a predetermined time period which allows the received data character to pass through the Parity Check circuit 98 is required, the Receive Control circuit 130 will output the signal LD INPUT BUF over line 144 to the Input Buffer 54 (FIG. 3B) through the control bus 108 allowing the received data character stored in the Receive Register 50 to be transferred into the Input Buffer 54. Once the data character has been loaded into the Input Buffer 54, the Interrupt Control unit 84 (FIG. 3A) in response to the generation of the LD INPUT BUF signal will generate the interrupt signal INT over line 56 (FIGS. 1, 3A and 3B) notifying the host processor 21 of the available data character if the Control Register input enable bit is set. The Receive Control circuit 130 upon generating the signal LD INPUT BUF disables the Receive Handshake circuit 88 from loading the Input Buffer 50 with a received data character until the data character presently in the Input Buffer 54 is read by the processor 21.
When the processor 21 has a data character for transmission to a peripheral device, the address signals CS, A0, A1, RD, WR appearing on lines 58-66 inclusive (FIGS. 1 and 3E) will be decoded by the Address Decoder circuit 96 resulting in the decoded write output buffer signal WR OUT BUF appearing on the address bus 106. The data signals D0-D7 appearing on bus 32 (FIG. 1) will be transmitted to the Output Buffer 30 (FIG. 3D) over the data bus 112 in response to the WR OUT BUF signal appearing on line 133 (FIG. 3D). The write output buffer signal WR OUT BUF is also transmitted over the address bus 106 and over line 146 to a Send Control circuit 148 of the Send Handshake circuit 90 (FIG. 36) which enables a Clock Generator 150 to output the data clock signal CLK0 over line 24 (FIGS. 1, 3C and 3D) to the peripheral device receiving the data. The Send Control circuit 148 will also output the load signal LD SSR 1 over line 160 to the Serial Send Register 40 (FIG. 3D) through the control bus 108 to transfer the data character from the Output Buffer 30 to the Serial Send Register 40. The CLK0 Generator 150 receives over bus 152 the clock signals outputted from the Sync Counter 86 (FIG. 3A) corresponding to either 48 or 144 KHz. as was explained previously with respect to the operation of the Receive Handshake circuitry 88.
Operating in the same manner as the Receive Handshake circuit 88, a CLOCK 0 Counter 154 in the Send Handshake circuit will count the clock signals outputted by the Generator 150, which count is transmitted to a Counter Decoder 156 which in turn decodes the output count in accordance with the signal S/F appearing on line 138, thereby selecting the data format in the manner explained previously. The Decoder 156 will output the signal STOP SEND over line 158 upon completion of the transmission of the data character from the Send Register 40 (FIG. 3D) in accordance with the selected data format thereby disabling the signal LD SSR 1. The data character is shifted out of the Send Register 40 and over line 22 by the Data Driver 42 (FIG. 1B) synchronously with signal CLKO on line 24 to the peripheral device.
If the data format selected by the signal S/F indicates parity bits, the Parity Generator 100 (FIG. 3D) is operated by the signal to add the required parity bits to the data character transmitted from the Output Buffer 30 to the Send Register 40.
Once a data character has been transferred from the Output Buffer 30, a new character can be transferred into the Output Buffer 30 while the previous character is stored in the Send Register 40. The stop send signal appearing on line 158 (FIG. 3C) in the Send Handshake indicates the completion of the serial transfer of the data character and allows another character to be transferred to the Serial Send Register 40. This construction allows the processor 21 to do a double write operation, thereby increasing the performance of a write operation.
Referring now to FIG. 10, there is shown the location of the bonding pads for the input and output signals through the controller chip 15. The 1.152 MHz. clock signal CLK bonding pad was placed in the top edge 74 of the chip 15 adjacent the Clock Generator circuit 82 (FIG. 2). The bonding pads for the signal RST, RD, CS, WR, A1, A0 and D0-D3 inclusive generated by the processor 21 are located along the left portion of the top and bottom edges of the chip, together with the left edge of the chip to conveniently connect the host processor 21 to the controller chip 15. The bonding pads for the data signals D4-D7 and the interrupt signal INT transmitted between the processor 21 and the controller chip 15 are located adjacent the upper right hand corner adjacent the Interrupt Control 84 and Mode Register 70 (FIG. 2) which receive such signals. The bonding pad for the data and clock signals RDATA, SDATA, CLKO and CLKI associated with each communication channel are located on the right edge 80 and the right portion of the bottom edge 76 of the controller chip adjacent the Registers and Buffers associated with each channel. The double bonding pads for the voltages supplied in V DD located in the top edge 74 and V SS located in the bottom edge 76 of the chip optimizes power bus routing and substrate grounding.
The placement of the various circuits shown in FIG. 2 minimizes the length of the interconnected conductors, thereby reducing their associated capacitances and resistance. Numerous capacitance and resistance calculations and modifications of the topography of the circuitry were made to achieve optimum performance in data transmission between the processor and the peripheral devices.
It should be recognized that a very high level of creativity is required of the architect in designing MOS LSI random logic chips such as are used in microcomputers or microprocessor chips and the like because of the layout constraints for state-of-the-art manufacturing processes. For example, for silicon gate MOS manufacturing processes, the major constraints are the minimum widths and spacings of the diffused regions, the minimum widths and spacings for depletion mode gate implants, the minimum size required for pre-ohmic openings in the field oxide, the spacings required for the edge of pre-ohmic openings to the edge of diffused regions, the minimum widths and spacings of the polycrystalline silicon lines, the fact that such lines cannot cross over diffused regions and the minimum width and spacing between the metal lines, and of course the constraint that conductors in the same layer, that is, diffused regions, polycrystalline silicon lines or metallization lines cannot cross other of the same type conductors. The high amount of capacitance associated with diffused regions and the resistance of both diffused lines and polycrystalline silicon lines and to a less extent of metal lines provide further design constraints upon the chip architect. For logic circuits which may be characterized as random logic, such as those in the subject invention, a large number of lines between sections of logic circuitry are required and the very large number of possibilities for routing the various kinds of conductors to the various required sections of the chip taxes the ingenuity of even the most competent chip topology architect, and further taxes the capacity of the most sophisticated computer interconnection conductor routing programs yet available.
It should be noted that those skilled in the art can prepare a mask set for manufacturing the integrated chip on the basis of the scale reproductions of the photo mask disclosed in FIGS. 5-12 inclusive.
In a 28-pin dual-in-line semiconductor package suitable for housing the communication controller interface chip 15 described herein is illustrated in FIG. 13. The sequence of the pins is close to provide maximum utility in placing such a chip on a printed circuit board.
While the invention has been described with respect to a particular detailed layout of the communication controller chip, certain variations can be made by those skilled in the art without departing from the true spirit and scope of the invention as defined in the appended claims.
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An integrated circuit for operatively connecting a plurality of peripheral devices to a processor includes first, second, third and fourth sequentially located edges forming a rectangle. The integrated circuit includes two independent full duplex, master peripheral ports in which each port provides two character buffering on both input and output channels. Data may be transmitted using two message formats at two different clock frequencies with each channel having simultaneous sending and receiving capabilities. Data processing circuits are located adjacent the first edge which connects to the processor while the port control circuitry is located adjacent the third edge of the chip which connects to the peripheral devices.
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[0001] This application is a continuation-in-part of, and claims benefit under 35 U.S.C. Section 120 of U.S. patent application Ser. No. 10/492,850, filed Oct. 25, 2002, which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to biologically active peptides derived from the neurite out-growth-promoting domain of laminin-1, i.e. the γ1-chain of laminin-1. These peptides include the decapeptide RDIAEIIKDI and the truncated peptides derived therefrom comprising the biologically active domain thereof, the tri-peptide KDI. The invention is directed to a method for using biologically active peptide compounds comprising the tri-peptide motif KDI as inhibitors of ionotropic glutamate receptors. The peptide compounds are therefore useful in methods of treating disorders responsive to the blockade of these receptors.
BACKGROUND OF THE INVENTION
[0003] Laminins were identified in late 1970's as extracellular matrix proteins and components of basement membranes (Martin and Timpl, 1987) and they presently form a growing family of glycoproteins with diverse functions (Miner and Yurchenco, 2004). In recent years, the central nervous system functions of various laminins have been extensively studied, and their multiple roles in the developing and mature CNS have started to emerge (Liesi, 1990; Miners and Mercado, 2003). Numerous studies have established that laminins are widely expressed in both CNS neurons and glial cells (Wiksten et al., 2004b; Liesi et al., 2001a). One of the neurite outgrowth domains of laminin-1 has been mapped to the C-terminal decapeptide RDIAEIIKDI (Liesi et al., 1989) of the γ1-chain of laminin-1. Specifically, the γ1 laminin has been linked in promoting neurite outgrowth (Liesi et al., 2001b), neuronal migration (Liesi, 1990), and axon guidance (Wiksten et al., 2003).
[0004] Interestingly, the neurite outgrowth function of the γ1 laminin is mediated by a tri-peptide sequence KDI (Lys-Asp-Ile) located in C-terminus of the protein (Liesi et al. 2001b). This tri-peptide enhances both viability and directional neurite outgrowth of human spinal cord neurons in vitro (Wiksten et al., 2003; Liebkind et al., 2003). Recent data indicate that the KDI domain possesses dramatic neuroprotective functions in vivo: it was shown (1) to prevent kainic acid induced neuronal death in hippocampal and cortical areas of the rat (Wiksten et al., 2004b), and (2) to promote healing and functional regeneration of surgically induced spinal cord injury resulting in hind limb paralysis of adult rats (Wiksten et al., 2004a). Microscopic and molecular analyses of KDI-treated spinal cords and hippocampal tissues indicate that application of soluble KDI-peptide reduces tissue damage at the lesion site and enables both neurite outgrowth through the injured area and neuronal survival (Wiksten et al., 2004a and 2004b).
[0005] Previous studies have also shown aggregation of inwardly rectifying potassium channels (Guadagno and Moukhles, 2004) and most recently voltage gated calcium channels (Nishimune et al., 2004) by binding of a particular laminin to the channel protein, but no electrical responses were reported for this interaction.
[0006] Even though the adhesive properties have been shown to play an important role in such biological events as promotion of neurite outgrowth, neuronal migration and regeneration, the data of the present invention indicate that the neurite outgrowth KDI domain of γ1 laminin has additional diverse and important functions that shed new relevance for expression of γ1 laminin in adult CNS neurons (Wiksten et al., 2004b), and in CNS after trauma (Liesi and Kauppila, 2002) or in a neurological disorder, such as Alzheimer's disease (Murtomäki et al., 1992; Palu and Liesi, 2002).
[0007] As compelling evidence indicates that glutamate neurotoxicity (glutamate-mediated neuronal death, excitotoxicity) is a major player in all CNS trauma and neurodegenerative disorders (Mattson, 2003), most of the presently available novel drugs used clinically to treat patients with Alzheimer's disease and ALS or stroke are inhibitors of glutamate receptor function. However, many of these drugs cause significant side effects, e.g. neurotoxicity. Therefore, novel, effective, safe and non-toxic inhibitors of this receptor function are constantly needed.
SUMMARY OF THE INVENTION
[0008] In the present study we investigated the effect of γ1 laminin and its derivatives on glutamate receptor function. We found that laminin-1, and peptide derivatives of the γ1 laminin, including its previously characterized biologically active KDI domain, inhibit all known classes of ionotropic glutamate receptors. This inhibition is reversible, dose-dependent and non-competitive. Our present results elucidate a novel and unexpected function for γ1 laminin and provide one feasible mechanism for potent regenerative and neuroprotective actions of the KDI domain.
[0009] In the present invention we show that the KDI-domain of γ1 laminin is a universal and non-competitive inhibitor of both AMPA, kainate and NMDA subclasses of glutamate receptors. As glutamate neurotoxicity plays a key role in both CNS trauma and neurodegenerative disorders, this unexpected novel function of the γ1 laminin derived tri-peptide may prove clinically valuable in treatment of CNS trauma and/or disease.
[0010] Consequently, one object of the invention is a pharmaceutical composition useful for the treatment of disorders responsive to the blockade of ionotropic glutamate receptors, said composition comprising a therapeutically effective amount of a peptide compound comprising the tri-peptide KDI or a pharmaceutically acceptable salt thereof in combination with at least one pharmaceutically acceptable carrier, diluent or excipient.
[0011] Another object of the invention is a method for antagonizing the neurotoxicity mediated by ionotropic glutamate receptors in a patient, said method comprising providing to said patient a therapeutically effective amount of a pharmaceutical composition having inhibitory effect on ionotropic glutamate receptors, wherein the composition comprises the tri-peptide KDI or a pharmaceutically acceptable salt thereof in combination with at least one pharmaceutically acceptable carrier, diluent or excipient.
[0012] Disorders responsive to the blockade of ionotropic glutamate receptors include a variety of central nervous system degenerative disorders, such as stroke, traumatic brain and spinal cord injury, Alzheimer's disease, Parkinson's disease, Huntington's chorea, amyotrophic lateral sclerosis (ALS) and spinal muscular atrophy (SMA).
[0013] Glutamate neurotoxicity (recently named as excitotoxicity) has been implicated in the pathophysiology of numerous neurological disorders. Besides the above-mentioned disorders, excitotoxicity has been linked with the etiology of cerebral deficits subsequent to cardiac bypass surgery and grafting, cerebral ischemia, spinal cord lesions resulting from inflammation, perinatal hypoxia, cardiac arrest, and hypoglycemic neuronal damage. In addition, excitotoxicity has also been implicated in such chronic neurodegenerative conditions as inherited ataxias, AIDS-induced dementia, as well as ocular damage and retinopathy. Other neurological disorders implicated with excitotoxicity and/or glutamate dysfunction include muscular spasticity including tremors, drug tolerance and withdrawal, brain edema, convulsive disorders including epilepsy, depression, anxiety and anxiety related disorders such as post-traumatic stress syndrome, tardive dyskinesia, and psychosis related to depression, schizophrenia, bipolar disorder, mania, and drug intoxication or addiction. In addition, it has also been reported that glutamate excitotoxicity participates in the etiology of acute and chronic pain states including severe pain, intractable pain, neuropathic pain, post-traumatic pain and also migraine.
[0014] The use of a biological neuroprotective agent, such as KDI or its salt, as a glutamate receptor antagonist, is likely to be safer and more usable in treating or preventing these disorders and/or reducing the amount of neurological damage associated with these disorders than drugs having often detrimental side effects.
[0015] Consequently, a further object of the present invention is a method of selectively inhibiting ionotropic glutamate receptors in a human host, comprising administering to a human host in need of such treatment a peptide compound that selectively inhibits activity of ionotropic glutamate receptors and comprises the tri-peptide KDI or a pharmaceutically acceptable salt thereof.
[0016] A very specific object of the invention is a method for treatment of stroke, comprising administering to a patient in need of such treatment a therapeutically effective amount of a pharmaceutical composition having an inhibitory effect on ionotropic glutamate receptors, wherein the composition comprises the tri-peptide KDI or a pharmaceutically acceptable salt thereof in combination with at least one pharmaceutically acceptable carrier, diluent or excipient.
[0000] Abbreviations
[0000]
ALS Amyotrophic Lateral Sclerosis
AMPA α-amino-3-hydroxy-5-methyl-4-isoxazole-4-propionic acid
CNS Central Nervous System
KDI Lys-Asp-Ile
LRE Leu-Arg-Glu
NMDA N-methyl-D-aspartate
RT room temperature
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIGS. 1A and 1B .
[0025] 1 A: immunocytochemistry for AMPA (GluR1, GluR2/3, GluR4), and kainate (GluR5, GluR6/7, KA2) glutamate receptor subunits in human embryonic neocortical neurons. All cells are on poly-D-lysine at 14 days in vitro. Scale bar=20 μm.
[0026] 1 B: Immunocytochemistry for NMDA receptor subunits in human embryonic neocortical neurons. All cells are on poly-D-lysine at 14 days in vitro. Scale bar=20 μm.
[0027] FIGS. 2A and 2B .
[0028] 2 Å: Example traces of 20 mM glutamate evoked currents in human neocortical neurons in the absence and presence of the KDI peptide (0.1-10 μg/ml). (n=15).
[0029] 2 B: A column presentation of percentages of inhibition of laminin-1 and its various derivatives on AMPA receptor currents of human neocortical neurons. Lam-1: laminin-1, P10-OH: an acidic form of RDIAEIIKDI, (n=5), P10-NH 2 : an amide form of RDIAEIIKDI (n=5), P31: a control peptide from cell attachment domain of β1 laminin (CDPGYIGSR, n=6), and LRE: a control tri-peptide LRE from β2 laminin (n=5). Asterisks indicate statistical significance of inhibition between the control and the peptide treatment tested by t-test, p<0.001 (***), p<0.01 (**)
[0030] FIGS. 3A, 3B and 3 C.
[0031] Evaluation of KDI tri-peptide inhibition of AMPA currents of cultured human neocortical cells.
[0032] In 3 A, an inhibition curve of increasing concentrations of the KDI peptide on AMPA currents evoked by 20 mM glutamate indicate an IC 50 of 0.1 μg/ml of the peptide (n=10). P<0.001 (***), p<0.05 (*).
[0033] In 3 B, the glutamate dose-response curves indicate that 0.1 μg/ml of the KDI peptide does not essentially shift the EC 50 , which indicates a non-competitive nature of inhibition (n=6).
[0034] In 3 C, the significance of the length of KDI pre-application time for inhibition of AMPA receptor currents is demonstrated (n=6). The results show that the pre-application time is short (62±22 ms). In some experiments, a direct co-application of KDI and glutamate was tested. Under those conditions, the KDI peptide produced only a 37±20% inhibition of AMPA currents, which indicates that the KDI peptide directly interacts with the AMPA receptor.
[0035] FIGS. 4A and 4B .
[0036] In 4 A, both individual traces and column presentation indicate that the pre-applied KDI peptide is a potent inhibitor of NMDA currents at 0.1-10 μg/ml (n=7). p<0.001 (***), p<0.05 (*).
[0037] In 4 B, KDI inhibition of kainate receptor currents in HEK 293 cells transfected with GluR6 clones indicates almost 100% inhibition at 10 μg/ml (p<0.001 ***) of the KDI with an IC 50 at 0.1 μg/ml of the KDI peptide (n=6).
DETAILED DESCRIPTION OF THE INVENTION
[0038] To elucidate the possible interaction of the KDI-domain of γ1 laminin with the glutamate receptor function, we used immunocytochemistry and patch clamp configuration on human embryonic neocortical neurons cultured on a poly-D-lysine substratum. In addition, we applied patch clamp studies on HEK 293-cells expressing recombinant AMPA, and kainate receptor subunits. Immunocytochemically, neocortical neurons expressed all subclasses of glutamate receptors tested, but both expression patterns and subunit compositions showed considerable variation ( FIG. 1A -B).
[0039] Consequently, in FIG. 1A immunocytochemistry for AMPA (GluR1, GluR2/3, GluR4), and kainate (GluR5, GluR6/7, KA2) glutamate receptor subunits in human embryonic neocortical neurons indicates that several different ionotropic glutamate receptor proteins are expressed, and their expression patterns show considerable variation. For example, the GluR1 receptor subunits are mainly expressed in cell bodies, while the GluR2/3 subunits are strongly and specifically expressed along the long neurites as well as cell bodies. Expression of GluR4 receptor subclass is moderate along both neurites and cell bodies. The GluR5 kainate subclass of glutamate receptors is clearly the prevailing subtype of all neocortical neurons being expressed as punctate deposits along the neurites. However, a weaker but distinct expression of the GluR6/7 kainate receptors is visualized along the mature-looking pyramidal neurons, and KA2 receptors are moderately expressed along both neurites and cell bodies of some of the neocortical neurons.
[0040] In FIG. 1B immunocytochemistry for NMDA receptor subunits in human embryonic neocortical neurons indicate that the NMDAR1 subunit is expressed in a patchy fashion along neurites of the neocortical neurons. Both NMDAR2A and NMDAR2B subunits show weak expression patterns mainly in the cell bodies of neurons. Thus, the neocortical neurons express at least the R1/R2A and R1/R2B heterodimeric receptor proteins.
[0041] Application of glutamate to the cultured neocortical neurons under conditions that inhibit NMDA receptor currents, e.g., in the presence of 1.0 mM Mg 2+ in the external solution, produced a fast desensitizing current ( FIG. 2A ) that was effectively inhibited by 0.1-10 μg/ml of the KDI peptide ( FIG. 2A ). The glutamate-evoked current was solely AMPA receptor-mediated based on the fact that application of a selective kainate receptor agonist SYM 2081 together with 0.3 mg/ml of concanavalin A produced only a small (5 pA) insignificant current (data not shown). Thus, neocortical neurons on a poly-D-lysine substratum failed to express functional kainate receptors even though they showed expression of several kainate receptor subunit proteins ( FIG. 1A -B).
[0042] Laminin-1 and various peptide derivatives of the neurite outgrowth domain of γ1 laminin were found to inhibit AMPA receptor currents in cultured human neocortical neurons ( FIG. 2B ). Native laminin-1 (5 μg/ml=0.01 μM, α1β1γ1) inhibited currents evoked by 20 mM glutamate by 59±5% ( FIG. 2B ). Inhibition of a 10 amino acid long neurite outgrowth domain of γ1 laminin (RDIAEIIKDI) was dependent on the form of the synthesized amino acid chain. An acid (—OH) form of the peptide inhibited the AMPA receptor currents at the concentration of 10 μg/ml (10 μM) by 72±8% ( FIG. 2B ) whereas the amide (—NH 2 ) form only by 22±3% ( FIG. 2B ). The previously characterized shortest active domain of γ1 laminin, KDI, at a concentration of 10 μg/ml (30 μM) was also found active in inhibiting AMPA receptor currents by 90±13%, and at a concentration of 3 μg/ml (10 μM) by 75% ( FIG. 3A ). The cell attachment peptide CDPGYIGSR(P31) from the β1 laminin did not inhibit AMPA currents in a significant manner ( FIG. 2B ), and the previously identified active domain of the P2 laminin LRE was also inactive in modulating AMPA receptor currents of human neocortical neurons ( FIG. 2B ).
[0043] Example traces of 20 mM glutamate evoked currents in human neocortical neurons in the absence and presence of the KDI peptide (0.1-10 μg/ml) thus indicate that pre-application of KDI produces an inhibition, which is dose-dependent, washable and reproducible. A column presentation of FIG. 2B demonstrates a percentage of inhibition of laminin-1 and its various derivatives on AMPA receptor currents of human neocortical neurons. Laminin-1 (Lam-1), purified from mouse EHS-tumor (Martin and Timpl, 1987), produced a significant (***) inhibition of AMPA currents. P10-OH (RDIAEIIKDI-OH), an acid form of the neurite outgrowth domain of the γ1 laminin also produced effective (***) inhibition of AMPA receptors, whereas P10-NH 2 , an amide form of the same, was much less efficient (**). The KDI peptide was most efficient (***) in inhibiting AMPA currents, whereas a control peptide from cell attachment domain of β1 laminin (CDPGYIGSR), and a control tri-peptide LRE from β2 laminin did not affect AMPA receptor currents. Asterisks indicate statistical significance of inhibition between the control and the peptide treatment tested by t-test, p<0.001 (***), p<0.01 (**).
[0044] The acidic form of the KDI-peptide inhibited AMPA receptor currents of human neocortical neurons in a dose dependent manner, IC 50 being at 0.1 μg/ml (300 nM) of the tripeptide ( FIG. 3A ). Glutamate dose response curves were measured in the presence of 0.1 μg/ml of KDI ( FIG. 3B ). EC 50 values in the absence and presence of KDI were 2.5 and 1.9 mM, respectively, indicating a non-competitive inhibition of the receptor by the KDI peptide ( FIG. 3B ). The inhibitory effect of the KDI peptide on the AMPA receptor currents was a direct one. This was apparent from the fact that the KDI-induced inhibition required only a short pre-application of the peptide (62±22 ms) for maximal inhibition ( FIG. 3C ). Co-application of 3 μg/ml (10 μM) of the KDI with glutamate without KDI-pre-application produced an inhibition of only 37±20% ( FIG. 3C ), which was a minute one as compared to inhibition obtained with the KDI (3 μg/ml) pre-application (75%; see FIG. 2B ).
[0045] The effect of the KDI-peptide on NMDA receptor currents of human neocortical neurons was studied using 100 μM NMDA as an agonist, and an external solution without Mg 2+ ( FIG. 4A ). At 0.1-10 μg/ml (300 nM-30 μM), the KDI peptide produced an inhibition of 25-50% of the NMDA receptor currents ( FIG. 4A ).
[0046] As we were unable to detect kainate receptor currents in human neocortical neurons even though they looked mature, healthy and expressed several kainate receptor subunits at the protein level ( FIG. 1A ), we used HEK 293 cells transfected with the GluR6 receptor subunit, also expressed by human cortical pyramidal neurons ( FIG. 1A ), to study the effects of the KDI-peptide on kainate receptor currents. Our results indicate that the GluR6 kainate receptors of the HEK 293 cells were equally sensitive to KDI-inhibition as the AMPA receptors of the human neocortical neurons showing an IC 50 at 0.1 μg/ml of KDI peptide ( FIG. 4B ). Recombinant AMPA receptors (GluR4 subtype) of the transfected HEK 293 cells, similar to human neocortical neurons ( FIGS. 2-3 ), were highly sensitive to the inhibitory effect of KDI peptide. The KDI peptide at 10 μg/ml (30 μM) inhibited GluR4 currents evoked by 10 mM glutamate by 83±14%, IC 50 being approximately 0.1 μg/ml (data not shown).
[0047] In the present invention we thus show that laminin-1, and various peptide derivatives of the γ1 laminin, in particular the neurite outgrowth promoting KDI domain, inhibit AMPA receptor currents in human neocortical neurons in a dose-dependent and non-competitive manner. Similarly, the KDI-domain also inhibits NMDA receptor currents in neocortical neurons and recombinant kainate and AMPA receptor currents in transfected HEK 293-cells. The KDI peptide produces almost complete inhibition of AMPA and kainate receptors at 10 μg/ml (30 μM) and a 50% inhibition of the NMDA receptor currents. Thus, the KDI domain of γ1 laminin is a novel, extremely potent and universal antagonist of the major subclasses of ionotropic glutamate receptors.
[0048] The direct inhibition of glutamate receptor function by the KDI tri-peptide shown here reveals an entirely novel and biologically highly relevant function for the γ1 laminin and its KDI domain. Until now, the effects of extracellular matrix proteins, including the γ1 laminin, in the nervous system have been considered indirect and mediated via signalling cascades initiated by cell-matrix contacts.
[0049] That laminin-1 (composed of disulphide bonded α1β1γ laminins) and both the 10 amino acid neurite outgrowth domain (RDIAEIIKDI) of γ1 laminin, e.g., the amphiphilic peak of the γ1 laminin, and its shortest active KDI-domain all act as antagonists of AMPA-receptors indicate that the 10 amino acid neurite outgrowth domain, indeed, is facing the outside of the alpha-helical domain I of the C-terminus of laminin-1. That the acid form of the 10 amino acid peptide is far more efficient than its amide form and the acid form of the KDI domain is the most efficient antagonist of glutamate receptors indicate that these domains are likely to be cleaved by proteolysis from the laminin-1 molecule rather than being synthesized and secreted as naturally occurring peptides.
[0050] Never before has an extra-cellular matrix protein or its functionally active domain been shown to directly regulate the activity of a neurotransmitter activated ligand-gated ion channel. Even if previous studies have shown interaction between laminin and calcium and potassium channels, no electrical responses have been reported for this interaction. Thus, the present results are revolutionary in showing that the role of γ1 laminin in the CNS is not limited to promotion of neurite outgrowth, neuronal migration and regeneration with the assumption that all these functions are mediated solely by its adhesive properties. Even though the adhesive properties have been shown to play an important role in these biological events, the present data indicate that the neurite outgrowth KDI domain of γ1 laminin has additional diverse and important functions that shed new relevance for expression of γ1 laminin in adult CNS neurons, and in CNS after trauma or in a neurological disorder, such as Alzheimer's disease. The inhibitory function of the KDI domain on glutamate receptor function indicates that γ1 laminin may be expressed in adult neocortical and hippocampal neurons for protective and regulatory reasons essential for normal functioning of the CNS.
[0051] Recent studies from this laboratory offer the first practical examples on the regulatory and neuroprotective potential of the KDI domain in vivo. As compelling evidence indicates that glutamate neurotoxicity is a major player in all CNS trauma and neurodegenerative disorders, novel drugs used clinically to treat patients with Alzheimer's disease, ALS or stroke, are inhibitors of glutamate receptor function. In the present invention we show that the KDI tri-peptide is the only so far known universal inhibitor of ionotropic glutamate receptor function with already demonstrated ability to protect adult rat CNS against excitotoxicity. These results strongly imply that the KDI peptide may become one of the most efficient targeted medications for CNS trauma and disease.
[0052] The present invention thus provides natural, biologically active peptide compounds for medical use. The peptides are useful in soluble or substrate-bound forms in the treatment of disorders responsive to the blockade of ionotropic glutamate receptors. Consequently, the KDI peptide can be used in treating neurodegenerative diseases, such as Parkinson's or Alzheimer's disease, ALS or stroke. A suitable pharmaceutical composition for that purpose is an injectable liquid to be administered to the intrathecal space or injected to the brain tissue.
[0053] The peptides of the present invention may be prepared using conventional methods for peptide synthesis, as described, for instance, by Liesi et al. (1989).
[0054] The term “pharmaceutically acceptable salt” as used herein, refers to salts of the peptides employed in the present invention which are substantially non-toxic to living organisms. Typical pharmaceutically acceptable salts include salts prepared by reaction of the peptide compounds of the present invention with a pharmaceutically acceptable mineral or organic acid or an organic or inorganic base. Such salts are known as acid addition and base addition salts.
[0055] The peptide compounds employed in the methods of this invention may also occur in any other pharmaceutically acceptable form which a peptide compound may take by a reaction characteristic of the functional groups of such a peptide compound.
[0056] The term “pharmaceutically acceptable carriers, diluents and excipients” as used herein refers to vehicles or additives conventionally used in formulating pharmaceutical compositions.
[0057] Pharmaceutical compositions containing the peptides of the invention for the treatment of neurodegenerative diseases are preferably liquid preparations suitable for injection. The peptides may be dissolved in sterile saline or water. A pharmaceutical composition may include a modification of the KDI peptide that allows its direct access to the CNS through the blood-brain-barrier, and also include biodegradable polymers, which slowly release the peptide and simultaneously, as an additional advantage, provide a direction for the growing axons.
[0058] The peptides of the present invention may thus be administered in a therapeutically effective amount within a wide dosage range. The therapeutically effective amount depends on the age and condition of the tissue in question. Peptides of the present invention may be administered either as a single dose, or as continuous administration using, for instance, a mini pump system. In the latter case, the daily dosage will not exceed the dose of a single injection, and must be pre-determined by animal experimentation.
[0059] The concentrations of a peptide of the invention in a pharmaceutical composition are generally between 0.01 and 100 μg/ml. However, it should be noted that the optimal concentration of the KDI peptide may be domain dependent or tissue dependent, and therefore pre-testing of the dosage is of utmost importance. Determining of the suitable dosage for individual treatments is within the skills of those familiar with the art.
[0060] The pharmaceutical composition of the present invention can be administered by any means that achieve the intended purpose. For instance, for the treatment of stroke the composition can be administered to the injury site via a catheter, or intravenously. In Alzheimer's disease and Parkinson's disease the pharmaceutical composition of the present invention may be continuously administered by using local application via a catheter or patch, or systemically via intravenous infusion or a pill, provided that KDI or any of its pharmaceutically acceptable form can be orally administered and will cross blood-brain-barrier.
[0061] In spinal cord trauma or injury a most preferable way of administration is using a mini pump system to administer the peptide composition directly to the trauma area of the spinal cord. This can be easily carried out in connection with orthopaedic surgery for disclosing the trauma area.
[0062] In ALS, the administration may be carried out directly into the cerebrospinal fluid at the lumbar level via a mini pump or patch or, alternatively, orally or intravenously.
[0063] The pharmaceutical compositions of the present invention can be administered to any animal that can experience the beneficial effects of the peptides of the invention. Human beings are foremost among such animals, although the invention is not intended to be limited to the medical treatment of human beings.
[0064] An advantageous feature of the KDI peptide is the fact that it is a short peptide, being not immunogenic, and therefore risks for immunological reactions are minimal. Furthermore, as the peptide has previously been disclosed as a flavoring ingredient, it should be safe for human use.
EXPERIMENTAL
[0000] Human CNS-tissues
[0065] Human fetal CNS-tissues were obtained from 8-11 week old fetuses after legal abortion, and after informed consent from the patients. The tissues were collected within 2-4 hrs by the permission of the Ethics Committee of the Maternity Hospital of the Central University Hospital.
[0000] Neuronal Cultures
[0066] The CNS tissues were first placed in cold saline. The neocortical areas of 11-week embryos were identified under a stereomicroscope, and carefully freed of meningeal membranes. Neuronal cultures were prepared as described previously (Liesi et al., 2001) and plated at 2×10 4 on glass coverslips pre-coated with poly-D-lysine (10 mg/ml, Collaborative Research) in Neurobasal medium (Gibco, U.K.) with B27-supplement (Gibco, U.K.), antibiotics and 500 μM L-glutamine. After 14-30 days in culture, the cultures were fixed in 2% paraformaldehyde/PBS pH 7.4 for 15 min at room temperature (RT), and processed for immunocytochemistry.
[0000] Analysis of Glutamate Receptors in Cultured Human Neocortical Neurons
[0067] Highly specific rabbit polyclonal antibodies (Upstate, NY, USA) against AMPA, kainate and NMDA receptor subunits were used at 5-10 μg/ml. After fixation, the cultures were treated in 0.05% Tween-20 in PBS pH 7.4 for 30 min at RT, washed in PBS and incubated with polyclonal anti-glutamate receptor antibodies diluted in PBS for 1 hr at RT. After a brief wash in PBS, the cultures were incubated with anti-rabbit immunoglobulins coupled to FITC for 30 min at RT, washed once in PBS and mounted in PBS:Glycerol (1:1). The cultures were viewed using an Olympus BX51 microscope with appropriate filters and photographed using an Olympus DP70 digital camera.
[0000] Electrophysiology of Human Neocortical Neurons and HEK 293 Cells
[0068] For whole cell patch clamp recordings, cultures were placed under an inverted microscope (Olympus IX71). During recordings neurons were continuously superfused with an external solution (pH 7.4) containing in mM: 150 NaCl, 2.5 KCl, 2.5 CaCl 2 , 1 MgCl 2 , 10 HEPES, and 10 glucose. Experiments were carried out at room temperature. Patch clamp pipettes had a resistance of 4 to 7 MΩ when filled with an internal solution containing in mM: 100 N-methyl-D-glucamine, 100 CH 3 SO 3 H, 40 CsF, 10 MgCl 2 , 10 HEPES, and 5 EGTA, pH adjusted with CsOH to 7.4. Cells were clamped at a holding potential of −60 mV. Drugs were diluted in external solution and applied to cells with a multi-barrel fast solution application system (Warner Instrument, Hamden, Conn.). In most experiments, the test-drugs (e.g., laminin-1 and various laminin peptides) were first pre-applied to cells followed by co-application of the agonist and the test-drug. Currents were recorded using Axopatch 200B amplifier and pClamp 8.0 software (Axon Instruments, Inc., Foster City, Calif.) and stored to the hard drive of PC computer. Recordings were sampled at 20 Hz and filtered with 1 Kz lowpass bessel filter. Data were analyzed with pClamp8.0 software. Statistical analysis of results was done with the Prism 3.02 software (Graphpad, San Diego, Calif.) using a repeated Measures ANOVA and Dunnett's post-test. L-glutamate and concanavalin A were from Sigma (St. Louis, Mo.) and SYM 2081 and NMDA were from Tocris (Avonmouth, UK). Mouse native laminin-1 was from Boehringer-Mannheim (Germany). All synthetic peptides were from Multiple Peptide Systems (San Diego, Calif.).
[0069] Human embryonic kidney cells (HEK 293 cells) were cultured in Dulbecco's modified Eagle's medium supplemented with 10% fetal calf serum and 2 mM L-glutamine and 1% penicillin-streptomycin solution. Cells were transfected with recombinant GluR4 (AMPA) and GluR6 (kainate) receptor subunit cDNA-clones using calcium phosphate method as previously described (Pasternack et al., 2002).
REFERENCES
[0000]
Guadagno, E. and Moukhles, H. Laminin-induced aggregation of the inwardly rectifying potassium channel, Kir4.1, and the water-permeable channel, AQP4, via a dystroglycan-containing complex in astrocytes. Glia 47:138 (2004).
Liebkind, R., Laatikainen, T. and Liesi, P. Is the soluble KDI domain of gamma-1 laminin a regeneration factor for the mammalian central nervous system? J. Neuroscience Res. 73:637 (2003).
Liesi, P., Närvänen, A., Soos, J., Sariola, H. and Snounou, G. Identification of a neurite outgrowth promoting domain of laminin using synthetic peptides. FEBS Lett. 244:141 (1989).
Liesi, P. Extracellular matrix and neuronal movement. Experientia 46:900 (1990).
Liesi, P., Fried, G. and Stewart, R. Neurons and glial cells of the embryonic human brain and spinal cord express multiple and distinct isoforms of laminin. J. Neuroscience Res. 64: 144 (2001a).
Liesi, P., Laatikainen, T. and Wright, J. M. A biologically active sequence (KDI) mediates the neurite outgrowth function of the gamma-1 chain of laminin-1. J. Neuroscience Res. 66:1046 (2001b).
Liesi, P. and Kauppila, T. Induction of type IV collagen and other basement membrane associated proteins after spinal cord injury of the adult rat may participate in formation of the glial scar. Exp. Neurol. 173:31 (2002).
Martin, G. R. and Timpl, R. Laminin and other Basement Membrane Components. Annual Review of Cell Biology 3:57 (1987).
Mattson, M. P. Excitotoxic and excitoprotective mechanisms: abundant targets for the prevention and treatment of neurodegenerative disorders. Neuromolecular Med. 3:65 (2003).
Meiners, S. and Mercado, M. L. Functional peptide sequences derived from extracellular matrix glycoproteins and their receptors: strategies to improve neuronal regeneration. Mol. Neurobiol. 27:177 (2003).
Miner, J. H. and Yurchenco, P. D. Laminin functions in tissue morphogenesis. Annu. Rev. Cell Dev. Biol. 20:255 (2004).
Murtomäki, S., Risteli, L., Risteli, J., Johansson, S., Koivisto, U-M. and Liesi, P. Laminin and its neurite outgrowth promoting domain associate with the Alzheimer's and Down's syndrome brains. J. Neuroscience Res. 32:261 (1992).
Nishimune, H., Sanes, J. R. and Carlson, S. S. A synaptic laminin-calcium channel interaction organizes active zones in motor nerve terminals. Nature 432:580 (2004).
Palu, E. and Liesi, P. Differential distribution of laminins in Alzheimer's and normal brain tissues. J. Neuroscience Res. 69:243 (2002).
Pasternack, A., Coleman, S. K., Jouppila, A., Mottershead, D. G., Lindfors, M., Pasternack, M. and Keinänen, K. Alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptor channels lacking the N-terminal domain. J. Biol. Chem. 277:49662 (2002).
Wiksten, M., Liebkind, R., Laatikainen, T. and Liesi, P. γ1 laminin and its biologically active KDI-domain may guide axons in the floor plate of the embryonic human spinal cord. J. Neuroscience Res. 71:338 (2003).
Wiksten, M., Väänänen, A. J., Liebkind, R. and Liesi, P. Regeneration of adult spinal cord is promoted by the soluble KDI-domain of γ1 laminin. J. Neuroscience Res. 78:403 (2004a).
Wiksten, M., Väänänen, A. J., Liebkind, R., Rauhala, P. and Liesi, P. The soluble KDI-domain of γ1 laminin protects adult rat hippocampus from excitotoxicity of kainic acid. J. Neuroscience Res. 78:411 (2004b).
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The present invention relates to biologically active peptides derived from the neurite outgrowth-promoting domain of luminin-1, i.e. the γ1-chain of laminin-1. These peptides include the decapeptide RDIAEIIKDI (SEQ ID NO: 1) and the truncated peptides derived therefrom comprising the biologically active domain thereof, the tripeptide KDI. The invention is directed to the biologically active tripeptide motifKDI, and to its use in promoting regeneration of neuronal or non-neuronal tissues and, in specific, to its use in the treatment of spinal cord injuries.
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DESCRIPTION
The present invention relates to portable transaction terminals which provide for the entry of data by optical code reading or keyboard entry and particularly to an improved terminal where data entry operations do not interfere with other operations as may be required to handle products thereby reducing the time and increasing the efficiency and productivity in inventory management operations.
The invention is especially suitable for providing a portable transaction or data entry terminal which is battery operated and which may be used to gather data concerning products, both by manual entry of the data and operation of an optical reader of codes containing the data, all of which are embodied in a glove which is worn by the operator on one hand so that the data acquisition and entry operations do not interfere with the use of the hands by the operator to pick and place products in the course of inventory management operations.
Portable transactions terminals, including bar code scanners and readers and keyboards integrated into the terminal to provide a universal device, are in general use for inventory management and control. These terminals include housings for the optics of the scanner and the electronics associated therewith, computers, keyboards and displays. The forms of such terminals vary, but most comprise a trigger operated scanner and a keyboard on the surface of the scanner housing (see U.S. Pat. No. 4,758,717 issued Jul. 19, 1988). Operation of the terminal either to enter data via the keyboard or for manual actuation of the scanner requires operations separate, distinct and apart from the normal operation of personnel which manage inventory such as picking and placing of products in racks. In addition, operators are called on to pull triggers thousands of times in a workday and to actuate keyboards by pressing buttons. Such repetitive motion causes stress and has been found to cause physical injury in certain cases, sometimes called carpal motion syndrome.
It is the principal object of this invention to provide an improved portable transaction terminal for entry of data by code reading or by entering the data, either digits or alphanumeric data without the need for triggers or keys or special manipulations which interfere with the performance by the operator of inventory management tasks such as picking and placing of products.
It is a further object of the present invention to provide an improved portable transaction or data entry terminal where entry of digits*, and code scanning facilities are integrated into a glove which is worn by the operator on one hand and enables the operator to carry on normal operations, such as picking and placing of products on shelves or racks.
It is a still further object of the present invention to provide an improved portable transaction terminal which may be implemented in a glove at cost competitive with conventional data entry terminals for similar purposes.
Briefly described, a portable transaction terminal embodying the invention, which does not require manual keyboard or code reader actuation, makes use of a hand receiving glove having a plurality of sheaths for a plurality of fingers and a cover extending rearwardly from the sheaths for the back of the hand. An optical code reader is mounted on the cover for scanning and reading a code at which the hand is pointed. A plurality of sensors are disposed in the sheaths and are responsive to the motion of the joints of the fingers (between flexion and extension) for entering the transaction data and also for actuation of the reader. A character display may also be mounted on the cover, preferrably in the same housing as the code reader, for displaying the code which is read. The terminal may also be in communication, as by radio, with a dispatcher for displaying operator prompts. The prompts (a menu of instructions) for the operator which is selected, as by flexing of the fingers, may also be stored in memory of the reader.
The foregoing and other objects, features and advantages of the invention, as well as a presently preferred embodiment thereof will become more apparent from a reading of the following description in connection with the accompanying drawings in which:
FIG. 1 is a perspective view of glove apparatus providing a portable transaction terminal which embodies the invention;
FIG. 2 is a schematic perspective view illustrating the operation of the terminal in entering numerical values and commands;
FIG. 3 is a perspective view similar to FIG. 1 wherein the strips on the finger sheaths are removed to illustrate the location of the sensors in the vicinity of the joints of the fingers;
FIG. 4 is a sectional view of the glove in the portion thereof penetrated by the index finger; and
FIG. 5 is a block diagram of the electronic system of sensors and data gathering elements which are integrated into the terminal shown in the preceding figures.
Referring more particularly to FIG. 1, there is shown a glove 10 having sheaths 11 which contain the thumb 12, the index finger 14, the long finger 16, the ring finger 18 and the small finger 20. These sheaths 11 are provided by strips 15 of flexible plastic material, such as polyethylene having grooves in the vicinity of the interphalangeal joints of the fingers (these grooves for the index finger 14 are shown at 22 and 24 in FIG. 4). These joints are the distal and proximal joints, which are known as the DIP and PIP joints. The DIP joint is the joint below the groove 22 and the PIP joint is the joint below the groove 24. There is another joint in the fingers between the body of the hand (between the dorsal and palmar surfaces thereof) known as the metacarpophalangeal joints which are usually abbreviated as MP joints. There is one joint in the thumb which has a great deal of motion and that is shown below the groove 26. One side of the grooves is higher than the other; providing a "bumper" for protection of the strain gauge pads 50, 52, 54, 56 thereunder.
The top or posterior surface of each finger is covered by the strips 15 of flexible plastic material. This strip extends into a cover section 28 which extends rearwardly from the MP joints (from the fingers) into a gauntlet section 30 which extends over the wrist. The cover section 28 and the strips over the posterior of each finger have attached thereto a cloth material in the shape of the fingers and palm portion of the hand. This fabric is connected, as by heat sealing or sewing, along the edges of the strips covering the fingers and under the cover and gauntlet section 28 and 30. A wrist strap 32, which may have loop connectors (Velcro), may be used to tighten the glove in place.
On the cover 28 is a housing 34 containing a bar code reader or scanner 35, the optical output port of which is shown at 36. A beam of light which scans the code extends through the port and scattered light representing the code which is scanned is received through the port. Such a bar code scanner or reader of the type which is shown in U.S. Pat. No. 5,015,831 issued May 14, 1991 or U.S. patent application Ser. No. 07/543,950 filed Jun. 26, 1990 (now U.S Pat. No. 5,115,120, issued May 19, 1992) in the name of J. M. Eastman is presently preferred because of its miniaturized configuration.
The housing has an opening in which an LCD display showing a plurality of characters of alphanumeric data appears on the top of the housing 34 and is visible to the operator whose hand is in the glove 10. The bar code scanner is connected by a cable 40 to a battery and transmission pack 42 (FIG. 5) which may be carried on the belt of the operator and may contain a transceiver 43 and an antenna for transmission via a radio link of the data collected by the terminal integrated into the glove 10.
As shown in FIG. 3, there are sensors 50, 52 and 54 embedded in the strips of flexible plastic material sheathing the posterior of the index long and ring finger respectively in the vicinity of the DIP, PIP and MP joints of these fingers. There are single sensors 56 over a joint, suitably the DIP joint of the thumb, and the PIP joint of the small finger. These sensors are strain gauges and may suitably be pads called "force sensing resistors" and sold by Interlink Electronics, 1110 Mark Ave. Carpinteria, Calif. 93013, U.S.A.
As shown in FIGS. 2 and 4, as the index, long and ring finger are selectively bent between the extension position shown in full in FIG. 4 for the index finger and the flexion position shown in the dash line in FIG. 4. The strain gauge pads are therefore selectively bent. A clicker may be embodied in the strips 15 to give a feel or an audible indication of when sufficient bending of the joints occur. There are 11 strain gauge pads in the illustrated embodiment of the invention. Additional strain gauges may be incorporated in the glove, for instance, in the areas of the palm to sense other hand motions, for example, contraction of the palm. The strain gauge pads on the thumb and on the three joints of the index, long and ring finger correspond to the digits 0 to 9 as shown in FIG. 2. The strain gauge pad on the small finger corresponds to an "enter" command. By bending these fingers, signals are generated as current through the strain gauge elements modulated by the strain imposed when the finger is bent. A command to "trigger" (turn on) the reader 35 to energize the light source and the scanning mechanism therein is provided by a closely spaced sequence of enter commands or a combination of finger flexions. In a similar manner, alphabetical characters can be encoded and entered with the terminal, as with combinations of movements, as used in executing sign language for communicating with hearing impaired persons.
These signals are translated in a digitizer 60 (FIG. 5) into data which is decoded in a decoder 62. The decoder has output lines corresponding to the 0 to 9 and E for "enter". It may be desirable, especially where alphanumeric data is to be entered, that the signals from the strain gauge elements be applied to the microprocessor which then includes facility of analog to digital conversion and decoding of the signal combinations corresponding to different numbers and letters in an alphanumeric character set. These output lines are applied to an input port of a microprocessor 64.
The microprocessor, in the illustrated embodiment, has control and data lines to the code reader 66 in the housing 34. When an appropriate code is generated by the flexing, say of the index finger alone accompanied by a flexure of the small finger to enter the data into the microprocessor 64, power is applied from the battery (between plus V and ground) to operate the scanner.
Upon detection of the bar code, a lamp or audible signal denoting a "good read", as is conventional, is provided. The data is entered into memory in the microprocessor 64 and may be stored therein until commanded to be read out as via a modem 68 which receives commands from a host computer via a radio control link using a transceiver 43 optical (e.g., infrared) or acoustic (e.g., ultrasonic) links may alternatively be used. Alternatively, the microprocessor may have an output port which plugs into the host computer for readout of data. The display 38 is also driven by the microprocessor and indicates the code which is read and the digits which are entered by bending of the fingers. It will be apparent that the operator has full control of his or her hands and may pick or place objects pausing only when necessary to actuate the code reader or to enter data by moving the glove fingers between extension and flexion positions.
Preferably, the housing 34 of the code reader 66 contains the microprocessor (including associated memory RAM and ROM), the decoder and the digitizer and the liquid crystal display. These elements are provided by integrated circuit chips mounted on a printed circuit board disposed within the housing 34. The housing 34 may, if desired, be extended to contain the battery and modem. Presently, the use of a separate pack 42 for the battery and modem is preferred. Instructions or prompts for dispatching the operator to different locations (e.g., rack areas where products to be picked up are located) may be transmitted via the radio link and displayed on the display 38. These prompts may alternatively be in a succession (a menu) stored in the memory associated with the microprocessor selected by the operator, by finger manipulations, read out and displayed on the display 38.
From the foregoing description, it will be apparent that there has been provided an improved portable data entry or transaction termination which enables inventory management with higher efficiency and productivity than conventional portable transaction terminals. Variations and modifications in the herein described terminal, within the scope of the invention, will undoubtedly suggest themselves to those skilled in the art. Accordingly, the foregoing description should be taken as illustrative and not in a limiting sense.
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To increase the efficiency of personnel conducting inventory management operations, including data entry of products and information as to their absence, presence or location, the operator is provided with a glove having finger sheaths and a portion for the posterior or dorsal surface of the hand which covers that surface. A bar code reader is located in a housing on the cover and flexural strain gauge elements are located in the sheaths in the vicinity of the joints of the fingers. Signals from these elements are digitized and provide for manual data entry and also for commands to operate the bar code reader. The glove and the sensors constitute a portable transaction or data entry terminal which does not require manual actuation of a trigger to operate the bar code scanner or a keyboard for manual entry of data concerning the products to be managed. Electronics for processing signals from the sensors, for operating a display to indicate the data entered upon selective movement of the fingers between flexion and extension and from the bar code reading operations, are all contained in a housing which also contains the bar code reader.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. Patent application Ser. No. 11/444,751 filed May 31, 2006, which claims the benefit of U.S. provisional application No. 60/704,273 filed Aug. 1, 2005, the contents of which are incorporated by reference herein as if fully set forth.
FIELD OF INVENTION
[0002] The present invention is related to wireless communication systems. More particularly, the present invention is related to a method and apparatus for controlling enhanced dedicated channel (E-DCH) transmissions.
BACKGROUND
[0003] Methods for improving uplink (UL) coverage, throughput and transmission latency are currently being investigated in the third generation partnership project (3GPP). In order to achieve these goals with respect to an E-DCH, the control of UL resources, (i.e., physical channels), has been moved from the radio network controller (RNC) to the Node-B.
[0004] In order to reduce complexity and power consumption, execution of wireless transmit/receive unit (WTRU) side enhanced uplink medium access control (MAC-e/es) functions, such as E-DCH transport format combination (E-TFC) selection and multiplexing, remaining transmit power calculation, and processing of absolute grants (AGs) and relative grants (RGs), needs to be properly controlled and coordinated.
SUMMARY
[0005] The present invention is related to a method and apparatus for controlling E-DCH transmissions. A MAC-e/es entity of the WTRU receives a scheduling grant and processes the scheduling grant to calculate a serving grant. The MAC-e/es entity determines whether both a hybrid automatic repeat request (H-ARQ) process for scheduled data and the scheduled data are available. If an H-ARQ process for scheduled data and the scheduled data are both available, the MAC-e/es entity determines whether a serving grant exists. The MAC-e/es entity then calculates a remaining power based on the maximum allowed power and restricts an E-TFC based on the remaining power. The MAC-e/es entity selects an E-TFC using the serving grant and generates a MAC-e protocol data unit (PDU) for transmission. The MAC-e/es entity may process the received scheduled grant at each transmission time interval (TTI), or may store the received scheduled grant in a grant list until there is E-DCH data to transmit.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a block diagram of a wireless communication system configured in accordance with the present invention.
[0007] FIG. 2 is a block diagram of a protocol architecture of a WTRU in accordance with the present invention.
[0008] FIG. 3 is a block diagram of a MAC-e/es entity of a WTRU in accordance with the present invention.
[0009] FIG. 4 is a flow diagram of a process for controlling E-DCH transmissions in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] When referred to hereafter, the terminology “WTRU” includes but is not limited to a user equipment (UE), a mobile station, a fixed or mobile subscriber unit, a pager, or any other type of device capable of operating in a wireless environment. When referred to hereafter, the terminology “Node-B” includes but is not limited to a base station, a site controller, an access point (AP) or any other type of interfacing device in a wireless environment.
[0011] The present invention is applicable to any wireless communication systems including, but not limited to, universal mobile telecommunication systems (UMTS) frequency division duplex (FDD), UMTS time division duplex (TDD) and time division synchronous code division multiple access (TD-SCDMA) systems.
[0012] The features of the present invention may be incorporated into an integrated circuit (IC) or be configured in a circuit comprising a multitude of interconnecting components.
[0013] FIG. 1 is a block diagram of a wireless communication system 100 configured in accordance with the present invention. The system 100 comprises a WTRU 102 , a Node-B 104 and an RNC 106 . The RNC 106 controls overall E-DCH operation by configuring E-DCH parameters for the Node-B 104 and the WTRU 102 , such as initial transmit power level, maximum allowed transmit power or available channel resources per Node-B. Between the WTRU 102 and the Node-B 104 , an E-DCH 108 , an E-DCH dedicated physical control channel (E-DPCCH), an absolute grant channel (E-AGCH) 112 , a relative grant channel (E-RGCH) 114 and an H-ARQ information channel (E-HICH) 116 are established for supporting E-DCH operations.
[0014] For E-DCH transmissions, the WTRU 102 sends scheduling information, (also known as a rate request), to the Node-B 104 via the E-DPCCH 110 . The Node-B 104 sends a scheduling grant to the WTRU 102 via the E-AGCH 112 or the E-RGCH 114 . After E-DCH radio resources are allocated for the WTRU 102 , the WTRU 102 transmits UL data via the E-DCH 108 . In response to the E-DCH transmissions, the Node-B 104 sends an acknowledgement (ACK) or non-acknowledgement (NACK) message for H-ARQ operation via the E-HICH 116 . The Node-B 104 may also respond with rate grants to the WTRU 102 in response to E-DCH data transmissions.
[0015] FIG. 2 is a block diagram of a protocol architecture of the WTRU 102 in accordance with the present invention. The protocol architecture of the WTRU 102 includes higher layers 202 , a radio link control (RLC) layer 204 , a MAC layer 206 and a physical layer 208 . The MAC layer 206 includes a dedicated channel medium access control (MAC-d) entity 210 and a MAC-e/es entity 212 . The MAC-e/es entity 212 handles all functions related to the transmission and reception of an E-DCH including, but not limited to, H-ARQ transmissions and retransmissions, priority of data, MAC-d and MAC-es multiplexing, and E-TFC selection. The RLC layer 204 is provided for in-sequence delivery of data. A re-ordering function is provided in the RLC layer 204 to organize the received data blocks according to the sequence.
[0016] FIG. 3 is a block diagram of the MAC-e/es entity 212 in accordance with the present invention. The MAC-e/es entity 212 includes an E-TFC selection entity 302 , a multiplexing and transmission sequence number (TSN) setting entity 304 , an H-ARQ entity 306 , a serving grant processing entity 308 and a memory 310 . The serving grant processing entity 308 receives an AG 312 and a RG(s) 314 from the physical layer 208 and processes the AG 312 and the RG(s) 314 to generate a serving grant or stores them in the memory 310 . There may be one or more RGs 314 . The E-TFC selection entity 302 selects an E-TFC based on the serving grant and performs an arbitration among different data flows mapped on the E-DCH.
[0017] The multiplexing and TSN setting entity 304 concatenates multiple MAC-d PDUs into MAC-es PDUs, and multiplexes one or multiple MAC-es PDUs into a single MAC-e PDU to be transmitted in the next TTI as instructed by the E-TFC selection entity 302 . The multiplexing and TSN setting entity 304 also manages and sets a TSN per logical channel for each MAC-es PDU.
[0018] The H-ARQ entity 306 controls a plurality of H-ARQ processes for storing MAC-e PDUs and retransmitting the MAC-e PDUs when a transmission failure is signaled via the E-HICH. An active H-ARQ process is used for transmission of scheduled data, while a non-active H-ARQ process is not used for transmission of scheduled data. At a given TTI, the H-ARQ entity 306 identifies an H-ARQ process for which a transmission should take place. At the time of a new transmission, the H-ARQ entity 306 provides an H-ARQ profile for all new transmissions and retransmissions of a MAC-e PDU. The H-ARQ profile includes information on the maximum number of transmissions and a power offset with which to configure the physical layer.
[0019] The execution of the E-TFC selection by the E-TFC entity 302 depends on the availability of data mapped to the E-DCH with a grant (including an occurrence of a scheduling information rate request trigger) and the availability of an H-ARQ process. An H-ARQ process should be available before E-TFC selection is performed by the E-TFC selection entity 302 . The H-ARQ entity 306 identifies to the E-TFC selection entity 302 the availability of H-ARQ processes. H-ARQ processes may be available upon initial configuration, ACK reception, or exceeding the maximum number of retransmissions for any H-ARQ processes.
[0020] FIG. 4 is a flow diagram of a process 400 for controlling E-DCH transmissions in accordance with the present invention. A physical layer receives a scheduling grant via an E-AGCH 112 and E-RGCHs 114 (step 402 ). After decoding of E-AGCH and E-RGCH, an AG 312 and RG(s) 314 are sent to the serving grant processing entity 308 in the MAC-e/es entity 212 . The serving grant processing entity 308 processes the AG 312 and RG(s) 314 to determine a serving grant. The scheduling grant may be an AG 312 from a serving E-DCH cell or an RG(s) 314 from either all cells in a serving E-DCH radio link set (RLS) or a non-serving radio link (RL). The scheduling grant is applied to a specific transmission time interval (TTI). This association is implicit based on the timing of the AG 312 and the RG(s) 314 .
[0021] Upon reception of the scheduling grant, the serving grant processing entity 308 has two options when there is no data to transmit in the TTI associated to the scheduling grant. The serving grant processing entity 308 may process the received scheduling grant to determine a current serving grant each TTI (step 404 ). Alternatively, the serving grant processing entity 308 may store the received scheduling grant in a memory 310 , (i.e., a grant list), and process the stored scheduling grants when there are E-DCH data to transmit.
[0022] The E-TFC selection entity 302 determines whether any H-ARQ processes for scheduled data, (i.e., an active H-ARQ process) and scheduled data are both available (step 406 ). If an H-ARQ process for scheduled data and scheduled data are both available, the process 400 proceeds to step 410 to determine whether a serving grant exists. Alternatively, if both the H-ARQ process for scheduled data and the scheduled data are both available, and if the second option is implemented, (i.e., the received scheduling grant is stored in the memory 310 ), the serving grant processing entity 308 processes the scheduling grant stored in the memory 310 to determine a serving grant at step 408 before proceeding to the step 410 .
[0023] A serving grant indicates a maximum E-DPDCH to dedicated physical control channel (DPCCH) power ratio that the WTRU is allowed to allocate for the upcoming transmission for scheduled data. The serving grant is updated based on the AG and the RG.
[0024] In processing the scheduling grant stored in the grant list, the serving grant processing entity 308 may process the last N AGs among the stored scheduling grants to generate the serving grant. The value of N is larger than one.
[0025] Alternatively, the serving grant processing entity 308 may maintain only the most recent primary AG and subsequent RGs, including the latest secondary AG in the grant list. A primary AG is an AG received with a primary radio network temporary ID (RNTI) and a secondary AG is an AG received with a secondary RNTI. When a new primary AG is received previous AG and RGs except for the last secondary AG are removed from the grant list when the next transmission requiring a scheduling grant occurs. This reduces significant processing overhead following transmission idle periods.
[0026] In addition, whenever a serving cell change occurs, the serving grant processing entity 308 discards all stored AGs and RGs in the grant list. This operation is equivalent to setting an AG to zero and discarding all RGs.
[0027] At step 410 if it is determined that there is no serving grant, (i.e., a current serving grant is zero), the E-TFC selection entity 302 limits an E-TFC to a minimum set of E-TFCs (step 412 ) and calculates a remaining power based on the minimum set of E-TFCs (step 414 ). If it is determined that there is a serving grant at step 410 , the E-TFC selection entity 302 calculates a remaining power based on a maximum allowed power (step 414 ).
[0028] After the remaining power is calculated, the E-TFC selection entity 302 restricts E-TFCs for this TTI based on the remaining power (step 416 ). The E-TFC selection entity 302 then selects an E-TFC and the multiplexing and TSN setting entity 304 generates a MAC-e PDU by multiplexing MAC-d flows and MAC-es PDUs (step 418 ). A happy bit which indicates whether the WTRU is satisfied with a current scheduling grant is then set for transmission in this TTI (step 420 ) and the MAC-e/es entity waits for the next TTI (step 422 ).
[0029] If it is determined at step 406 that either an H-ARQ process for scheduled data, (i.e., an active H-ARQ process), is not available or scheduled data is not available, the E-TFC selection entity 302 then determines whether an H-ARQ process for non-scheduled data and the non-scheduled data are both available (step 424 ). If an H-ARQ process for non-scheduled data and the non-scheduled data are both available, the E-TFC selection entity 302 further determines whether there is any non-scheduled grant (step 426 ). The non-scheduled grant is set by an RNC in terms of maximum number of non-scheduled bits that can be included in a MAC-e PDU. The WTRU is allowed to transmit non-scheduled transmissions up to the sum of the non-scheduled grant if multiplexed in the same TTI. If there is a non-scheduled grant, the process proceeds to step 414 to calculate a remaining power and subsequent MAC-e functions, (i.e., steps 416 - 422 ), are performed as described hereinbefore.
[0030] If it is determined at step 426 that there is no non-scheduled grant, it is determined whether there is any H-ARQ processes available (step 428 ). If there is an available H-ARQ process, it is determined if scheduling information needs to be reported, (i.e., whether a triggering event occurs) (step 430 ).
[0031] Reporting of scheduling information is triggered by a plurality of different events, which are configurable. Generation of scheduling information is well known in the art and is not within the scope of the present invention. If it is determined at step 430 that there is scheduling information that needs to be transmitted, scheduling information bits are generated (step 432 ) and the process proceeds to step 414 to calculate a remaining power. Subsequent MAC-e functions, (i.e., steps 416 - 422 ), are then performed as described hereinbefore. If there is no scheduling information to be transmitted, no new transmission occurs in this TTI and the MAC-e entity waits for the next TTI (step 422 ).
[0032] If it is determined at step 428 that there is no available H-ARQ process, (which means that the transmission in this TTI is a retransmission), a happy bit is set for the transmission in this TTI to indicate whether the WTRU is satisfied with the scheduling grant (step 434 ) and the MAC-e entity waits for the next TTI (step 422 ).
[0033] Although the features and elements of the present invention are described in the preferred embodiments in particular combinations, each feature or element can be used alone without the other features and elements of the preferred embodiments or in various combinations with or without other features and elements of the present invention.
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A method and apparatus for controlling enhanced dedicated channel (E-DCH) transmissions are disclosed. An enhanced uplink medium access control (MAC-e/es) entity processes a received scheduling grant to calculate a serving grant. The MAC-e/es entity determines whether both a hybrid automatic repeat request (H-ARQ) process for scheduled data and scheduled data are available. If an H-ARQ process for scheduled data and scheduled data are available, the MAC-e/es entity determines whether a serving grant exists. The MAC-e/es entity calculates a remaining power based on maximum allowed power and restricts an E-DCH transport format combination (E-TFC) based on the remaining power. The MAC-e/es entity selects an E-TFC using the serving grant and generates a MAC-e protocol data unit. The MAC-e/es entity may process the received scheduled grant is at each transmission time interval or may store the received scheduled grant in a grant list until there is E-DCH data to transmit.
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TECHNICAL FIELD OF THE INVENTION
The invention is directed, in general, to signal processing and, more specifically, to a Doppler radar cardiopulmonary (CP) sensor and signal processing system and method for use therewith.
BACKGROUND OF THE INVENTION
This section introduces aspects that may help facilitate a better understanding of the invention. Accordingly, the statements of this Background of the Invention section are to be read in this light and are not to be understood as admissions about what is, or what is not, prior art.
Many potential applications exist for a non-invasive technique to monitor respiration, heartbeat or both. Doppler radar, operating at microwave frequencies in the range of 1-10 GHz, has long been suggested as a means to accomplish this (see, e.g., Lin, “Noninvasive Microwave Measurement of Respiration,” Proc. IEEE, vol. 63, p. 1530, October 1975; Pedersen, et al., “An Investigation of the employ of Microwave Radiation for Pulmonary Diagnostics,” IEEE Trans. Biomed. Eng, vol. BME-23, pp. 410-412, September 1976; Griffin, “MW Interferometers for Biological Studies,” Microw. J., vol. 21, pp. 69-72, May 1978; Lin, et al., “Microwave Apexcardiography,” IEEE Trans. Microw. Theory Tech., vol. MTT-27, pp. 618-620, June 1979; and Chen, et al., “An X-band Microwave Life-Detections System,” IEEE Trans. Biomed. Eng., vol. BME-33, pp. 697-701, July 1986).
More recently, radio frequency (RF) technology developed for mobile telephones (i.e., cellphones) has been applied to implement such devices (see, e.g., Droitcour, et al., “A Microwave Radio for Doppler Radar Sensing of Vital Signs,” in IEEE MTT-S Int. Microwave Symp. Dig., 2001, vol. 1, pp. 175-178; Lohman, et al., “A Digital Signal Processor for Doppler Radar Sensing of Vital Signs,” in Proc. IEEE 23rd Annual Engineering in Medicine and Biology Soc. Conf., 2001, vol. 4, pp. 3359-3362; Boric-Lubecke, et al., “10 GHz Doppler Sensing of Respiration and Heart Movement,” in Proc. IEEE 28th Annual Northeast Bioengineering Conf., 2002, pp. 55-56; Droitcour, et al., “Range Correlation Effect on ISM Band I/Q CMOS Radar for Non-contact Vital Signs Sensing,” in IEEE MTT-S Int. Microwave Symp. Dig., 2003, vol. 3, pp. 1945-1948; and Droitcour, et al., “Range correlation and I/Q performance benefits in Single-Chip Silicon Doppler Radars for Noncontact Cardiopulmonary Monitoring,” IEEE Trans. Microw. Theory Tech., vol. 52, pp. 838-848, March 2004).
Mobile telephone RF technology has also been generalized to sensing of multiple subjects (see, e.g., Boric-Lubecke, et al., “Doppler Radar Sensing of Multiple Subjects in Single and Multiple Antenna Systems,” in Proc. 7th Int. Conf. Telecommunications in Modern Satellite, Cable, Broadcasting Services, 2005, vol. 1, pp. 7-11; Smardzija, et al., “Applications of MIMO Techniques to Sensing of Cardiopulmonary Activity,” in Proc. IEEE/ACES Int. Conf. Wireless Communications, Applied Computational Electromagnetics, 2005, pp. 618-621; and Zhou, et al., “Detection of Multiple Heartbeats Using Doppler Radar,” in Proc. IEEE Int. Conf. Acoustics, Speech, Signal Processing (ICASSP), 2006, vol. 2, pp. II-1160-11-1163). A particularly comprehensive discourse on the subject including physiological background can be found in Droitcour, Non - Contact Measurement of Heart and Respiration Rates with a Single - Chip Microwave Doppler Radar , Ph.D. Dissertation, Stanford University, 2006.
Most of the studies to date have been done in the form of laboratory experiments under ideal conditions, so substantial concern exists that the technology can ever be developed into reliable products. Some potential problems that have yet to be addressed include the effects of background scatter, the motion of the subject as well as the background and interference between the respiration and heartbeat signals. Background scatter both from the ambient surroundings as well as from parts of the subject's body exclusive of the relevant chest-wall area (see, e.g., Ramachandran, et al., “Reconstruction of Out-Of-Plane Cardiac Displacement Patterns as Observed on the Chest Wall During Various Phases of ECG by Capacitance Transducer,” IEEE Trans. Biomed. Eng., vol. BME-38, pp. 383-385, April 1991) adds a component to the desired signal that must be dealt with. Gross motion of the subject, as well as other objects in the background will introduce undesired dynamics into the desired signal, making the problem even more difficult. Finally, the problem remains of respiration harmonics falling close to the heartbeat frequency so as to make reliable heart rate estimation difficult. What is needed in the art is a way to overcome these problems. More specifically, what is needed in the art are CP signal processing systems and methods that ameliorate some or all of the above-described disruptive effects and an improved Doppler radar that takes advantage of the systems and methods.
SUMMARY OF THE INVENTION
To address the above-described deficiencies of the prior art, the invention provides a Doppler radar signal processing system. In one embodiment, the system includes: (1) an input configured to receive at least one radar output signal representing a reflected Doppler radar signal, (2) signal processing circuitry coupled to the input and configured to produce an arc-length cardiopulmonary signal from the at least one radar output signal and employ a respiration fundamental frequency estimate to extract a heart rate signal from the arc-length cardiopulmonary signal and (3) an output coupled to the signal processing circuitry and configured to provide the heart rate signal.
Another aspect of the invention provides a method of CP signal processing. In one embodiment, the method includes: (1) receiving at least one radar output signal representing a reflected Doppler radar signal, (2) producing an arc-length cardiopulmonary signal from the at least one radar output signal, (3) employing a respiration fundamental frequency estimate to extract a heart rate signal from the arc-length cardiopulmonary signal and (4) providing the heart rate signal at an output.
Yet another aspect of the invention provides a Doppler radar. In one embodiment, the Doppler radar includes: (1) Doppler radar circuitry configured to transmit a Doppler radar signal, receive and demodulate a reflected Doppler radar signal and produce in-phase and quadrature radar output signals representing the reflected Doppler radar signal, (2) signal processing circuitry coupled to the input and configured to produce an arc-length cardiopulmonary signal from the in-phase and quadrature radar output signals and employ a respiration fundamental frequency estimate to extract a heart rate signal from the arc-length cardiopulmonary signal and (3) an output coupled to the signal processing circuitry and configured to provide the heart rate signal.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a block diagram of one embodiment of a Doppler radar with which a CP signal processing system or method may be contained or carried out;
FIG. 2A is a schematic geometrical diagram showing an example of propagation that may occur with respect to the Doppler radar of FIG. 1 ;
FIG. 2B is a phasor diagram showing received backscatter that the Doppler radar of FIG. 1 may encounter;
FIG. 3 is a geometrical diagram showing zero-mean I and Q data along the CP reflex arc;
FIG. 4 is a geometrical diagram showing quadratic peak interpolation of the power spectrum;
FIG. 5 is a block diagram of one embodiment of a harmonic canceller;
FIG. 6 is a plot showing the effect of normalized perturbation on the refined normalized error for different values of initial normalized error;
FIG. 7A is a plot of 100 samples of a heartbeat component of a test signal at a sampling rate f s =50 Hz over N=1000 samples, with pulse parameters τ=0.05 s and f 0 =1 Hz, a peak-to-peak amplitude A H =0.03 and a heart rate of 82.5 bpm (f H =1.375 Hz);
FIG. 7B is a plot of 400 samples of a respiration component of the test signal of FIG. 7A , with a characteristic exponent p=3, a peak-to-peak amplitude A R =1 and a respiration rate of 15 bpm (f R =0.25 Hz);
FIG. 7C is a plot of all 1000 samples of the combined heartbeat and respiration components of the test signal of FIG. 7A ;
FIG. 8 is a plot of the power spectrum of the test signal of FIG. 7C ;
FIGS. 9A-C are plots representing cancellation of the first L=5 respiration harmonics of the test signal of FIG. 7C , showing the test signal input ( FIG. 9A ), an enhanced heartbeat output ( FIG. 9B ) and an enhanced respiration signal ( FIG. 9C ) obtained by subtracting the output from the input;
FIG. 10 is a plot of the power spectrum of the test signal of FIG. 7C after the respiration harmonic cancellation of FIG. 9B ;
FIGS. 11A-D are plots reflecting a sensitivity of harmonic cancellation to the fundamental frequency estimate, showing from top to bottom, the input test signal of FIG. 6C ( FIG. 11A ) and output signals with −1% error ( FIG. 11B ), 0% error ( FIG. 11C ) and +1% error ( FIG. 11A );
FIGS. 12A-D are plots of the power spectra of the respective signals of FIGS. 11A-D ;
FIG. 13 is a block diagram of an experimental apparatus;
FIGS. 14A-C are plots of a raw I signal ( FIG. 14A ), a raw Q signal ( FIG. 14B ) and a reference signal ( FIG. 14C ) for Experiment 1 under three conditions: subject stationary at 1 m from antenna, remaining still and holding breath;
FIG. 14D is a plot of the arc length signal relating to the I and Q signals of FIGS. 14A and 14B , respectively;
FIG. 14E is a plot of the arc length signal relating to the reference signal of FIG. 14C ;
FIG. 14F is a plot of the power spectrum of the arc length signal of FIG. 14D , also showing the estimated respiration and heart rates (solid vertical lines) as well as the actual heart rate (dashed vertical line, obscured in this case);
FIGS. 15A-C are plots of a raw I signal ( FIG. 15A ), a raw Q signal ( FIG. 15B ) and a reference signal ( FIG. 15C ) for Experiment 2 under three conditions: subject stationary at 1 m from antenna, remaining still and breathing regularly;
FIG. 15D is a plot of the arc length signal relating to the I and Q signals of FIGS. 15A and 15B , respectively;
FIG. 15E is a plot of the arc length signal relating to the reference signal of FIG. 15C ;
FIG. 15F is a plot of the power spectrum of the arc length signal of FIG. 15D , also showing the estimated respiration and heart rates (solid vertical lines) as well as the actual heart rate (dashed vertical line);
FIGS. 16A-C are plots of an input signal ( FIG. 16A ), an enhanced heartbeat output signal ( FIG. 16B ) and an enhanced respiration signal ( FIG. 16C ) showing cancellation of the first L=5 respiration harmonics using the arc length signals of FIGS. 15D and E as an input and the respiration rate estimate of 15.1083 bpm from FIG. 15E ;
FIG. 16D is a plot of the power spectrum of the enhanced heartbeat output signal of FIG. 16B ;
FIGS. 17A-C are plots of a raw I signal ( FIG. 17A ), a raw Q signal ( FIG. 17B ) and a reference signal ( FIG. 17C ) for Experiment 3 under three conditions: subject reciprocating at 1 m from antenna and breathing regularly;
FIG. 17D is a plot of the unwrapped phase arctangent of the I and Q signals of FIGS. 17A and 17B ;
FIG. 17E is a plot of the arc length signal relating to the reference signal of FIG. 17C ;
FIG. 17F is a plot of the power spectrum of the unwrapped phase arctangent of FIG. 17D , also showing the estimated respiration and heart rates (solid vertical lines) as well as the actual heart rate (dashed vertical line);
FIG. 18 is a plot of I and Q components of Experiment 3 employed for absolute distance calibration;
FIGS. 19A-C are plots of a raw I signal ( FIG. 19A ), a raw Q signal ( FIG. 19B ) and a reference signal ( FIG. 19C ) for Experiment 4 over an entire 20-s interval under three conditions: subject slowly walking toward antenna and breathing regularly;
FIGS. 20A-C are plots of 5-s to 12-s windows of the respective raw I, Q and reference signals of FIGS. 19A-C ;
FIG. 20D is a plot of the unwrapped phase arctangent of the I and Q signals of FIGS. 20A and 20B ;
FIG. 20E is a plot of the arc length signal relating to the reference signal of FIG. 20C ;
FIG. 20F is a diagram of the power spectrum of unwrapped phase arctangent of FIG. 20D , also showing the estimated respiration and heart rates (solid vertical lines) as well as the actual heart rate (dashed vertical line);
FIG. 21 is a plot of I and Q components of Experiment 4 employed for absolute distance calibration; and
FIG. 22 is a flow diagram of one embodiment of a method of CP signal processing.
DETAILED DESCRIPTION
I. Introduction
Disclosed herein are various signal processing systems and methods for Doppler radar CP sensing. These systems and methods enable independent recovery of respiration and heartbeat signals from measurements of chest-wall dynamic motion, which may then be employed to generate independent respiration and heart rate estimates. A generic model in the complex plane will be formulated to visualize production of the desired chest-wall displacement signal along with various interfering signals. From this, systems and methods will be derived for arc length demodulation and cardio/pulmonary separation. A test generator is developed to simulate actual signals. Also, an experimental setup is presented and several sets of real data are analyzed using the new signal processing techniques.
Section II, below, develops a physical model of the signal and propagation scenario to set the stage for a description of signal processing systems and methods. Then Section III describes some signal processing systems and method embodiments, including prefiltering and analog-to-digital conversion, raw CP signal extraction and spectral analysis. Section IV introduces a technique for mitigating heartbeat signal interference from the respiratory component. Section V introduces simulation techniques, particularly including a test signal to represent chest-wall motion which may be employed to demonstrate the signal processing systems and methods. Section VI validates and extends the simulation results using experimental data collected with a real RF Doppler radar system using a live subject.
FIG. 1 shows a block diagram of a conventional Doppler radar. A continuous-wave (CW) source 110 feeds an antenna 120 through a circulator 130 . The antenna 120 radiates to a desired object 140 in a field of view (not referenced) that experiences motion x(t). The object 140 reflects the signal back to the same antenna 120 . In an alternative embodiment, the object 140 reflects the signal to another antenna (not shown).
The circulator 130 then captures the reflected Doppler radar signal and directs it to a demodulator 150 . The demodulator 150 uses a portion of the CW source signal to demodulate the reflected Doppler radar signal. In one embodiment, the demodulator 150 produces a single output signal. However, in the illustrated embodiment, the demodulator 150 is an I/Q (complex) demodulator 150 . The I/Q demodulator takes a portion of the CW source signal, splits it into two components with 90° relative phase shifter 151 , and mixes it with the reflected signal in respective mixers 152 , 153 to derive in-phase and quadrature (I/Q) outputs, i(t) and q(t), respectively. In the illustrated embodiment, lowpass filters (LPFs) 154 , 155 are employed to remove images and retain only signals that are changing relatively slowly compared to the CW source signal frequency.
As the scattering object moves, the phase of the return signal varies as
2 π x ( t ) λ 2 , where λ = c f c
is the wavelength of the CW signal, c is the velocity of light, and f c is the CW carrier frequency. (The divisor of 2 on λ is due to the two-way propagation path to and from the scatterer.) Therefore, as the scattering object moves radially, the phase rotates 360° every
λ
2
.
For example, if f c =2.4 GHz, then the wavelength is approximately ⅛ m or 12.5 cm for c=3×10 8 m/s and the phase rotates 360° for every 6.25 cm of motion.
II. Signal Model
FIG. 2A shows a schematic geometrical diagram of the propagation scenario. The desired backscattered signal comes from objects ( 140 of FIG. 1 ) in the field of view, including a subject 140 a . A chest-wall area 140 b of the subject 140 a produces the desired component. Undesired interfering components often arise from other backscattering areas on the subject (e.g., 140 c ), as well as from other background objects in the antenna field of view, e.g., objects 140 d . An antenna with a narrow beam pattern (i.e., a high gain) can significantly reduce interference from background objects 140 d , although the desired subject is restricted to a smaller area, since he should remain in the beam at all times. Also, for many applications, it is probably not feasible to employ the antenna pattern to exclude undesired returns from subject areas outside of the chest wall. Accordingly, for purposes of the present description, two subject backscatter components are defined: CP and non-CP (NCP). All other backscatter is defined as a background (BG) component, including backscatter from walls, ceilings or other objects within the field of view.
Turning to FIG. 2B , the return from each backscattering object within the antenna field of view can be visualized as a vector in a complex plane, where its length is proportional to the reflection coefficient, and its orientation represents the RF phase, which as previously described varies with radial distance. The various CP, NCP, and BG components described and defined above are then added in this vector space as shown in FIG. 2B , where the resultant vector represents the composite return from all scatterers. In this diagram, the BG component is presumed stationary, but the position of the CP and NCP subject components can lie anywhere along the dashed circle loci. As the subject moves, either voluntarily or involuntarily, the NCP component will wander along an arc of its locus. On the other hand, the motion of the desired CP component will be relatively much smaller, since chest-wall movement due to respiration is only a centimeter or so at most and the motion due heartbeat is typically only a fraction of a millimeter (see, e.g., Droitcour, Non-Contact Measurement supra). Therefore, the CP component will only vary over a small arc, which for all practical purposes can be considered as a straight line.
III. Basic Signal Processing
A. Prefiltering and Analog-to-Digital Conversion
In a digital embodiment (which is preferred for many applications), it is necessary to digitize the I/Q analog output signals of the complex demodulator 150 of FIG. 1 . Since the CP component, shown as the small arc in FIG. 2B , is of primary interest, it might at first seem best to AC-couple, or highpass-filter, the analog outputs to the analog-to-digital converters (ADCs), to reduce the dynamic range requirements and number of bits needed for accurate representation. Furthermore, the cutoff frequency of the highpass filter could be made high enough to exclude most of the respiration signal, thereby enhancing the much smaller, and more elusive, heartbeat signal. However, AC coupling has two disadvantages: a long settling time and a loss of possibly useful DC and low-frequency information, as described below.
It is envisaged that CP data for a given subject under given conditions will be acquired over a time frame on the order of 5-30 s for most applications. If AC coupling is employed, some time must be allotted for the filter to settle after the subject is in position and ready to begin the test. The settling time of a highpass filter is roughly the inverse of its cutoff frequency. The respiration rate for a seated subject at rest is typically in the range of 5-20 breaths per minute (bpm), i.e., 0.083-0.33 Hz. Therefore, with a cutoff frequency of 0.03 Hz, the settling time will be on the order of 30 seconds, which is long compared to the envisaged time frames for valid data acquisition. Increasing the cutoff frequency can reduce this settling time, but at the expense of losing some of the low-frequency information, as described next.
It will be shown herein that harmonics of the fundamental respiration frequency can seriously limit heart-rate estimation accuracy. As will be described below in Section IV, various ways of dealing with this interference require an estimate of the respiration rate. Therefore, the highpass cutoff should be set below the lowest expected respiration frequency, thereby increasing the settling time, as described above. Another reason that low-frequency data might be useful is for applications in which the actual respiration waveform might be diagnostically useful.
Another consideration for the prefiltering is the lowpass anti-aliasing filter required. Heart rate for a seated subject at rest is typically in the range of 45-90 beats per minute (bpm), i.e., 0.75-1.5 Hz. Also, within a heartbeat period, fine detail exists that may be of diagnostic value, so that frequencies of 10-100 times the highest heartbeat frequency may be of interest. Therefore, the lowpass cutoff frequency should be on the order of 15-150 Hz, requiring sampling rates in the range 30-300 Hz. Various experiments described below employ sampling rates of 25 Hz and 50 Hz. With activity, such as on a treadmill, heart rate can easily increase to 120 bpm (2 Hz) (An oft-cited rule of thumb for maximum heart rate is 220 minus the subject's age in years.) Some applications may require a somewhat higher sampling rate.
For all of the above reasons, DC coupling to the ADC appears preferable to AC coupling. However, both fall within the scope of the invention. The DC can still be removed after collection by subtracting out the mean over the data block. In steady state, this is equivalent to highpass filtering with a very low cutoff frequency. However, subtracting out the mean after collection avoids the transient settling time problem.
The penalty paid for DC coupling is that the ADC then requires more bits because of the vastly increased dynamic range. However, considering the relatively low sampling rates, the requirements are readily achievable with today's technology. Indeed, commercially available 24-bit ADCs are available at relatively modest cost and small size. Moreover, if the background ( 140 d of FIG. 2A ) is immobile, then the BG component in FIG. 2B is a DC component that can be offset prior to the ADC to reduce some of the dynamic range.
B. Extraction of Raw CP Signal
Ideally, a DC offset should be employed to reference the data to the center of the smaller dashed circle (CP) in FIG. 2B . Then the desired chest-wall displacement signal (shown as x(t) in FIG. 1 ) could be reconstructed by merely taking the arctangent of the complex I/Q data. It is possible and desirable to offset the DC corresponding to the BG return in FIG. 2A , assuming that the constituent scattering objects are not moving. However, it is difficult to avoid the NCP component, which is induced as a result of voluntary or involuntary body movement. Since the NCP component is unpredictable, the focus should be on the small CP arc, which contains the signal of interest.
If the subject is moving at a steady velocity, the sum of the CP and NCP vectors in FIG. 2B rotates about the center of the larger dashed circle, i.e., the head of the presumably static BG vector. As the subject moves in this manner, the CP and NCP components maintain a rough alignment, because the chest wall nominally moves with the rest of the body. However, some angular motion of one exists with respect to the other because of relative local motion and, of course, the actual desired CP motion of the chest wall. As will be shown in the experiments below, the CP signal may not always be able to be extracted reliably in this case. Thus, for the remainder of theoretical description, it will be assumed that the subject is nominally stationary at rest.
If the subject is at rest, the CP component can be extracted by first removing the mean over the data block, as described above, and then combining the I/Q components in such a way as to render the best estimate of chest-wall motion. As previously mentioned, the relatively small motion of the chest wall means that the CP arc can for all practical purposes be considered as a straight line. Therefore the I/Q components of the CP signal are essentially linearly related. Typically, the I/Q signals will be unequal in magnitude, depending on the orientation of this line in the complex plane (see FIG. 2B ). For example, if the resultant phase is oriented mostly toward the right (real), the Q component of the CP signal will be larger than the I component; conversely, the I component will be larger than the Q signal if the resultant phase points mostly upward (imaginary).
In recent work, various means have been employed to extract the CP signal from the I/Q signals for further processing, including selection of the largest, and principal component analysis. Here, employ linear regression may be employed to establish the best mean-square fit of a straight line to the CP arc. This is roughly equivalent to the principal component approach, however, it is somewhat more straightforward to implement.
If the sampled I/Q signals after A/D conversion are denoted as i(n) and q(n),n=1, 2, . . . , N, where N is the block length of the collected data, subtracting the mean value over the data block yields the zero-mean data:
i
~
(
n
)
=
i
(
n
)
-
1
N
∑
n
=
1
N
i
(
n
)
,
and
(
1
a
)
q
~
(
n
)
=
q
(
n
)
-
1
N
∑
n
=
1
N
q
(
n
)
.
(
1
b
)
A nominal linear relationship is assumed to exist between the I/Q components, so:
{tilde over ( q )}( n )= aĩ ( n )+ v ( n ), (2)
where a is the slope and v(n) represents additive noise or interference. FIG. 3 shows a diagram of what a typical data set (x's) might look like relative to the CP arc (solid) and its straight-line tangent (dashed). Linear regression determines the best estimate of the slope in the sense of minimizing the mean-square residual, and is given by:
a
^
=
∑
n
=
1
N
i
~
(
n
)
q
~
(
n
)
∑
n
=
1
N
i
~
2
(
n
)
.
(
3
)
With this slope estimate, the distance along the arc can be calculated as:
s ( n ) = i ~ ( n ) + a ^ q ~ ( n ) a ^ 2 + 1 . ( 4 )
Thus, s(n)=ĩ(n) for the limiting case when â=0, and likewise s(n)={tilde over (q)}(n) when â=∞. For intermediate values, â acts as a weighing factor to combine ĩ(n) and {tilde over (q)}(n) optimally.
Note that although arc length is an appropriate measure of chest-wall motion, its scale is not inherently calibrated since the amplitude of the I/Q signals depends on transmitted power, chest-wall reflection coefficient, antenna and receiver gain and perhaps other factors. Therefore, if an absolute chest-wall displacement measurement is desired, it is necessary to calibrate the system under specified conditions. This can be most conveniently accomplished by having the subject rock back and fourth at a slow rate (e.g., period of 1-5 seconds) over at least a half wavelength (e.g., 6.25 am at 2.4 GHz), so that the I/Q signals trace out a full circle in the complex plane (c.f., FIG. 2B ). Then, the voltage corresponding to the diameter of the circle thus traced out is known to correspond to an absolute arc length of λ/2 over π (1.99 cm at 2.4 GHz). This calibration thus enables absolute measurements of chest-wall displacement due to respiration or heartbeat. An example of this will be given later in the experimental section.
C. Spectral Analysis
Conventional spectrum analysis is useful for estimating heart and respiration rates from the extracted CP signal. In this domain, the fundamental frequency along with associated harmonics appears as peaks in the spectrum, and the location of the fundamental determines an estimate of the rate. The well-known Welch weighted overlapped segment averaging (WOSA) method may be used, whereby a data record of N samples is subdivided into (possibly overlapping) M-sample sub-blocks, which are then weighted for sidelobe control, transformed using an M-point fast Fourier transform (FFT), magnitude-squared, and average. The higher the value of N/M, the more spectra are averaged, reducing the statistical variance of the power spectral density by a factor of approximately √{square root over (N/M)}. From this standpoint, small values of the FFT size M are desirable. However, spectral resolution suffers as M is decreased, so a tradeoff exists between variance and resolution.
Alternatively, the extracted CP signal may be autocorrelated, windowed, and transformed by FFT (Blackman-Tukey method). In this case, windowing the autocorrelation reduces statistical variation of the spectrum at the expense of reduced spectral resolution, just like the tradeoff in WOSA spectrum analysis. The two techniques are roughly equivalent in this respect; no particular theoretical advantage of one over the other exists (see, e.g., Stoica, et al., Introduction to Spectral Analysis , Upper Saddle River, N.J.: Prentice Hall, 1997, ch. 2). However, the Welch method is usually preferred from implementation considerations.
With limited spectral resolution (necessitated by the desire to reduce spectral variation), the actual peak of the spectrum should be interpolated to achieve accurate heart and respiration rates. In one embodiment, a three-point quadratic interpolation is sufficient for this purpose. First the highest spectral value S 2 and corresponding frequency f 2 are identified within an appropriate range of the power spectrum. Then, values f 1 and f 3 are identified as the adjacent frequencies below and above f 2 respectively, along with their associated spectral values S 1 and S 3 . A quadratic function is then fitted to the three points S 1 , S 2 , S 3 , as depicted in FIG. 4 , which yields the estimated peak frequency according to:
f peak = Δ 2 · S 3 - S 1 2 S 2 - S 1 - S 3 + f 2 , ( 5 )
where it is assumed that f 1 , f 2 , f 3 are equally spaced by Δ, i.e.:
Δ= f 3 −f 2 =f 2 −f 1 . (6)
If the actual peak value is desired, that can also be easily determined, and is expressed as:
S
peak
=
S
2
+
(
S
3
-
S
1
)
f
peak
-
f
2
4
Δ
=
(
4
S
2
-
S
1
-
S
3
)
2
-
4
S
1
S
3
8
(
2
S
2
-
S
1
-
S
3
)
.
(
7
)
IV. Enhancement of Heartbeat Signal
It will be demonstrated in the experiments below that periodic chest-wall motion due to respiration typically has many significant harmonics, which can interfere with reliable detection of the much smaller heartbeat signal. A technique will now be presented to enhance the weak heartbeat signal by subtracting out respiration harmonics.
The general signal processing problem in abstract terms is formulated as follows. x(n)=s(n)+v(n) is a real signal composed of a desired signal component s(n) and a periodic component v(n) that is desired to be removed. The fundamental frequency of v(n) is denoted as f 0 , and an amplitude and a phase specify each of the harmonic components. If a single complex number h 1 is used to represent the amplitude and phase of the l th harmonic, the periodic disturbance can be expressed as:
v ( n ) = ℜ ( ∑ l = 1 L h l ⅇ j l ω 0 n ) , ( 8 )
where L is the number of significant harmonics, R denotes the real part, and ω 0 =2πf 0 . The effect of v(n) over the data block of N samples should be minimized. Therefore, the cost function to be minimized is defined to be the mean-square error (MSE):
J = 1 N ∑ n = 1 N [ x ( n ) - v ^ ( n ) - w 0 ] 2 ,
where ( 9 ) v ^ ( n ) = ℜ ( ∑ l = 1 L w l ⅇ j l ω ^ 0 n ) ( 10 )
is an estimate of v(n), parameterized by the complex weights w 1 , l=1, . . . , L and the estimated fundamental (angular) frequency {circumflex over (ω)} 0 , and where a (complex) DC term w 0 is included for completeness. The DC value that minimizes J is given by:
w 0 , min = 1 N ∑ n = 1 N [ x ( n ) - v ^ ( n ) ] . ( 11 )
Therefore, J can be replaced with the modified cost function:
J ~ = 1 N ∑ n = 1 N [ x ~ ( n ) - ( ∑ l = 1 L w l e ~ l ( n ) ) ] 2 ,
where : ( 12 ) x ~ ( n ) = x ( n ) - 1 N ∑ m = 1 N x ( m ) , and ( 13 ) e ~ l ( n ) = ⅇ j l ω ^ 0 n - 1 N ∑ m = 1 N ⅇ j l ω ^ 0 m ( 14 )
are of zero-mean over the data block, so that now only the L coefficients ω 1 , L=1, . . . , L need to be minimized.
FIG. 5 is a block diagram of an embodiment of a harmonic canceller. s(n) and v(n) are summed in a summing junction 505 and the mean removed in a remove mean block 510 . f 0 is received into a harmonic generator 515 , which produces harmonics thereof. The means of the harmonics are removed in a remove mean block 520 . The output of the remove mean blocks 510 , 520 are provided to a minimum MSE weight computation block 525 , which produces weights based thereon. These weights are then applied to the outputs of the remove mean block 520 in various multiplication junctions 530 a , 530 b , 530 n . The resulting weighted outputs are then summed in a summer 535 . A resultant is computed in a block 540 . That resultant is applied to the output of the remove mean block 510 in a summing junction 545 to yield the output y(n).
A mathematical expression for the weights that minimize {tilde over (J)} can now be derived. First, a cross correlation vector r is defined having components:
r l = 1 N ∑ n = 1 N x ~ ( n ) e ~ l * ( n ) , ( 15 )
and the Hermitian and (symmetric) complementary correlation matrices R and C are defined having components:
R lm = 1 N ∑ n = 1 N e ~ l ( n ) e ~ m * ( n ) , and ( 16 ) C lm = 1 N ∑ n = 1 N e ~ l * ( n ) e ~ m * ( n ) . ( 17 )
Using these definitions, the cost function of Equation (12) can be rewritten as:
J ~ = P x ~ + 2 ( r H w ) + 1 2 w H Rw + 1 2 ( w T C * w )
where : ( 18 ) P x ~ = 1 N ∑ n = 1 N x ~ 2 ( n ) ( 19 )
is the input power, w=[w 1 w 2 . . . w L ] T , and the superscripts T and H denote, respectively, the transpose and the (Hermitian) complex conjugate transpose.
The cost function {tilde over (J)} is minimized by differentiating Equation (18) with respect to w* and equating to zero, giving:
ⅆ J ~ ⅆ w * = - r + 1 2 Rw + 1 2 Cw * = 0. ( 20 )
In minimizing such quadratic forms, w and w* can be considered as independent variables; see, e.g., Brandwood, “A Complex Gradient Operator and Its Application in Adaptive Array Theory,” IEEE Proc, Pts. F and H, vol. 130, pp. 11-16, February 1983). Premultiplying the conjugate of Equation (20) by CR − * gives:
CR - * ( ⅆ J ~ ⅆ w * ) * = - CR - * r * + 1 2 Cw * + 1 2 CR - * C * w = 0. ( 21 )
Subtracting Equation (21) from Equation (20) and solving for w then gives the optimal weight:
w min =2( R−CR − *C *) −1 ( r−CR − *r *). (22)
The Orthogonality Principle dictates that the error inside the brackets of Equation (12) is orthogonal to each {tilde over (e)} 1 (n) and {tilde over (e)} 1 *(n), l=1, 2, . . . , L, hence, the minimum cost function is:
J
~
min
=
1
N
∑
n
=
1
N
[
x
~
(
n
)
-
(
∑
l
=
1
L
ω
l
,
min
e
~
l
(
n
)
)
]
x
~
(
n
)
=
P
x
~
-
(
r
H
w
min
)
.
(
23
)
As the block size N becomes very large, R→I, the identity matrix, and C→0, the latter because the average value of a sinusoid tends to zero over a long interval. Also, in this case, Equations (15) and (8) show that
r → h 2 ,
where h=[h 1 h 2 . . . h L ] T , assuming that s(n) has no harmonic components in common with those of the disturbance v(n). Hence, from Equation (22), w min →h, which is the desired solution. Thus, when N is very large, C can be neglected. However, for short, and even moderate-size, data blocks, C is not negligible and must be included to achieve accurate harmonic cancellation.
What remains is estimating the fundamental frequency f 0 . For the heartbeat enhancement application, the fundamental frequency of the respiration should be estimated. The fundamental frequency of the respiration may be estimated in the same way that the heart rate was estimated above, i.e., spectrum analysis with three-point quadratic interpolation. However, in some cases three-point quadratic interpolation may not be accurate enough, since respiration occurs at a lower frequency, and also because more accuracy is required for the higher harmonic frequencies to achieve good cancellation. In this case, a second step may be taken to refine the estimate, whereby the residual signal power variation is observed as the initial estimate is slightly perturbed.
Consider a single discrete-time sinusoid cos ωn of an (imprecisely known) normalized frequency
f = ω 2 π ,
and suppose that this tone may be canceled by subtracting another scaled and phase-shifted sinusoid of normalized frequency
f ^ = ω ^ 2 π
(which is an estimate of f). This may be handled as a special case of Equations (12) through (14) for L=1, in which case the MSE cost function is:
J ~ 1 = 1 N ∑ n = 0 N = 1 { x ~ ( n ) - [ w e ~ ( n ) ] } 2 ,
where : ( 24 ) x ~ ( n ) = cos ω n - 1 N ∑ m = 0 N - 1 cos ω m = cos ω n - 1 N ( 1 - ⅇ jω N 1 - ⅇ jω ) , ( 25 )
w is a single complex weight,
e ~ ( n ) ≡ ⅇ j ω ^ n - 1 N ∑ m = 0 N - 1 ⅇ j ω ^ m = ⅇ j ω ^ n - 1 N · 1 - ⅇ j ω ^ N 1 - ⅇ j ω ^ ( 26 )
and where, for mathematical convenience in this analysis, the N-sample data block is indexed from 0 to N−1. Similarly, as special cases of Equations (23), (19), (22), (15), (16) and (17):
J ~ 1 , min = P x ~ - ( r * w min ) .
where : ( 27 ) P x ~ = 1 N ∑ n = 0 N - 1 x ~ 2 ( n ) = 1 N ∑ n = 0 N - 1 [ cos ω n - 1 N ( 1 - ⅇ jω N 1 - ⅇ jω ) ] cos ω n = 1 2 [ 1 + 1 N ( 1 - ⅇ j2ω N 1 - ⅇ j 2 ω ) ] - 1 N 2 [ ( 1 - ⅇ jω N 1 - ⅇ jω ) ] 2 ( 28 )
in which the zero-mean property of {tilde over (x)}(n) and the identity
cos 2 ω n = 1 + cos 2 ω n 2
have been employed, and:
w min = 2 R - C 2 R ( r - C R r * ) ,
with ( 29 ) r = 1 N ∑ n = 0 N - 1 x ~ ( n ) e ~ * ( n ) = 1 N ∑ n = 0 N - 1 [ cos ω n - 1 N ( 1 - ⅇ jω N 1 - ⅇ jω ) ] ⅇ - j ω ^ n = 1 2 N [ 1 - ⅇ - j ( ω ^ + ω ) N 1 - ⅇ - j ( ω ^ + ω ) + 1 - ⅇ - j ( ω ^ - ω ) N 1 - ⅇ - j ( ω ^ - ω ) ] - 1 N 2 ( 1 - ⅇ jω N 1 - ⅇ jω ) 1 - ⅇ - j ω ^ N 1 - ⅇ - j ω ^ ( 30 )
in which the zero-mean property of {tilde over (x)}(n) has again been employed and the exponential of cos ωn,
R = 1 N ∑ n = 0 N - 1 e ~ ( n ) 2 = 1 - 1 N 2 1 - ⅇ j ω ^ N 1 - ⅇ j ω ^ 2 ( 31 )
in which the zero-mean property of {tilde over (e)}(n) has been employed, and
C
=
1
N
∑
n
=
0
N
-
1
[
e
~
*
(
n
)
]
2
=
1
N
·
1
-
ⅇ
-
j2
ω
^
N
1
-
ⅇ
-
j2
ω
^
-
1
N
2
(
1
-
ⅇ
-
j
ω
^
N
1
-
ⅇ
-
j
ω
^
)
2
.
(
32
)
For large N, R→1, C→0, and w min →2r, where, from Equation (30):
r → 1 2 N [ 1 - ⅇ - j ( ω ^ + ω ) N 1 - ⅇ - j ( ω ^ + ω ) + 1 - ⅇ - j ( ω ^ - ω ) N 1 - ⅇ - j ( ω ^ - ω ) ] , ( 33 )
and from Equation (28),
P x ~ → 1 2 .
In addition, when |{tilde over (f)}−f| is small, the first term of Equation (33) can be neglected. Therefore, from Equation (27), the normalized MSE is approximated as:
1
,
min
P
x
~
≈
1
-
sin
(
ω
^
-
ω
)
N
2
(
ω
^
-
ω
)
N
2
2
,
N
⪢
1
and
f
⋒
-
f
N
⪡
1
(
34
)
ω
^
→
ω
→
N
2
-
1
12
(
ω
^
-
ω
)
2
.
(
35
)
Thus, when the frequency estimate is close to its optimal value, the selectivity of the harmonic canceller MSE varies as the square of the frequency error. This means that three-point quadratic interpolation can be applied with substantial accuracy to refine the initial estimate {tilde over (ω)}. Accordingly, {tilde over (ω)} is perturbed slightly as {tilde over (ω)}±Δ to yield three measurements of the MSE, which are then interpolated to yield the refined estimate. If J 1 , J 2 , J 3 denote the MSE at frequencies {tilde over (ω)}−Δ, {tilde over (ω)}, {tilde over (ω)}+Δ, respectively, fitting a quadratic to this data to find the minimum yields the refined estimate:
ω
^
^
=
Δ
2
·
J
3
-
J
1
2
J
2
-
J
1
-
J
3
+
ω
^
.
(
36
)
In the above process, the question naturally arises as to just how large the perturbation Δ may be to obtain the best accuracy of the refined estimate. If Δ is too small, the minimum for accurate interpolation may not be approached. On the other hand, if Δ is too large, the MSE may no longer be well-characterized as quadratic. To give some idea on the choice of Δ, N is assumed to be large enough, and |f−{circumflex over (f)}|N is assumed to be small enough so that Equation (34) is a good approximation to the MSE. FIG. 6 , which was calculated from Equation (36) using the simplified model of Equation (34), shows how the refined normalized error (f−{circumflex over ({circumflex over (f)})N depends on the initial normalized error (f−{circumflex over (f)})N and the normalized perturbation ΔN. Naturally, as {circumflex over (f)} becomes close to f, {circumflex over ({circumflex over (f)} also becomes close to f over a very large range of Δ. However, as {circumflex over (f)} becomes further away from f, the range of “good” values of Δ becomes smaller.
As an example, suppose that the actual frequency of the tone to be cancelled is 0.25 Hz over T=20 s with a 50 Hz sampling rate, so that the normalized frequency is
0.25 50 = 0.005
and N=50·20=1000 is the number of samples. For a 2% error in the initial estimate, (f−{circumflex over (f)})N=0.02·0.005·1000=0.1, which is small enough to allow Equation (34) to apply. FIG. 6 shows that ΔN≈0.3 is optimal. This means that an optimal normalized frequency perturbation lies at ±Δ=±0.0003, or ±6%, for realizing the best refined estimate.
The analysis may now be extended to the case where the tone to be cancelled is slowly varying in a random way, thus forming a nonstationary process. Suppose that the frequency variation is Gaussian with probability density:
f ( ω ) = 1 2 π σ exp [ - ( ω - ω _ ) 2 2 σ 2 ] , ( 37 )
where ω is the mean frequency and σ is the standard deviation. Using the approximation of Equation (35) with Equation (37), the expected value of the MSE is calculated as:
E J ~ 1 , min ≈ N 2 - 1 12 ∫ ( ω - ω ^ ) 2 f ( ω ) ⅆ ω = N 2 - 1 12 [ σ 2 + ( ω _ - ω ^ ) 2 ] . ( 38 )
Therefore, the expected MSE is still quadratic as it was in Equation (35), the only difference being a shift due to the additional term σ 2 . Note that Equation (38) is consistent with Equation (35) as σ→0.
If ω remains substantially constant over the interval T, Equation (38) can be interpreted in an ensemble sense, i.e., the result one that would be obtained were many realizations averaged. On the other hand, if ω varies considerably over T, yet not too fast, Equation (38) reasonably describes the MSE over a single realization.
Finally, the case where a harmonic complex with a fundamental frequency ω should be canceled is considered, viz.:
∑ l = 1 L 2 P l cos ( l ω n + ϕ l ) , ( 39 )
where P 1 and φ, l=1, 2, . . . , L, are, respectively, arbitrary powers and phases of the fundamental and its L−1 harmonics. If N is large enough to encompass many cycles of the fundamental, all of the harmonics will be virtually uncorrelated over the interval and the total minimum MSE can be approximated as the sum of the individual MSEs, giving:
J
~
L
,
min
≈
N
2
-
1
12
∑
l
=
1
L
P
l
(
l
ω
-
l
ω
^
)
2
=
N
2
-
1
12
(
ω
-
ω
^
)
2
∑
l
=
1
L
l
2
P
l
.
(
40
)
Thus, for cancellation of multiple harmonics, the MSE will still be proportional to the square of the difference between the fundamental frequency and its initial estimate. And, of course, for L=1 and P 1 =1, Equation (40) reduces to Equation (35) as it should.
To summarize the above, when the frequency estimate is close to the true value, the selectivity of the canceller output MSE varies as the square of the frequency error. Therefore, the three-point quadratic interpolation process can be applied with great accuracy to the total MSE in order to refine the estimate of the fundamental respiration frequency.
V. Simulation
A test signal that represents chest-wall motion due to both heartbeat and respiration will now be developed and employed to demonstrate the above-described signal processing techniques. Section VI will then validate and extend the simulation results using experimental data collected with a real RF Doppler radar system using a live, human subject.
A. Test Signal
The test signal represents chest-wall motion at discrete times
t = n f s , n = 1 , 2 , … , N ,
where f s is the sampling frequency, and is denoted:
x ( n )= x H ( n )+ x R ( n ), (41)
where x H (n) and x R (n) are, respectively, the heartbeat and respiration signal components.
For the heartbeat signal component, a characteristic analog pulse shape p H (t) that periodically repeats every
1 f H
s is assumed, where f H is the heartbeat frequency in Hz (heart rate of 60 f H in bpm). The analog pulse shape described herein is an exponential
ⅇ - t τ ,
with time constant τ, filtered by a second-order Butterworth (critically-damped) filter with cutoff frequency f 0 . Motivating this model is the realization that the emptying of the heart ventricles that occurs during the systolic phase likely imparts a short impulsive motion that is subsequently filtered by the bone and tissue before being sensed on the chest wall.
The Laplace transforms of the exponential and Butterworth filter impulse response are expressed as, respectively:
L { ⅇ - t τ } = 1 s + 1 τ .
and ( 42 ) L { 2 ω 0 ⅇ - ω 0 t 2 sin ω 0 t 2 } = 1 s 2 + 2 ω 0 s + ω 0 2 , ( 43 )
where ω 0 =2πf 0 . Thus, the Laplace transform of the pulse shape is taken as the product of Equations (42) and (43), which can be expressed using a partial fraction expansion as:
1 s + 1 τ · 1 s 2 + 2 ω 0 s + ω 0 2 = 1 C ( 1 s + 1 τ + - s + 1 τ - 2 ω 0 s 2 + 2 ω 0 s + ω 0 2 ) ,
where : ( 44 ) C = 1 τ 2 + 2 ω 0 τ + ω 0 2 ( 45 )
is an unimportant constant that will be subsequently neglected. The inverse Laplace transform of the first term in parentheses above can be immediately identified from Equation (42), while the inverse Laplace transform of the second term can be determined from Equation (43) and by differentiating the impulse response on the left side of Equation (43), yielding:
L { ⅇ - ω 0 t 2 ( cos ω 0 t 2 - sin ω 0 t 2 ) } = s s 2 + 2 ω 0 s + ω 0 2 , ( 46 )
With some algebra, the normalized pulse shape is determined as:
p
H
(
t
)
=
L
-
1
{
1
s
+
1
τ
+
-
s
+
1
τ
-
2
ω
0
s
2
+
2
ω
0
s
+
ω
0
2
}
=
ⅇ
-
t
τ
+
[
(
2
ω
0
τ
-
1
)
sin
ω
0
t
2
-
cos
ω
0
t
2
]
ⅇ
-
ω
0
t
2
.
(
47
)
Finally, p H periodically repeats at intervals of
1 f H
and sampled at f s to obtain the discrete-time heartbeat signal component:
x H ( n ) = p H ( n f s - ⌊ n f s f H ⌋ · 1 f H ) , ( 48 )
where └x┘ (the “floor”) is defined as the greatest integer less than or equal to x. Thus, samples
p H ( n f s )
are sequentially taken until
n f s
reaches the heart-rate period
1 f H ,
at which point the next pulse is started, and so on. The resulting signal component is then scaled to the peak-to-peak value A H .
In a similar way, a prototype respiration pulse may be defined as:
p R ( t ) = sin p π f R t , 0 ≤ t ≤ 1 f R , ( 49 )
which is a half-cycle of a sinusoid raised to the p th power. The motivation for this comes from the examination of real data, where the respiratory chest-wall motion is similar to a sinusoidal half-cycle with a rounded cusp. The exponent p controls the rounding of the cusp as well as the general shape. p R (t) is regularly repeated at intervals of
1 f R
and sampled to obtain the discrete-time respiration signal component:
x R ( n ) = p R ( n f s - ⌊ n f s f R ⌋ · 1 f R ) , ( 50 )
which is then scaled to peak-to-peak value A R .
FIGS. 7A-C show the components of the test signal for parameter values that simulate a typical real signal from a live subject. A total of N=1000 samples (20 s) are generated at a sampling rate f s =50 Hz. The heartbeat component is of peak-to-peak amplitude A H =0.03 (3%) relative to the respiration peak-to-peak amplitude A R =1. The heart rate is 82.5 bpm (f H =1.375 Hz), and the respiration rate is 15 bpm (f R =0.25 Hz). The other waveform parameters were selected to best match typical data. FIG. 7A shows the heartbeat component (100 samples displayed) with pulse parameters τ=0.05 s and f 0 =1 Hz, where the repeated Butterworth-like pulse shapes are readily apparent. FIG. 7B shows the respiration component (400 samples displayed) for p=3 and exhibits the prototypical half cycle pulse with rounded cusps. Finally, FIG. 7C shows the combined signal (all 1000 samples).
B. Spectral Analysis
FIG. 8 shows the power spectrum of the simulated test signal of FIG. 7C . The respiration fundamental is apparent at 0.25 Hz (15 bpm), and the heartbeat signal is apparent at 1.375 Hz (82.5 bpm), with relative amplitudes about 30 dB apart. Also seen are at least ten harmonics of the respiration and the second and third harmonics of the heartbeat.
In the illustrated embodiment, the estimated respiration frequency is calculated by first finding the largest spectral value in the frequency range of 0.1-1 Hz (6-60 bpm) and then using the three-point peak interpolation of Equation (5). The result of this calculation is an estimated respiration rate of 14.8296 bpm (0.2472 Hz), which is plotted in FIG. 8 as a solid vertical line. This estimate is within about 1% of the actual respiration rate of 15 bpm (0.25 Hz).
The estimated heartbeat frequency can be calculated in a similar manner, in this case by first finding the largest spectral value in the frequency range of 0.75-5 Hz (45-300 bpm) and again using Equation (5), giving an estimated heart rate of 82.2949 bpm (1.3716 Hz), which is plotted in FIG. 8 as a solid vertical line. This estimate is within 0.25% of the actual heart rate of 82.5 bpm (1.375 Hz), being even more accurate than the respiration rate estimate because the higher frequency is more resolvable for a fixed FFT size.
In general, the success of heart-rate estimation depends on the particular rates and amplitudes of the heartbeat and respiration components, as well as the frequency range over which one searches. In some cases, respiration harmonics can easily exceed the heartbeat component, thereby giving rise to false heart-rate estimates. In addition, for the example of FIG. 8 , the heartbeat spectral peak just happens to fall between two respiration harmonics. If one of the respiration harmonics is close to the heart rate, signal cancellation may actually occur, which is even more problematic. One remedy to this problem will now be described.
C. Harmonic Cancellation
Here, the harmonic cancellation technique of Section IV is demonstrated. FIGS. 9A-C show the result of canceling the first L=5 respiration harmonics of the test signal of FIG. 7C , showing the input ( FIG. 9A ), enhanced heartbeat output ( FIG. 9B ), and also the enhanced respiration signal ( FIG. 9C ) obtained by subtracting the output from the input.
FIG. 10 shows the power spectrum of the enhanced heartbeat signal. Comparing this with FIG. 8 shows that the first five respiration harmonics have been substantially reduced, enabling much more reliable estimation of the heart rate. Some judgment may be needed in selecting the number of harmonics, L, to be cancelled. Certainly, L should be large enough to reduce the significant respiration harmonics below the heart rate to eliminate this interference. But if L is too large, what starts out as small respiration harmonics above the heart rate will actually increase somewhat because of leakage from the heartbeat spectral component. The value L=5 was selected here after some trial and error, but the choice is not critical.
In the above harmonic cancellation, the respiration rate is known exactly because it is specified for the test signal. As a result, the cancellation of the respiration harmonics is perfect. However, in a real setting, the respiration rate should first be estimated and then employed instead. As described above, and making a transposition from relative frequency to actual frequency, the relative MSE is given by:
[ π ( f R - f ^ R ) T ] 2 3 , ( 51 )
where T is the processing interval and f R and {circumflex over (f)} R are, respectively, the actual and estimated respiration frequencies. Therefore, in the above example for f R =0.25 Hz and T=20 s, one would expect that for a 1% respiration rate error, the relative residual harmonic level would be about
( π · 0.01 · 0.25 · 20 ) 2 3 = 0.0082
(−20.8 dB), and would increase by 6 dB for every frequency error doubling above 1%.
FIGS. 11A-D show how the harmonic canceller output varies with the estimated respiration frequency. FIG. 11A shows the same test signal described above, FIGS. 11B-D respectively show the output signal for −1%, 0% and +1% error (14.85, 15, 15.15 bpm) in the fundamental frequency estimate.
FIGS. 12A-D show the associated power spectra of the respective signals of FIGS. 11A-D . As can be seen, a 1% error in the estimated respiration frequency causes the fundamental suppression to rise to about the −30 dB level relative to the uncanceled fundamental. Actually, the power spectral density somewhat exaggerates the suppression in this case because the output signal is highly nonstationary and the default (Hann) window reduces the signal at its highest point. A measurement of the unwindowed MSE reduction shows about −20 dB, which closely agrees with the −20.8 dB level calculated above.
In FIG. 8 , the estimated respiration rate was 14.8296 bpm, as determined from the power spectrum using three-point quadratic peak interpolation. This is close to the 1% error level examined above, so similar effects are expected. The estimate refinement technique described above was applied in this case, using a ±6% perturbation (consistent with an expected error level of 2%), and resulted in a refined estimate of 15.0211 bpm, which is close to the actual 15 bpm rate.
Thus, it is apparent that the harmonic canceller is effective in removing the respiration component of the test signal, provided that its fundamental frequency can be sufficiently well estimated. The performance with actual measured signals will now be described.
VI. EXPERIMENTAL RESULTS
A. Equipment Description and Setup
FIG. 13 shows a block diagram of the experimental apparatus. The Doppler radar setup is configured by employing a Doppler transceiver printed circuit board (PCB) 1310 having balanced I and Q output signal ports 1311 , 1312 . The I and Q signals are each processed in a separate chain. The following description details the I chain, which is identical to the Q chain.
The balanced I signal from PCB (IN and IP) is fed into the balanced A and B input ports of a first preamplifier (preamp)/filter 1321 , e.g., one commercially available from Stanford Research Systems of Sunnyvale, Calif., as part no. SR560. The first preamp/filter 1321 not only provides amplification and filtering, but also converts the balanced input signal to a single-ended 50-ohm output (a 600-ohm output is also provided, but not used). The output of the first preamp/filter 1321 is then connected to the balanced A input of a second preamp/filter 1322 . The other balanced input (B) is connected to a DC power supply 1323 that is employed to correct the DC offset of the I signal. The single-ended 50-ohm output of the second preamp/filter 1322 is then connected to one of the input ports of an oscilloscope 1330 , which may be an Infinium oscilloscope commercially available from the Hewlett-Packard Company of Palo Alto, Calif. An output of the oscilloscope 1330 is connected to a personal computer (PC) 1350 running mathematical analysis software, e.g., Matlab, which is commercially available from The MathWorks of Natick, Mass.
As mentioned previously, the Q chain is the same (containing a first preamp/filter 1324 , a second preamp/filter 1325 and a DC power supply 1326 ) and is terminated into another one of the input ports of the oscilloscope 1330 . Another input to the oscilloscope 1330 comes from a piezoelectric finger pulse transducer 1340 (e.g., a Model 1010 piezoelectric pulse plethysmograph commercially available from UFI of Morro Bay, Calif.), which may be employed as a reference in the experiments described below. The input ports of the oscilloscope 1330 are all set to 50-ohms.
Lastly, the antenna 120 (e.g., an ARC A-1123-02, 19 dBi antenna, commercially available from ARC Wireless Solutions, Inc., of Wheat Ridge, Colo.) is hooked up via a 50-ohm cable to the antenna port of the PCB 1310 . The antenna 120 is placed approximately at chest level on the edge of a bench pointing directly at the subject.
B. Methodology
For all experiments, the first- and second-stage preamp/filters 1321 , 1322 , 1324 , 1325 were set at LP (lowpass), DC coupling, 12 dB/octave, and 10 Hz cutoff frequency. In addition, the first preamp/filters 1321 , 1324 were set to the low-noise mode (for least contamination of low-level inputs) and the second preamp/filters 1322 , 1325 to high-dynamic-reserve mode (to best accommodate high-level transients without saturating). The Table, below, shows the other equipment settings that were employed in the experiments.
TABLE
Equipment Settings for Experimental System
Settings
Experiments 1 & 2
Experiment 3
Experiment 4
SR560 gain
1st Stage
5
5
5
2nd Stage
10
5
5
Overall
50
25
25
DC Offset
I
3.09
V
−0.98
V
−0.98
V
Q
1.39
V
−2.57
V
−2.57
V
HP Infinium
I/Q
200
mV/div
500
mV/div
1
V/div
R
100
mV/div
100
mV/div
100
mV/div
T
2
s/div
2
s/div
2
s/div
Once everything is configured, the following initialization may then be performed. Without a subject in front of the antenna 120 , both the I and Q offset power supplies may be varied one at a time until the oscilloscope 1330 reads a steady 0 V on each trace. This stop is done mainly to keep the varying signals within the viewing scale chosen, so as not to saturate the captured signals.
Following the initialization, the subject is introduced into the antenna 120 field of view. For most of the static experiments, the subject is seated on a chair at a 1-m distance from the antenna 120 . For the dynamic experiments, the subject distance varies from about 1 m to 4 m.
The oscilloscope 1330 is set on a long sweep (typically 20 s) and when the trace is complete, the oscilloscope 1330 is set to stop. The captured signals are then one-by-one exported as .csv files, which are in turn converted to a single formatted ASCII test file (four columns [t i q r] that the Matlab routines can read.
C. Experiment 1
Subject Stationary at 1 m from Antenna, Remaining Still and Holding Breath
In the first experiment, the subject is seated at a distance of 1 m from the antenna and holds his breath so that no interference from respiration occurs. FIGS. 14A-C show plots of the raw I and Q signals ( FIGS. 14A and B), along with the reference pulse signal ( FIG. 14C ). The heartbeat signal is apparent, which is strongly correlated with the reference signal. FIG. 14D shows the arc-length signal calculated from Equation (4), which optimally combines the I and Q signals.
The spectrum of the arc-length signal is plotted in FIG. 14F , which also displays the estimated respiration and heart rates (solid vertical lines), as well as the actual heart rate (dashed vertical line) from the reference signal. (In this case, the estimated respiration rate is probably spurious since the subject is purposely holding his breath. Also, the dashed line is obscured in this case since the estimated heart rate is so close to the actual heart rate.) The numerical value of the estimated respiration (spurious in this case) and heart rates, along with the actual heart rate are displayed in FIG. 14F . The estimated heart rate is 90.9324 bpm, which is virtually identical to the actual displayed heart rate of 91.0008 bpm. These results are typical under idealized conditions, so near-perfect heart-rate estimates may be obtained. Experiment 2 is then undertaken to assess the effects of respiration when the subject is breathing normally.
Experiment 2
Subject Stationary at 1 m from Antenna, Remaining Still and Breathing Regularly
In Experiment 2, the same subject is seated in the same position, but is now breathing in a regular manner. FIGS. 15A-F display the same information as FIGS. 14A-F for Experiment 1. Comparing the two, FIG. 15A-C show that the respiration component is now dominant and the heartbeat component is difficult to see. The respiration rate is roughly 5 cycles over 20 s, or 15 bpm. Comparing FIG. 15D with FIG. 14D shows that the peak-to-peak heartbeat component in the former is roughly 0.015 V as compared to a peak-to-peak respiration component of about 0.3 V in the latter, i.e., a ratio of 1:20 or 26 dB. FIG. 15C can also be compared to the test signal of FIG. 7C , showing much similarity.
As compared to FIG. 14F , the power spectrum of FIG. 15F is now cluttered with many respiration harmonics, making it difficult to decide which peak corresponds to the heartbeat component. Indeed, the heart-rate estimation algorithm (see description in Section V-B) fails in this case, as the estimated heart rate is captured by the fourth harmonic of the respiration. However, the respiration rate estimate of 15.1083 bpm (0.2518 Hz) seems to be in line with the observed period in FIG. 15F , and this will be employed next to apply the harmonic cancellation technique.
Following the same procedure set forth in Section V-C above, the harmonic cancellation technique of Section IV is applied to the above data. Using the estimation respiration rate of 15.1083 bpm that appears FIG. 15F and canceling the first five harmonics, FIGS. 16A-C show that most of the respiration component has been successfully removed. Moreover, the 83.5317 bmp estimated heart rate displayed in FIG. 16D is now within 1% of the true 82.8988 bpm rate shown in FIG. 15F . (The estimated respiration rate is irrelevant in this case because the respiration component has been canceled.)
A refined respiration rate estimate was calculated as 15.2261 bpm by applying the technique of Section IV using a ±6% perturbation (consistent with an expected error level of 2%), which is within 1% of the initial estimate of 15.1083 bpm, and hence is good for about 20 dB of cancellation, according to theory of Section IV and described in Section V-C. Therefore, in this particular example, refinement is not necessary, since the initial estimate is close enough.
E. Experiment 3
Subject Reciprocating at 1 m from Antenna and Breathing Regularly
Experiment 3 introduces movement for the first time. Now the same subject is standing 1 m in front of the antenna, and slowly takes one step forward, one step back, one step back, and one step forward, with the same foot moving in both directions, the other foot immobile, and a slight pause after each move. The subject repeats this four-move reciprocating cycle about 3½ times over the 20 s data collection period. The I/Q and reference data are plotted in FIG. 17A-C . In comparison with the still data of Experiments 1 and 2 shown in FIGS. 14A-C and 15 A-C, large sinusoidal variations corresponding to the motion over many λ/2 (6.25 cm at 2.4 GHz) Doppler cycles are apparent. For this example, about nine cycles exist from trough to peak and from peak to trough, corresponding to a peak-to-peak motion of 9×6.25 cm≈0.56 m. Thus, considering the nominal 1 m distance to the antenna, the range varies from about 0.72 m to 1.28 m, i.e., a max/min ratio of about 1.8.
In this case, the arc-length transformation is not appropriate due to the large-scale motion, so this data should be examined from a different perspective. FIG. 17D plots the unwrapped phase in terms of Doppler cycles. This is in agreement with the previous observation that the peak-to-peak motion consists of about nine cycles, i.e., approximately 0.56 m.
The arc-length power spectrum, employed in FIGS. 14F and 15F would also not be appropriate here because of the large-scale motion. Instead, FIG. 17F plots the power spectrum of the unwrapped phase arctangent. In this case, the estimated respiration rate of 9.82236 bpm (0.1637 Hz) that appears is clearly in error because its period of
1 0.1637 = 6.1085
s is instead identified as the period of the reciprocating motion in FIG. 17D . Likewise, the estimated heart rate of 49.9788 bpm (0.8330 Hz) is erroneous, having been captured as the fifth harmonic of the periodic motion. By coincidence the “true” heart rate is also in error here because of some problems with extraneous noise pickup in the reference channel. However, the reference time waveform in FIG. 17D indicates that the true heart rate is about 90 bpm (1.5 Hz) in this case, which cannot be reliably detected in FIG. 17F .
Experiment 3 also enables absolute motion calibration of the system. FIG. 18 plots the relationship between the I and Q components. (The skewed line in FIG. 18 is a linear regression fit, which is only relevant over small arcs and so is not useful here.) It is apparent that the data rotates one cycle for each λ/2 (6.25 cm) of motion, and also the amplitude peaks and ebbs as the subject is closer to and then further away from the antenna. The diameter of the circles traced out varies between about 0.6 V and 3 V, i.e., a voltage ratio of about 5:1. In the far field, the voltage would be expected to be inversely proportional to range, which would imply a range ratio of about 5. However, this is significantly higher than the 1.8 ratio calculated above by counting cycles. The disparity may be due to antenna near-field effects, since at times the subject may be closer than 1 m from the antenna, or random scattering effects as the subject's aspect angle changes slightly during forward and backward motion.
In any case, the observed voltage may be employed to calibrate the system by associating the harmonic mean diameter of
1 ( 1 0.6 + 1 3 ) = 0.5
V with the nominal 1 m range. (Note that absolute phase cannot be employed for calibration in the non-moving scenario because small arcs have no easily obtainable absolute reference point—see FIG. 2 .) Therefore, according to the description in Section III-B, 0.5 V would correspond to an arc length of λ/2 over π, which equals 1.99 cm at 2.4 GHz, i.e., about 4 cm/V. The Table shows that the overall gain for Experiments 1 and 2 was twice the gain for Experiment 3, so for Experiments 1 and 2, the calibration would be 2 cm/V. Accordingly, the 0.015 V peak-to-peak heartbeat signal previously estimated from FIG. 14D corresponds to 2×0.015=0.03 cm, or 0.3 mm peak-to-peak chest-wall motion, which is within the range of expected values. Likewise, the 0.3 V peak-to-peak respiration signal previously estimated from FIG. 15D corresponds to 2×0.3=0.6 cm=6 mm peak-to-peak chest-wall motion, which is again within range of expected values.
Experiment 4
Subject Slowly Walking Toward Antenna and Breathing Regularly
Experiment 4 demonstrates the performance when the same subject is slowly walking towards the antenna, starting at a distance of about 5 m and ending at about 1 m (“longwalk”). FIGS. 19A-C shows the raw I/Q data, in which the amplitude of the Doppler cycles slowly builds up until the subject reaches the 1 m distance at about 12 s. The segment from about 10 s to 12 s roughly corresponds to similar 2 s segments in FIG. 17A-C . Since the subject covers the entire 4 m distance in about 12 s, the average velocity of the subject is about
4
12
=
1
3
m
/
s
.
Over the first 5 s, the signal is too weak to get reliable phase measurements. Accordingly, the data is windowed from 5 s to 12 s. FIGS. 20A-C show the resulting raw I/Q data and the reference signal over this 7 s interval, in which the amplitude of the Doppler cycles slowly builds up until the subject reaches the 1 m distance.
FIG. 20D plots the phase. Here, due to the apparent baseline drift in FIG. 20A-C from about 2 s to 3 s, some Doppler cycles are missing, which results in a flat spot in the phase plot. Over the last two seconds, the subject is slowing down as the 1 m distance is reached. Fitting a straight line to the interval from 3 s to 5 s shows about eight Doppler cycles, i.e., 8×6.25 cm=50 cm, over 2 s for a velocity of 0.25 m/s, being roughly consistent with the previously estimated overall velocity of ⅓ m/s.
The unwrapped phase arctangent spectrum is displayed in FIG. 20F . Here again, as with the data in FIG. 17F , it is difficult to extract any kind of reliable estimate of either respiration rate or heart rate. In these cases, the dynamics of motion seem to overwhelm the small variations that respiration rate or heart rate cause. For completeness, FIG. 21 also plots I/Q data, where the spiral pattern that was evident in FIG. 18 is seen again.
FIG. 22 is a flow diagram of one embodiment of a method of CP signal processing. The method begins in a start step 2210 by calibrating a Doppler radar. In a step 2220 , at least one radar output signal that represents a reflected Doppler radar signal is received from the Doppler radar. In a step 2230 , the at least one radar output signal is converted to digital form with an ADC. In a step 2240 , an arc-length CP signal is produced from the at least one radar output signal. In a step 2250 , a respiration fundamental frequency estimate is employed to extract a heart rate signal from the arc-length cardiopulmonary signal. In a step 2260 , a respiration signal is extracted from the arc-length cardiopulmonary signal. In a step 2270 , the heart rate signal and the respiration signal are provided at an output. The method ends in an end step 2280 .
VII. CONCLUSIONS
Disclosed herein are signal processing systems and methods for Doppler radar CP sensing that enable estimation of respiration and heart rate from measurements of chest-wall dynamic motion. A generic model was formulated in the complex plane to visualize production of the desired chest-wall displacement signal as well as possible interfering signals, and various signal processing routines were developed based on that model. A harmonic cancellation technique was developed for reducing the large respiration component so that the weaker heartbeat signal can be reliably extracted, thereby greatly improving the accuracy of heart rate estimation. The signal processing techniques were studied and evaluated using both a simulated test signal and experiments involving actual data collected from a laboratory setup using a live subject. The results of this study and evaluation show that reliable respiration and heart rate estimation is possible when the subject is seated at rest. However, with dynamic motion of the subject, as when walking or jogging, the relatively large body motion can overwhelm the relatively small respiration and heartbeat signals, making reliable estimation of rates difficult.
Those skilled in the art to which the invention relates will appreciate that other and further additions, deletions, substitutions and modifications may be made to the described embodiments without departing from the scope of the invention.
|
A Doppler radar signal processing system and method and a Doppler radar employing the system or the method. In one embodiment, the system includes: (1) an input configured to receive at least one radar output signal representing a reflected Doppler radar signal, (2) signal processing circuitry coupled to the input and configured to produce an arc-length cardiopulmonary signal from the at least one radar output signal and employ a respiration fundamental frequency estimate to extract a heart rate signal from the arc-length cardiopulmonary signal and (3) an output coupled to the signal processing circuitry and configured to provide the heart rate signal.
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RELATED DISCLOSURES
This patent application relates to subject matter disclosed in Disclosure Document Numbers 411,887; 417,369; 417,458 and 442,322.
RELATED APPLICATIONS
This patent application is a continuation of Ser. No. 09/684,209 filed Oct. 6, 2000 now U.S. Pat. No. 6,539,377, which is a continuation of Ser. No. 09/259,600 filed Mar. 1, 1999 now U.S. Pat. No. 6,182,068, which is a continuation in part of three co-pending patent applications, Ser. No. 08/904,795 now U.S. Pat. No. 6,006,222, Ser. No. 08/960,140 now U.S. Pat. No. 6,014,665 and Ser. No. 09/041,411 now U.S. Pat. No. 6,078,916, filed Aug. 1, 1997, Oct. 29, 1997 and Mar. 12, 1998, respectively, all entitled “Method For Organizing Information.”
FIELD OF THE INVENTION
The present invention relates to search engines, and more particularly pertains to a method for organizing information by monitoring the search activity and personal data of searchers.
BACKGROUND OF THE INVENTION
The Internet is an extensive network of computer systems containing hundreds of millions of documents, files, databases, text collections, audio clips, video clips and samples of any other type of information (collectively “articles”). As explained in my earlier referenced patent applications, search engines are used to locate articles over the Internet. Given the large amount of information available over the Internet, it is desirable to reduce this information down to a manageable number of articles which fit the needs of a particular user.
OBJECTS AND SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to organize articles available over the Internet or within any other collection of information.
It is another object of the present invention to monitor searching activity to organize articles in accordance with the searching activity of one or more users.
It is another object of the present invention to utilize personal data about a searcher to organize articles in accordance with the searching activity of one or more users.
To accomplish these and other objects, the present invention generally comprises a method for organizing information in which the search activity of previous users is monitored and such activity is used to organize articles for future users. Personal data about future users can be used to provide different article rankings depending on the search activity and personal data of the previous users.
This brief description sets forth rather broadly the more important features of the present invention in order that the detailed description thereof that follows may be better understood, and in order that the present contributions to the art may be better appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will be for the subject matter of the claims appended hereto.
In this respect, before explaining a preferred embodiment of the invention in detail, it is understood that the invention is not limited in its application to the details of the method set forth in the following description. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood, that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception, upon which disclosure is based, may readily be utilized as a basis for designing other methods and systems for carrying out the objects and purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The Internet is an extensive network of computer systems containing hundreds of millions of documents, files, databases, text collections, audio clips, video clips and samples of any other type of information, collectively referred to as articles and designated herein by the generic labels A 1 , A 2 , A 3 , etc.
As described in my previous applications, the present invention maintains an index of key words, terms, data or identifiers in English or other languages, computer code, or encryption which are collectively referred to as key terms and represented herein by the generic labels “Alpha, ” “Beta,” “Gamma,” “Delta,” “Epsilon,” etc.
The articles can each be associated with one or more of these key terms by any conceivable method of association now known or later developed. A key term score is associated with each article for each of the key terms. Optionally, a key term total score can also be associated with the article.
As described in my previous applications, the invention can accept a search query from a user and a search engine will identify matched articles and display squibs of the matched articles in accordance with their comparison scores. Articles can have their key term scores or key term total scores altered according to whether they were displayed to a user, whether they were selected by a user, how much time the user spent with the article, etc. In this application, the phrase previous-user relevancy score, designated by the generic label “PRS,” will be used to refer to any of the key term score, key term total score, key term probability score, comparison score, or other ranking score determined by the previous search activity of users.
For example, with the key term scores and key term total scores shown in parentheses, the index may look like this:
Index
Alpha
A1 (PRS), A2 (PRS), A3 (PRS)
Beta
A1 (PRS)
Gamma
A1 (PRS), A3 (PRS)
Delta
A2 (PRS), A3 (PRS)
Epsilon
A1 (PRS), A3 (PRS)
Etc.
Etc.
By storing key term groupings of two or more key terms, the index may look like this:
Index
Alpha-Beta
A1 (PRS), A2 (PRS), A3 (PRS)
Beta-Gamma
A1 (PRS)
Gamma-Delta
A1 (PRS), A3 (PRS)
Delta-Epsilon
A2 (PRS), A3 (PRS)
Epsilon-Zeta-Theta
A1 (PRS), A3 (PRS)
Etc.
Etc.
Personal Data
The present embodiment of the invention utilizes personal data to further refine search results. Personal data includes, but is not limited to, demographic data, psychographic data, personal interest data, personal activity data or other data about users. Personal data can be represented by the generic label “PS.” Individual elements of personal data can be represented by the generic labels “PS1,” “PS2,” “PS3,” etc.
Demographic data includes, but is not limited to, items such as age, gender, geographic location, country, city, state, zip code, income level, height, weight, race, creed, religion, sexual orientation, political orientation, country of origin, education level, criminal history, or health. Psychographic data is any data about attitudes, values, lifestyles, and opinions derived from demographic or other data about users.
Personal interest data includes items such as interests, hobbies, sports, profession or employment, areas of skill, areas of expert opinion, areas of deficiency, political orientation, or habits. Personal activity data includes data about past actions of the user, such as reading habits, viewing habits, searching habits, previous articles displayed or selected, previous search requests entered, previous or current site visits, previous key terms utilized within previous search requests, and time or date of any previous activity.
A searcher who does not possess certain personal data characteristics, such as being a doctor, for example, could also choose to see articles ranked according to the searching activity of previous searchers who were doctors, as described below. In this respect, then, it is possible for a search request to specify the type of personal data previous searchers should have had, even if the current (or second) searcher does not actually have that personal data characteristic.
Inferring Personal Data
Users can explicitly specify their own personal data, or it can be inferred from a history of their search requests or article viewing habits. In this respect, certain key words or terms, such as those relating to sports (i.e. “football” and “soccer”), can be detected within search requests and used to classify the user as someone interested in sports. Also, certain known articles or URLs can be detected in a users searching or browsing habits, such as those relating to CNNfn (www.cnnfn.com) or Quote.com (www.quote.com), and also used to classify the user as someone interested in finance.
A cumulative score can be kept with regard to these occurrences of certain classified key terms, queries or visited URLs to quantify how strongly someone is associated with a particular item of personal data. The score can be normalized over time, frequency or other activity such as the number of searches performed, the amount of time spent online, the amount of time spent browsing on a particular subject, the number of URLs or articles selected for a particular subject, or otherwise.
For example, assume a user has entered the following ten search requests and visited the following articles or URLs:
Index for Search Requests or Browsing Topics
stock quotes
sports scores
Cnnfn
junk bonds
Cars
down comforters
stock quotes
dow jones
Football
nba
Index for Articles or URLs
www.cnnfn.com
www.wsj.com
www.nba.com
www.sportsline.com
www.marketwatch.com
Etc.
Given a correlation chart between certain key terms and certain items or personal data such as the following:
Index for Search Requests or Browsing Topics
Item of Personal
Data
Key Words or Queries
Sports Interest
football
sports
scores
hockey
jets
nba
etc.
Finance Interest
stocks
bonds
tech stocks
cnnfn
dow jones
etc.
Index for Articles or URLs
Item of Personal
Data
Articles or URLs
Sports Interest
sportsline.com
nba.com
etc.
Finance Interest
cnnfn.com
wsj.com
marketwatch.com
etc.
Then, the user can be identified as having the personal data characteristic of being a sports fan and having an interest in finance because there are three queries relating to sports (“sports scores,” “football,” and “nba”) and five queries containing key words relating to finance (“stock quotes,” “cnnfn,” “junk bonds,” “stock quotes,” and “dow jones”) This can be done by keeping a cumulative score for a user for search requests or URLs. For example, whenever there is a match (whole or partial) between a search request or URL and an item of personal data, a record for the user can be updated to give a +1 for that item of personal data. A cumulative score can be developed for the user for each item of personal data, called a personal data item score. When the personal data item score of the user reaches a certain threshold, then the item of personal data can be said to be associated with the user. Additionally or alternatively, the strength of the association can be determined by the cumulative personal data item score. The personal data item score for each item of personal data can be normalized by any normalizing factor, such as the number of requests entered, the number of URLs visited, the average personal data item score for other users in that item of personal data, the median personal data item score for other users in that item of personal data or otherwise.
Similarly, the same analysis can be done with URLs or articles that are deemed to relate to certain items or personal data as well that the user has visited. Particular queries can include terms from more than one personal data classification and thus indicate more than one item of personal data for the user.
Tracking Personal Data
When a first user enters a search query, the personal data can be considered part of the request and stored within or added to the index, individually or in groupings with other items of data such as key terms, categories, or ratings. For example, after receiving a number of queries, the index may look like this:
Index
Alpha
A1 (RS), A2 (RS), A3 (RS)
Alpha-PS2
A1 (RS), A3 (RS)
Beta-Gamma
A1 (RS)
Gamma-Delta-PS4
A1 (RS), A3 (RS)
Delta-Epsilon
A2 (RS), A3 (RS)
Epsilon-Zeta-PS1
A1 (RS), A3 (RS)
Epsilon-PS3-PS7
A3 (RS)
Etc.
Etc.
The personal data can be used to recall different lists of articles in response to new queries from new users. In this respect, it is possible to simply store all elements of personal data, individually or in key term groupings, within the index separately, with components of the query or otherwise. When the next user enters a search request, the search request and the user's personal data are combined to form groupings containing key term groupings, key terms and personal data groupings, category and personal data groupings, rating and personal data groupings, etc. Articles associated with these groupings are then retrieved from the index, and their relevancy scores are used or combined to determine their rankings.
For example, if a first user enters a search request of Alpha and has personal data characteristics of PS1 and PS5, then the request can be combined with the personal data to form the following groupings: Alpha-PS1 and Alpha-PS5. In addition, other groupings or permutations such as PS1-PS5 and Alpha-PS1-PS5 are also possible and can be stored within the index. These groupings are stored within the index and the relevancy scores of selected articles are updated according to methods described in my previous applications To initially retrieve articles for presentation to the first user using a conventional search engine, just the key term “Alpha” can be used as a key term to pull articles from within an index.
When a second searcher actually having, or who has selected to see results from other searchers having, personal data characteristics of at least PS5 searches for Alpha, for example, then the relevancy scores of articles under at least the grouping Alpha-PS5 can be used to rank the articles according to methods described in my previous applications. Similarly, a searcher having or selecting personal data characteristic of PS1 searching for Alpha can see articles ranked according to methods described in my previous applications by the relevancy scores of articles under at least the grouping Alpha-PS1. A searcher having or selecting personal data characteristics of PS1 and PS5 searching for Alpha can see articles ranked according to methods described in my previous applications by the relevancy scores of articles under any of groupings Alpha-PS1, Alpha-PS5, and Alpha-PS1-PS5, as desired.
In this manner, the relevancy of articles is determined by the searching activity of previous searchers which share, or are indicated as having, certain personal data characteristics.
As mentioned above, a searcher who does not possess certain personal data characteristics, could also choose to see articles ranked according to the searching activity of previous searchers who have a certain characteristic, in which case the user should simply specify the personal data characteristic the user desires.
Identifying Relevant Personal Data
It is possible that not all elements of personal data will result in different rankings of articles under certain key terms or key term groupings. To save storage space and processing time, it is desirable to determine which personal data characteristics result in different rankings.
One way to determine which personal data characteristics result in different rankings is to compare the previous-user relevancy scores, or ranking determined at least in part by the previous user relevancy scores, of articles under certain key terms or key term groupings in which a particular personal data characteristic is different. For example, articles under a search query or key term such as “shoes” may have different relevancy scores depending on whether the previous searchers were women or men, whereas the rankings may not be different for a personal data characteristic such as political orientation.
For example, the index for the following key term groupings for the key term “shoes,” with the previous-user relevancy scores in parentheses, may look like this:
Index
Shoes
A1 (5), A2 (4), A3 (3), A4 (2), A5 (1)
Shoes-Women
A1 (1), A2 (2), A3 (3), A4 (4), A5 (5)
Shoes-Men
A1 (5), A2 (4), A3 (3), A4 (2), A5 (1)
Shoes-Republican
A1 (5), A2 (4), A3 (3), A4 (2), A5 (1)
Shoes-Democrat
A1 (5), A2 (4), A3 (3), A4 (2), A5 (1)
Here, the previous-user relevancy scores of the articles under Shoes-Men and Shoes-Women are different. The magnitude of difference deemed appropriate to identify relevant personal data for a particular key term, grouping of key terms, or query is adjustable. For example, one standard might be if the rankings of five or more of the top 10 articles when ranked in any manner according to their previous-user relevancy scores are significantly different, then the particular element of personal data can be deemed relevant. Of course, some articles may not even be listed under some groupings, indicating that their previous-user relevancy scores are quite different. By “significantly different” is meant different enough so that a user might prefer to see a different ranking based on his or her personal data.
When comparing different combinations of personal data, the aforementioned analysis is preferably performed on groupings in which one item of a similar type of personal data is varied. For example, the analysis may look at men compared to women, republicans compared to democrats, or certain professions compared to other professions, etc. Personal data which is not relevant to creating differently ranked articles can be tagged, removed from the index or not stored in the index at all.
When a new search request is submitted by a new or second user, the groupings containing parts of the search request and personal data of the second user (or selected by the second user) which are in the index, or are otherwise tagged as being relevant, can then be used to rank or alter the ranking of the articles according to the previous-user relevancy scores under the groupings.
Personalized Queries
Another embodiment of the present invention keeps track of the full queries, or portions thereof such as key terms groupings, which are entered by users having certain personal data characteristics. In this embodiment, queries or portions thereof such as key term groupings, are stored within an index, preferably along with the personal data and a previous-user relevancy score for each query.
The previous-user relevancy score for a particular query or portion thereof can be: the number of times the query was entered by all users; the number of times a query was entered by unique users; the number of times a query was entered by a particular group of unique users sharing a particular personal data characteristic; the product, sum or average of the previous-user relevancy scores of all or some of the articles under the query or portion(s) thereof for all users, unique users or a particular group of users; the product, sum or average of the previous-user relevancy scores of all or some of the articles under the query or portion(s) thereof for all users, unique users or a particular group of users and the number of times a query was entered by all users all users, unique users or a particular group of users: or any combination of these or other indicators of relevancy of the particular query, or portions thereof, to a particular person or group having certain personal data characteristics. These previous-user relevancy scores for the queries, or portions thereof, can be normalized by factors such as time, number of previous users sharing a particular personal data characteristic, or otherwise by dividing or otherwise altering the raw scores by the normalizing factor or factors.
For example, queries, such as those containing the word “shoes,” may be stored within the index, with a previous-user relevancy score in parentheses next to the query as follows:
Index
Shoes-Women (7)
A1 (5), A2 (4) , A3 (3) . . .
Shoes-Men (9)
A1 (3), A2 (1), A3 (3) . . .
Nike-Shoes-Women (3)
A4 (1), A5 (1), A6 (1) . . .
Nike-Shoes-Men (11)
A4 (5), A5 (4), A6 (3) . . .
Reebok-Shoes-Women (2)
A7 (1), A8 (1), A9 (3) . . .
Reebok-Shoes-Men (9)
A7 (5), A8 (4) , A9 (3) . . .
Converse-Shoes-Women (1)
A10 (1), A11 (1), A12 (1) . . .
Converse-Shoes-Men (8)
A10 (5), A11 (4) , A12 (3) . . .
Pump-Shoes-Women (14)
A13 (5) , A14 (4) , A15 (3) . . .
Pump-Shoes-Men (3)
A13 (1), A14 (1) , A15 (1) . . .
Enzo-Shoes-Women (12)
A16 (5), A17 (4) , A18 (3) . . .
Enzo-Shoes-Men (1)
A16 (1), A17 (1), A18 (1) . . .
Nine-West-Shoes-Women (16)
A19 (5), A20 (4), A21 (3) . . .
Nine-West-Shoes-Men (1)
A19 (1), A20 (1), A21 (1) . . .
It may be desirable to maintain a separate index of just the narrower related key term groupings or queries and the previous-user relevancy scores such as:
Index
Shoes-Women (7)
Shoes-Men (9)
Nike-Shoes-Women (3)
Nike-Shoes-Men (11)
Reebok-Shoes-Women (2)
Reebok-Shoes-Men (9)
Converse-Shoes-Women (1)
Converse-Shoes-Men (8)
Pump-Shoes-Women (14)
Pump-Shoes-Men (3)
Enzo-Shoes-Women (12)
Enzo-Shoes-Men (1)
Nine-West-Shoes-Women (16)
Nine-West-Shoes-Men (1)
In addition, any amount of personal data can be included in the index. For example, an index including both gender and age may look like this:
Index
Nike-Shoes-Women-Under30 (2)
Nike-Shoes-Women-Over30 (1)
Nike-Shoes-Men-Under30 (8)
Nike-Shoes-Men-Over30 (3)
Pump-Shoes-Women-Under30 (8)
Pump-Shoes-Women-Over30 (6)
Pump-Shoes-Men-Under30 (2)
Pump-Shoes-Men-Over30 (1)
It is possible that not all queries, or portions thereof, will have different previous-user relevancy scores depending on the element of personal data considered. To save storage space and processing time, it is desirable to determine which personal data characteristics result in different rankings (as determined all, or at least in part, by the previous-user relevancy score) of the queries or portions thereof.
One way to determine which personal data characteristics result in different query rankings is to compare the previous-user relevancy scores, or ranking determined at least in part by the previous user relevancy scores, of queries, key terms or key term groupings in which a particular personal data characteristic is different. For example, the query or key term grouping such as “pump shoes” may have different relevancy scores depending on whether the previous searchers were women or men, whereas the rankings may not be different for a personal data characteristic such as profession.
For example, the index for the following key term groupings for the key term “shoes,” with the previous-user relevancy scores in parentheses, may look like this:
Index
Pump-Shoes-Women (14)
A1 (5), A2 (2), A3 (3), A4 (4), A5 (5)
Pump-Shoes-Men (1)
A1 (1), A2 (1), A3 (3), A4 (2), A5 (1)
Pump-Shoes-Doctor (12)
A1 (5), A2 (4), A3 (3), A4 (2), A5 (1)
Pump-Shoes-Lawyer (12)
A1 (5), A2 (4), A3 (3), A4 (2), A5 (1)
Here, the previous-user relevancy scores of the queries or groupings Pump-Shoes-Men and Pump-Shoes-Women are different, whereas the previous-user relevancy scores of the queries or groupings Pump-Shoes-Doctor and Pump-Shoes-Lawyer are somewhat similar. The personal data of gender (i.e. male or female) is then considered relevant. The magnitude of difference in previous-user relevancy scores deemed appropriate to identify relevant personal data for a particular key term, grouping of key terms, or query is a variable that can be adjusted to make the system more or less sensitive to these differences.
For example, one standard might be if the rankings of five or more of the top 10 queries when ranked in any manner according to their previous-user relevancy scores are different, then the particular element of personal data can be deemed relevant.
When comparing different combinations of personal data, the aforementioned analysis is preferably performed on groupings in which one item of a similar type of personal data is varied. For example, the analysis may look at men compared to women (gender), republicans compared to democrats (political orientation), or certain professions compared to other professions (employment), etc. Personal data that is not relevant to creating differently ranked articles can be tagged, removed from the index or never stored in the index at all
If two different items of personal data (such as gender and geographic region) are determined to create different lists of queries (or URLs) for a particular search request, then it can be assumed that the combination of these two items of personal data will result in a split as well. For example, if Shoes-Women results in a different list of queries (or URLs) than Shoes-Men (gender) when other items of personal data are held constant and/or varied in a known manner (such as varied within a certain predetermined range), and Shoes-Southeast results in a different list of queries (or URLs) than Shoes-Northwest (geographic region), then we can assume that Shoes-Women-Southeast, Shoes-Women-Northwest, Shoes-Men-Southeast, and Shoes-Men-Northwest are different and should be tagged as such or maintained within the index. Then, when someone having these two items of personal data enters a search request, the relevancy scores for articles under these key term groupings can be used to rank the articles for presentation to the second user.
Presenting Personalized Queries Related to a Search Request
As described in my earlier applications, when a new or second user enters a search query containing one or more words, the system can look for related key term groupings or queries that contain the original query or portions thereof and suggest those additional words, groupings, or queries or portions thereof, of the narrower related key term groupings or queries to refine the search. Preferably, the related key term groupings or queries will be narrower related key term groupings or queries, which are more narrow in scope.
In addition, the system can also identify narrower related queries or narrower related key term groupings which do not necessarily contain a word or term from the original search request, but which are nonetheless related to the request, such as by being synonyms r subsets or species of a broader category. For example, the query “High-Heels” can be identified as related to the subject “shoes” as a particular narrower query of the broader request “shoes.” Accordingly, the query “High-Heels” should be considered along with other queries that actually contain the word “shoes.” One way these queries related to the subject of the original search query, but which do not actually contain portions of the original search query can be identified is by first utilizing a thesaurus database of equivalent terms for terms in the original search query. Narrower queries or narrower key term groupings that contain one or more of these equivalent terms can then be identified as narrower related key term groupings.
To present personalized narrower related key term groupings to a user, the system can present the narrower related key term groupings that include not only at least a portion of the original search request, but also at least a portion of the user's personal data. These narrower related key term groupings can be presented in order of superiority according to their previous-user relevancy scores.
For example, when a woman enters the search request “shoes,” the system can look for narrower related queries or key term groupings which contain or are related to the term “shoes” and which have been entered by previous users having similar personal data, such as that of being a “woman.”
As seen from the following index, the top three narrower related key term groupings or queries related to the original query “shoes” for women, when ranked by their previous-user relevancy score, are “Nine West Shoes,” “Pump-Shoes,” “Enzo-Shoes.”
Index
Shoes-Women (7)
A1 (5), A2 (4), A3 (3) . . .
Shoes-Men (9)
A1 (3), A2 (1), A3 (3) . . .
Nike-Shoes-Women (3)
A4 (1), A5 (1), A6 (1) . . .
Nike-Shoes-Men (11)
A4 (5), A5 (4), A6 (3) . . .
Reebok-Shoes-Women (2)
A7 (1), A8 (1), A9 (3) . . .
Reebok-Shoes-Men (9)
A7 (5), A8 (4), A9 (3) . . .
Converse-Shoes-Women (1)
A10 (1), A11 (1), A12 (1) . . .
Converse-Shoes-Men (8)
A10 (5), A11 (4), A12 (3) . . .
Pump-Shoes-Women (14)
A13 (5), A14 (4), A15 (3) . . .
Pump-Shoes-Men (3)
A13 (1), A14 (1), A15 (1) . . .
Enzo-Shoes-Women (12)
A16 (5), A17 (4), A18 (3) . . .
Enzo-Shoes-Men (1)
A16 (1), A17 (1), A18 (1) . . .
Nine-West-Shoes-Women (16)
A19 (5), A20 (4), A21 (3) . . .
Nine-West-Shoes-Men (1)
A19 (1), A20 (1), A21 (1) . . .
Similarly, the top three narrower related key term groupings or queries related to the original query “shoes” for men, when ranked by their previous-user relevancy score, are “Nike Shoes,” “Reebok Shoes,” and “Converse Shoes.”
Accordingly, the invention could present these narrower related key term groupings or queries to women or men entering the search request “shoes,” respectively. Narrower related key term groupings or queries can be presented for other queries and for other people having certain personal data as well.
Personalized Search Results from Personalized Queries
To present personalized search results to a particular person searching with a particular term or query, the present invention may display a number of articles from a number of the narrower related key term groupings or queries which are ranked by their respective previous-user relevancy scores.
For example, a user having the personal data of being a woman who is searching for “shoes” can be shown the first few of the top ranked (by previous-user relevancy scores) articles from each of the first few of the top ranked (by previous-user relevancy scores) narrower related key term groupings or queries. In this example, the top ranked narrower related key term groupings or queries for women are “Pump Shoes,” “Enzo Shoes,” and “Nine West Shoes.” Displaying the top few (i.e. 3, more or less) articles from these narrower related key term groupings or queries, ranked according to their respective previous-user relevancy score, in response to the search request of “shoes” from a woman results in the following list of articles (when considering only the previous-user relevancy scores for the articles under these narrower related key term groupings or queries): A13(5), A16(5), A19(5), A14(4), A17(4), A20(4), A15(3), A18(3), A21(3).
Index
Pump-Shoes-Women (14)
A13 (5), A14 (4), A15 (3) . . .
Enzo-Shoes-Women (12)
A16 (5), A17 (4), A18 (3) . . .
Nine-West-Shoes-Women (16)
A19 (5), A20 (4), A21 (3) . . .
It is also possible to consider both the previous-user relevancy score of the top narrower related key term groupings or queries, as well as the previous-user relevancy score of the articles under these narrower related key term groupings or queries. In this respect, the previous-user relevancy score of the top narrower related key term groupings or queries and the previous-user relevancy score of the articles under these narrower related key term groupings or queries can be combined in any possible manner, such as by adding, multiplying, or averaging together
When the previous-user relevancy score of the top narrower related key term groupings or queries is multiplied with the previous-user relevancy score of the articles under these narrower related key term groupings or queries for the search request of “shoes” from a woman, for example, the following list of articles results: A19(80), A13(70), A20(64), A16(60), A14(56), A17(48), A21(48), A15(42), A18(36).
These articles can then be presented to the woman user entering the search request “shoes.” Also, these computations described above can be completed offline or otherwise to populate, replace the articles, or update the previous-user relevancy scores under the queries or key term groupings, such as Shoes-Women, for example.
Implementation
The implementation notes of my previous applications are hereby incorporated by reference.
The personal data, scores for determining the personal data based on personal activity, etc can be stored in the form of what are commonly known in the computer industry as “cookies.”
The method can allow the index to further associate a key term total score with each key term score; alter the index such that the key term score for the selected article under at least one of the first matched key terms is altered relative to other key term scores; and alter the index such that key term total scores of at least one of the articles related to the first search query under at least one of the first matched key terms a e altered relative to other key term total scores, but only for articles that have had their squibs displayed to the first user.
The method can also alter the index such that the key term score for the selected article under at least one of the first personal data elements is altered relative to other key term scores; and alter the index such that key term total scores of at least one of the articles related to the first search query under at least one of the first matched personal data elements are altered relative to other key term total scores, but only for articles that have had their squibs displayed to the first user.
The method can also add a positive score to the key term scores for the selected article under at least one of the first matched key terms; and add a positive score to the key term scores for the selected article under at least one of the first matched personal data elements.
The method can also add a positive score to the key term scores for the selected article under all the first matched key terms; and add a positive score to the key term scores for the selected article under all the first matched personal data elements.
The method can also allow the first user to select at least one of the articles related to the first search query through any action allowing the first user to sense more than just the squib of the at least one of the articles related to the first search query, the article selected by the first user being a selected article.
The method can also allows the user to select at least one of the articles related to the first search query by clicking on a hypertext link portion of the squib of the at least one of the articles related to the first search query, the article selected by the user being a selected article.
The method can also allow the user to select at least one of the articles related to the first search query by opening the at least one of the articles related to the first search query, the article selected by the first user being a selected article.
The method can also allow the user to select at least one of the articles by retrieving the at least one of the articles related to the first search query from a remote server, the article selected by the first user being a selected article.
As to a further discussion of the manner of usage and operation of the present invention, the same should be apparent from the above description. Accordingly, no further discussion relating to the manner of usage and operation will be provided.
With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in form, function and manner of operation, implementation and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
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A method of organizing information in which the search activity of previous users is monitored and such activity is used to organize articles for future users. Personal data about future users can be used to provide different article rankings depending on the search activity and personal data of the previous users. The personal data is used in the development of an index, the index including entries for specific categories of personal data. The similarity or difference in the prior results for a query term determine if separate index entries are needed for the categories and terms being considered.
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This is the national phase Application of PCT EP01/03153 filed, Mar. 20, 2001.
BACKGROUND OF THE INVENTION
The invention concerns new lipopolysaccharides extracted from E. coli.
Endotoxins are bacterial structural components, which, unlike exotoxins, are not secreted, but rather are released, especially following autolysis. The classic endotoxins are heat-stable lipopolysaccharides (LPS) from the outer cell membrane of gram-negative bacteria. LPS consists of lipid A, which is responsible for the toxic effect of LPS, a core oligosaccharide and an O-specific chain.
In macroorganisms, endotoxins stimulate the production of immune system mediators, such as interleukin-1 (IL-1) and tumor necrosis factor (TNFα).
Many studies have already been conducted on the composition of the endotoxins of enterobacteria, especially E. coli , in which it was determined that S/R mutants generally contain only one repeating unit of their O specific chain (cf. FIG. 1 ). It is assumed that in these cases, the gene that codes for the polymerizing enzyme of the O-specific chain is defective, and therefore only one repeating unit it transferred to the core oligosaccharide. LPS structures of a similar type but different structure are also commonly found in bacteria that are pathogenic in man, such as Neisseria, Vibrio, Campylobacter, Helicobacter, etc. These bacteria have an LPS which allows them to evade the immune defense of the host by means of a special molecular mimicry, including the presence of sialic acid and oligosaccharides that contain sialic acid, which resemble glycoproteins and glycolipids in mammals. The 06 serotype was determined for E. coli DSM 6601. This structure was studied and published by P. E. Jansson et al., Carbohydr. Res . 131 (1984) 277-283. The structure corresponds to the formula shown in FIG. 2 . FIG. 2 is a representation of the structure of the O antigen of E. coli 06. All sugars are present in the D-pyranose form. In contrast to the structure of the O-specific chain of E. coli 06 published by Jannson et al., the first repeating unit of the S/R mutants of E. coli DSM 6601 is linked by a β-glycosidic bond and was determined as such for the first time in accordance with the present invention, together with the site of substitution at the side-chain glucose (Glc III ) of the core oligosaccharide. (See FIG. 4.)
The lipid A of the coli bacteria has also been investigated by various research groups, and it was found that the structure of the lipid A generally has the hexaacyl form and is consistent for all serotypes of E. coli (FIG. 3 ). The structure of the hexaacyl compound was published in 1984 by T. Rietschel et al., Structure and Conformation of the Lipid A Component of Lipopolysaccharides. Handbook of Endotoxins (Proctor, R., ed.), Vol. 1 , Chemistry of Endotoxin (E. T. Rietschel, ed.), Elsevier, Amsterdam (1984), pp. 187-220. The structure is shown in FIG. 3 . FIG. 3 is a representation of the structure of the hexaacyl lipid A of E. coli . (Zähringer, U., Lindner, B. and E. T. Rietschel, Molecular Structure of Lipid A, the Endotoxic Center of Bacterial Lipopolysaccharides, Adv. Carbohydr. Chem. Biochem ., 50 (1994) 211-276). The numbers in the circles indicate the number of carbon atoms in the given fatty acid. The free hydroxyl group of the GlcN (II) represents the bonding site for the Kdo (I) of the core oligosaccharide.
The O-specific chain and the lipid A are linked by the core oligosaccharide. There are five previously known core oligosaccharides of E. coli ; see O. Holst et al., Chemical Structure of the Core Region of Lipopolysachharide, IN: Bacterial Endotoxic Lipopolysaccharides , Vol. 1, Morrison, D. C. and Ryan, J. L. (eds.), Boca Raton, Fla., USA (1992) pp. 135-170 (cf. FIG. 4 ). FIG. 4 is a representation of the structure of the carbohydrate skeleton of the principal fraction in the core oligosaccharide of E. coli R1. (Vinogradov, E. V., van der Drift, K., Thomas Oates, J. E., Meshkov, S., Brade, H-. and O. Holst (1999) Eur. J. Biochem ., 261, 629-639.) The O-specific chain substitution at the side-chain glucose (Glc III ) and its anomerism were determined for the first time in accordance with the present invention. All sugars are present in the D-pyranose form. (L, D-Hep, L-glycero-D-manno-heptose; Kdo D-manno-oct-2-ulosonic acid; P, phosphate.)
SUMMARY OF THE INVENTION
The invention relates to lipopolysaccharides, for example, lipopolysaccharides that are extracted from E. coli DSM 6601. In one aspect of the present invention, a lipopolysaccharide is provided comprising a lipid A portion, a core oligosaccharide portion, and an O-specific chain having a single repeating unit of serotype 06. Preferably, the O-specific chain is linked to the core oligosaccharide portion. More preferably, the O-specific chain is linked to the core oligosaccharide by a β-glycosidic bond.
In accordance with another aspect of the invention, the linkages within the O-specific chain are linked by α-glycosidic bonds.
In another aspect of the invention, the lipid A portion of the lipopolysaccharide is linked to the core oligosaccharide portion of the lipopolysaccharide.
In another aspect of the invention, the lipopolysaccharide has eight (8) phosphate groups per molecule of lipopolysaccharide.
In another aspect of the invention, the lipopolysaccharide has a phosphate substituent P-Etn in a concentration of 0.5 moles per mole of lipopolysaccharide.
In accordance with another aspect of the invention, a process for producing lipopolysaccharides is provided. An E. coli bacterial mass is washed and dried, the washed and dried bacterial mass is subjected to a phenol/water extraction, and the phenol/water extract is treated with RNases, DNases and proteinase K. Preferably, the E. coli bacterial mass is derived from E. coli strain DSM 6601.
In yet another aspect of the invention, a process for the use of the lipopolysaccharide for microbiological, bioengineering, analytical, diagnostic or medical purposes is provided. Preferably, the lipopolysaccharide is E. coli strain DSM 6601 lipopolysaccharide.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a photograph of the results of an SDS-PAGE analysis of Escherichia coli DSM 6601 LPS preparations.
FIG. 2 is a schematic drawing of the structure of the O antigen of E. coli 06.
FIG. 3 is a schematic drawing of the structure of the hexaacyl lipid A of Escherichia coli.
FIG. 4 is a schematic representation of the structure of the carbohydrate skeleton of the principal fraction in core oligosaccharides of E. coli R1.
FIG. 5 is a representation of the results of analysis of dose-dependent IL-1 release from human monocytes induced by lipid A of Escherichia coli or lipid A from E. coli strain DSM 6601 and by LPS from S. friedenau and E. coli strain DSM 6601.
FIG. 6 is a representation of the results of analysis of dose-dependent TNFα release from human monocytes induced by lipid A of E. coli or lipid A. from E. coli strain DSM 6601 and by LPS from S. friedenau and E. coli strain DSM 6601.
FIG. 7 is a schematic representation of the structure of a complete lipopolysaccharide of E. coli DSM 6601.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Studies of the LPS of E. coli strain DSM 6601 revealed that the composition of the lipid A corresponds to the hexaacyl form of the lipid A otherwise described for E. coli.
The studies with respect to the release of IL-1 and TNFα in human monocytes confirm that this lipid A has the same activity as E. coli lipid A and therefore very probably corresponds in its structure to the known structure of E. coli lipid A (cf. FIG. 5, FIG. 6 ). FIG. 5 is a representation of the results of an analysis of dose-dependent IL-1 release from human monocytes induced by: 1) lipid A of Escherichia coli (top left) or lipid A from E. coli strain DSM 6601 (top right) and 2) by LPS from S. friedenau (bottom left) and Escherichia coli strain DSM 6601 (bottom right). FIG. 6 is a representation of the results of analysis of dose-dependent TNFα release from human monocytes induced by: 1) lipid A of Escherichia coli (top left) or lipid A from E. coil strain DSM 6601 (top right) and 2) by LPS from S friedenau (bottom left) and Escherichia coli strain DSM 6601 (bottom right). This assumption was confirmed by chemical analyses.
The structure of the specific O antigen of E. coli DSM 6601 is surprising due to the fact that apparently only a single repeating unit is normally present in the chain (cf. FIG. 1 ), which leads to the conclusion that the strain DSM 6601 is an S/R mutant, which is extremely unusual for a human isolate. However, as the serologic analysis shows, the structure of this repeating unit corresponds to the basic pattern of the O-specific chain of E. coli 06. FIG. 1 is a photograph of the results of an SDS-PAGE analysis of E. coli DSM 6601 (16% separation gel). Lane 1 is an LPS preparation 1 (phenol/water extract UM II.82); lane 2 is LPS preparation 2; lane 3 is LPS preparation 3; lane 4 is free; lane 5 is E. coli 0111 LPS; lane 6 is Pseudomonas aeruginosa Fischer type 2 LPS; lane 7 is Salmonella minnesota R60 LPS. Arrows point to the LPS bands of core oligosaccharide and a repeating unit (R/S mutant, arrow A) and to an LPS with a complete core oligosaccharide (arrow B).
Although the core region in strain DSM 6601 corresponds to the well-known R1 structure, structural peculiarities are present. Specifically, 8 phosphate groups were analytically determined per LPS molecule, and the lipid A generally has only 2 phosphate groups. Furthermore, a nonstoichiometric content of pyrophosphoethanolamine was found.
Therefore, the LPS of the strain DSM 6601 differs significantly from the previously known LPS from E. coli , especially with respect to the phosphorylated sugar moiety of the core and the degree of polymerization of the O-specific chain. The lipid A corresponds structurally and biologically to the usual type for E. coli . The LPS described here not only is well suited for identifying the coli strain that carries it, but also reduces the pathogenicity of the coli strain while allowing it to retain its immunomodulatory effect. The fact that the O-specific chain is linked by a β-glycosidic bond instead of an α-glycosidic bond could be clearly shown for the first time for E. coli with the example of the S/R mutant DSM 6601.
The lipopolysaccharide (LPS) of E. coli DSM 6601 is a new smooth-rough (S/R) structure, which, on the one hand, is composed of previously known partial structures (O-specific chain, core oligosaccharide and lipid A) and, on the other hand, was completely structurally characterized for the first time in the complex form that exists here (cf. FIG. 7 ). The O-specific chain, which consists of only a single repeating unit of the serotype 06, is linked to the core oligosaccharide by a β-glycosidic bond, which differs from the linkages within the O-specific chain (α-glycosidic). The core oligosaccharide has the R1 structure, a chemical finding that is confirmed by serologic tests with R1-specific antibodies. The lipid A component has a specific chemical structure that is characteristic of E. coli lipid A.
The LPS of E. coli strain DSM 6601 exhibits astonishing homogeneity. Heterogeneity can be observed only with respect to the phosphate substituents (PP and P-Etn vs. P and P), which is being described in this form for the first time. The P-Etn substituent could be definitely determined in the core oligosaccharide, the R1-core oligosaccharide, at the 2 position of the second heptose (Hep II ) by complex NMR analyses.
The complete structure of the LPS of the strain DSM 6601 is shown in FIG. 7 . FIG. 7 is a representation of the structure of the complete lipopolysaccharide of E. coli DSM 6601. The phosphate substituents P and Etn in the two heptoses Hep I and Hep II are not stoichiometric in the core oligosaccharide and are therefore indicated by a broken line. The position and anomeric bond of the Kdo I to the lipid A are analogous to other E. coli LPS structures, likewise the position and anormeric bond of the Kdo II .
The invention is explained in greater detail below by examples.
EXAMPLE 1
Preparation of the LPS
The LPS was obtained from the washed and dried bacterial mass by a modified phenol/water extraction; for further details on this aspect of the preparation, see O. Westphal et al., Bacterial Lipopolysaccharides, Extraction with Phenol-Water and Further Applications of the Procedure, Meth. Carbohydr. Chem ., Vol. V (1965), pp. 83-91.
47 g of the lyophilized bacteria, which had first been washed twice with distilled water, were extracted by a modified method of Westphal and Jann. The modification consisted in a subsequent enzyme treatment (DNase, RNase, proteinase K) of the aqueous extract, the purpose of which was to remove possible foreign proteins and DNA/RNA components. To this end, the aqueous phase (about 1.2 L) is treated at room temperature with 20 mg of RNase (ribonuclease A, bovine pancreas, Sigma) and 20 mg of DNase (DNase I, bovine pancreas, grade II, Sigma). The mixture is stirred for 30 h at room temperature, treated with 20 mg of proteinase K ( Tritirachium album , Boehringer, Mannheim), and stirred for another 12 h. The suspension is dialyzed three times against 15 L of distilled water over 24 h at 4° C. and then lyophilized. The enzyme-treated extract is resuspended in distilled water to an end concentration of 50 mg/mL. This suspension is ultracentrifuged three times at low temperature (155,000×g, 4° C., 4 h). The sediment (LPS) is suspended in 150 mL of distilled water, dialyzed again for three days against water, and then lyophilized (yield of LPS: 1.45 g, 3.1% m/m).
EXAMPLE 2
Analysis of the LPS Extracted From E. coli Strain DSM 6601
Hexosamine (HexN) (meaning here glucosamine+galactosamine, GlcN+GalN) was determined by the modified Morgan-Elson test (Strominger, J. L., Park, J. T., Thompson, R. E., J. Biol. Chem . 234, 3263-3268 (1959)) or alternatively by HPLC (PICO-TAG, Waters). In contrast to the Morgan-Elson test, in this analytical method, it is possible not only separately to determine and quantify GlcN and GalN, but also to make parallel determinations of the presence of GlcN phosphate, 2-ethanolamine (Etn) and 2-ethanolamine phosphate (Etn-P), which often occur in LPS. Gas-liquid chromatography (GC) was performed in a Varian 3700 GC or Hewlett Packard (HP 5890 Series II) gas chromatograph on a capillary column (fused-silica SPB-5®, 30 m, Supelco). The combined gas-liquid chromatography/mass spectrometry (GC-MS) was performed in a mass spectrometer (HP model 5989) equipped with an HP-1 capillary column (30 m, Hewlett Packard). The GC and GC-MS analyses were used to determine the neutral sugars (Glc, Gal, Hep, Man) as their alditol acetates (Sawardeker, J. S., Slonerker, J. H., Jeanes, A., Anal. Chem . 37, 1602-1604 (1967)) and to determine and quantify the fatty acids as their fatty acid methyl ester derivatives after intense methanolysis (2 M HCl/MeOH, 120° C., 16 h) (Wollenweber, H.-W. and Rietschel, E. T., Analysis of Lipopolysaccharide (Lipid A) Fatty Acids, J. Microbiol. Meth . 11, (1990) 195-211) and extraction with chloroform. In both GC analytical methods, the initial temperature was 150° C. (isothermal for 3 min), and then the temperature was increased to 320° C. by a linear temperature gradient of 5° C./min. Phosphate was determined by the method of Lowry et al. (Lowry, O. H., Roberts, N. R. , Leiner, K. Y., Wu, M. Kl., Farr, A. L., J. Biol. Chem . 207, 1-17 (1954)), and the 2-keto-3-deoxy-D-manno-octulosonic acid (Kdo) was determined by the thiobarbituric acid test (Waravdekar, V. C. and Saslaw, L. D., J. Biol. Chem . 234, 1945-1950 (1959)).
Preparation and Purification of the Free Lipid A and the Core Oligosarcharide
LPS (258.8 mg) was suspended in 25 mL of 0.1 M NaOAc/HOAc (ph 4.4) and subjected to gentle acid hydrolysis at 100° C. for 1 h. The lipophilic fraction (lipid A) was then extracted three times from the hydrolysate with 25 mL of chloroform (yield: 23.2 mg). The lipid A from the organic phase was further purified by preparative thin-layer chromatography (PTLC) (2 mm PTLC silica gel 60 plate, E. Merck, Darmstadt), which was chromatographed with chloroform-methanol-water 100:75:15 (v/v/v) and developed by immersion in distilled water. In this way, six fractions were obtained, of which the principal fraction (R f ≈0.4) represents the purified diphosphorylated hexaacyl lipid A (DPHLA-Ec 6601 ). The purified DPHLA-EC 6601 (yield: 2.06 mg) was dissolved in chloroform-methanol 8:2 (v/v) and treated with ion exchanger (Amberlite IRA 120, H + form) before the MALDI-TOF-MS. An aliquot portion (250 μg) of the purified DPHLA-EC 6601 was used for the biological experiments.
The aqueous phase from the chloroform extraction was lyophilized (yield: 272 mg), and the oligosaccharide was further purified by means of a TSK column [3.5×90 cm, TSK HW-40(S), E. Merck] in pyridine-acetic acid-water 8:20:2000 (v/v/v). The individual oligosaccharide fractions (pool A, B, C, D) were analyzed by GC-MS and NMR spectroscopy. The principal fraction (pool A, #28-41; 49.05 mg), which contained both sugar components of the O-specific chain (Man, GalNac) and sugar components of the core oligosaccharide (Hep, Kdo), was further purified. The other fractions contained monosaccharides, artifacts of Kdo (anhydro- and lactones), which were not further analyzed, and, finally, salt. The principal fraction of the TSK separation showed all components of the core oligosaccharide (Kdo, Gal, Hep) and of the O-specific chain (Man, GalNac) in both the GC-MS analysis and the NMR analysis and therefore was worked up further.
Whether analytical high-pressure anion-exchange chromatography (HPAEC) is suitable for purifying the oligosaccharides to homogeneity was determined. A specific HPLC method for the analysis of complex sugar structures (DIONEX system) with an analytical CarboPac PAl column (4.6 mm×250 mm) and a linear salt gradient (5 min at 0 M NaOAc, then increased to 0.5 M NaOAc in 50 min) at a flow rate of 1 mL/min was used. The eluate was detected by a pulse-amperometric detector (PAD) for reduction equivalences (sugar molecules). Four oligosaccharide fractions were obtained in this way, which were then similarly further purified by semipreparative HPAEC.
The semipreparative HPAEC was carried out with a CarboPac PA1 column [(9 mm×250 mm) Dionex system] with the same salt gradient as in the analytical HPAEC (5 min at 0 M NaOAc, then increased to 0.5 M NaOAc in 50 min) and a flow rate of 4 mL/min. The application of the oligosaccharide (42 mg; pool A from the TSK column) to the semipreparative HPAEC column was performed in two analogous HPAEC runs. The eluate was collected in fractions of one minute each, and the individual fractions were analyzed by analytical HPAEC. Two principal fractions were obtained in this way by semipreparative HPAEC (fraction I, retention time t R ˜12 min and fraction II, t R ˜15 min). The salt had to be removed from both HPAEC fractions by means of a G-10 column (2.5×120 cm) before the MALDI-TOF-MS and NMR analysis (yield: fraction I: 4.68 mg; fraction II: 4.39 mg).
Matrix-assissted Laser Desorption/Ionization Time-of-flight (MALDI-TOF) Mass Spectrometry
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was recorded in a Bruker-Reflex II time-of-flight spectrometer (Bruker-Franzen Analytik, Bremen) exclusively in the linear configuration and in the negative mode at an accelerating voltage of 20 kV and with delayed ion extraction. The samples were first dissolved in chloroform (lipid A) or distilled water (oligosaccharide fractions) in a concentration of 10 μg/μL. 2-μL aliquots of these solutions were dissolved with 2 μL of a matrix solution consisting of 0.5 M 2,4,6-trihydroxyacetophenone (Aldrich, Steinheim) in methanol. Aliquots (0.5 μL) of this mixture were applied to a metal holder and dried with a hair drier.
NMR Spectroscopy
One-dimensional (1D) 1 H- and 31 P-NMR spectra and two-dimensional (2D) NMR spectra were recorded with a Bruker Avance DRX-600 spectrometer (Bruker, Rheinstetten), and 13 C NMR spectra were recorded with a Bruker AMX-360 spectrometer at 300 K in 2 H 2 O. Before each measurement, the samples were lyophilized twice with heavy water ( 2 H 2 O). Acetone (δ H 2.225 ppm, δ C 31.45 ppm) or 85% H 3 PO 4 (δ P 0 ppm) was used as the external reference signal. Standard Bruker software (XWINNMR 1.3) was used to record the NMR data. The mixing times for the TOCSY (total correlated spectroscopy) and NOESY (nuclear Overhauser enhancement spectroscopy) were 100 and 500 ms, respectively.
Serologic Analyses
The serologic analyses were performed as Western blots, which were developed with three different antibodies.
Polyclonal anti-06 antiserum (rabbit) was prepared with E. coli strain DSM 6601 (serotype 06: K5: H1) at the Institute of Hygiene in Hamburg (Prof. Bockemühl).
Polyclonal anti- E. coli R1-antiserum (rabbit, internal designation: K299/d58) was obtained by immunization with a rough-form mutant that possesses an R1-core (anti-R1).
A monoclonal antibody (WN1-222-5, internal designation: F 167) was used, which broadly cross-reacts against all E. coli core oligosaccharides above a minimal structure (>Rd).
TABLE
Component analysis of E. coli LPS extracted from the strain
DSM 6601.
Amount of the
component
nmoles/mg
Component
(moles/LPS) a
Carbohydrates
Analysis 1
Analysis 2
GlcN b
283
(1.8)
not
determined
GalN
139
(0.9)
not
determined
HexN c
591
(3.8)
589
(2.9)
Kdo
248
(1.6)
242
(1.2)
Man
321
(2.1)
383
(1.9)
Gal
474
(3.0)
557
(2.8)
Glc
1069
(6.9)
1291
(6.4)
L,D-Hep
566
(3.6)
442
(2.2)
Polar Head Groups
P
1188
(7.6)
1146
(5.7)
Etn-P
85
(0.5)
not
determined
Fatty Acids
12:0
130
(0.8)
162
(0.8)
14:0
156
(1.0)
201
(1.0)
14:0(3-OH)
460
(3.0)
504
(2.5)
16:0
Traces
traces
a The molar ratio of the individual components in parentheses) was standardized to the value of myristic acid (14:0) (1.0 mole 14:0/mole LPS)due to the presence of GalNac and GlcNac in the O-specific chain.
b GlcN determined by amino acid analyzer. The value is obtained from the sum of GlcN and GlcN-6P.
c HexN photometrically determined by the Morgan-Elson test.
The LPS preparations obtained by the method described above and comparative samples of LPS were subjected to polyacrylamide gel electrophoresis (cf. FIG. 1 ). In the preparation of the SDS-PAGE analysis of the LPS, we worked with 16% polyacrylamide gels (U.K., Laemmli, Cleavage of Structural Proteins during Assembly of Head of Bacteriophage T4, Nature, 227, 680-685 (1970)). The LPS bands were stained by the sensitive alkaline silver stain method (C. M. Tsai and Frasch, C. F., A Sensitive Silver Stain for Detecting Lipopolysaccharides in Polyacrylamide Gels, Anal. Biochem., 119, 1982, 115-119).
The results of the analyses are shown in FIG. 1 .
EXAMPLE 3
Biological Activity
(a) IL-1 Activity
The IL-1 activity is determined by an MNC proliferation assay in a culture supernatant. Human monocytes (MNC) are isolated from the peripheral blood of volunteer donors (8×10 5 MNC/200 mL), transferred into a glass and simultaneously treated with test substance. To test the biological activity in vitro, the cells are first stimulated with LPS (10 ng/mL). After an incubation period of 8 hours, 150 mL of the culture supernatant are analyzed for cytokine release. The IL-1 activity is determined by a fibroblast proliferation assay in a culture supernatant. The fibroblasts needed for this were obtained from human prepuce. The proliferation of these fibroblasts was increased by IL-1. The biological activity in the culture supernatant is determined by comparing the dose-response curve of the culture supernatant with the curve of the standard in a probit analysis. The LPS from a bacterial strain known to be endotoxically active (Salmonella friedenau) serves as the reference (positive control) and therefore is included in FIG. 5 .
(b) TNFα Activity
The TNFα activity in a culture supernatant is determined in a cytotoxicity assay with the TNF-sensitive cell line L929. The TNF activity can be determined by comparing the dos-response curve of the culture supernatant with the curve of the standard in a probit analysis. Here again, a Salmonella friedenau LPS that is known to be endotoxically active serves as the positive control. The results are graphically represented in FIG. 6 .
The results show that, with respect to IL-1 and TNFα release, there are no significant differences between the LPS from Salmonella friedenau , which serves as the standard and positive control, and the LPS from the strain DSM 6601 (FIGS. 5 and 6, lower graphs) This is also confirmed by the fact that the lipid A of the strain DSM 6601 shows virtually the same activity as the highly purified lipid A of E. coli (FIGS. 5 and 6, upper graphs).
All embodiments of the invention have been described by way of illustration, and will be understood that the invention can be carried out by persons skilled in the art with many modifications, variations and adaptations, without departing from its spirit or exceeding the scope of the claims.
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Lipopolysaccharides and processes for producting the lipopolysaccharides are provided. The lipopolysaccharide has a lipid A portion, a core oligosaccharide portion, and an O-specific chain having a single repeating unit 06. A lipopolysaccharide may be produced by washing and drying and E. coli bacterial mass, subjecting the washed and dried bacterial mass to a phenol/water extraction, and treating the extract with RNases, DNases, and proteinase K.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a refillable ink ribbon cartridge for use in an electronic typewriter or a printer and more particularly, to an ink ribbon cartridge for use in an electronic typewriter which includes a changeable feed spool replaced through one side opening and a winding spool about which is wound a used ribbon which is taken out of the cartridge by operation of a spring arm through the other side opening of the cartridge wherein the winding spool can be easily converted to the supply spool, whereby the used cartridge can be reused without creating waste materials.
2. Description of the Prior Art
Various types of disposal ink ribbon cartridges are well known in the art. For example, in such disposal ink ribbon cartridges, the feed spool and the winding spool are operatively maintained the resilience of an ink ribbon by a feed spool spring as described in U.S. Pat. No. 4,406,554 to Nally et al and U.S. Pat. No. 4,655,623 to Gasser. However, such ink ribbon cartridges are incapable of allowing replacement of the feed spool and have to be thrown away with the used ribbon after one use so as to create large amounts of waste materials. Furthermore, such ribbon cartridges do not disclose the use of a winding spool to be easily converted to a supply spool
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a refillable ink ribbon cartridge for use in an electronic typewriter.
Another object of the present invention is to provide an ink ribbon cartridge which includes a changeable feed spool replaced through one side opening and a winding spool about which is wound a used ribbon which may be removed therefrom by operation of a spring arm through the other side opening of the cartridge.
A further object of the present invention is to provide a refillable ribbon cartridge which includes a feed spool member having a semi-global member for slidably inserting into and removing from an aperture of a tensible plate supported on the cartridge, and a winding spool member having a semi-global engagement for converting into the feed spool member whereby the feed spool and winding spool members can be reused.
Still another object of the present invention is to provide a refillable ink ribbon cartridge for use in an electronic typewriter which includes a winding spool member having a winding spool spring and a plurality of stoppers for easily controlling the tensibility of the winding spool spring.
Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Briefly described, the present invention relates to a refillable ink ribbon cartridge for use in an electronic typewriter which includes a housing, a changeable feed spool member having a semi-global member for slidably inserting into and removing from an aperture of a tensible plate supported on the cartridge through one side opening, a winding spool member having a semi-global head engagement for converting into the feed spool member, a spring arm for easily removing the winding spool member from the cartridge through the other side opening of the cartridge, and a plurality of stoppers for easily controlling the tensibility of winding spool spring, and a jagged wheel, whereby the used ink ribbon cartridge can be reused and maintains a constant tension on an ink ribbon between the feed and winding spools.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a top plan view of a refillable ink ribbon cartridge in accordance with the present invention;
FIG. 2 is a front elevational view of FIG. 1;
FIG. 3 is a left side elevational view of FIG. 1;
FIG. 4 is a right side elevational view of FIG. 1;
FIG. 5 is a top plan view illustrating how to remove the used ribbon in accordance with the present invention;
FIG. 6 is a top plan view illustrating another embodiment of a feed spool member in accordance with the present invention;
FIG. 7 is a right side elevational view of FIG. 6;
FIG. 8 is a front elevational view of a hub having a semi-global member of a feed spool in FIG. 7;
FIG. 9 is a front elevational view of a hub having a semi-global member of a feed spool in FIG. 2.;
FIG. 10 is a cross-sectional view of the cartridge of FIG. 6, taken along line A--A;
FIG. 11 is a top plan view of another additional embodiment of a winding spool member;
FIG. 12 is a front elevational view of FIG. 11;
FIG. 13 is a left side elevational view of FIG. 11;
FIG. 14 is a perspective view illustrating another embodiment of a winding spool spring with the winding spool in accordance with the present invention;
FIG. 15 is a perspective view of a further embodiment of the winding spool spring with the winding spool;
FIG. 16 is an enlarged perspective view of the winding spool spring with the winding spool of FIG. 1;
FIG. 17 is a front elevational view of FIG. 11;
FIG. 18A is a perspective view of the cartridge in accordance with the present invention containing cut-away portions in order to illustrate the construction of a tension spring and the feed spool;
FIG. 18B is a perspective view of the cartridge in accordance with the present invention containing cut-away portions in order to illustrate the construction of a plastic plate spring;
FIG. 19 is an exploded perspective view of the winding spool having a semi-global member to be converted into the feed spool in accordance with the present invention;
FIG. 20 is a front elevational view of the winding spool having the semi-global member;
FIG. 21 is an exploded perspective view of still another embodiment of the winding spool spring according to the present invention;
FIG. 22 is an exploded perspective view of yet another embodiment of the winding spool spring according to the present invention;
FIG. 23 is a perspective view of another embodiment of the feed spool holding plate according to the present invention;
FIG. 24 is a top plan view of a further embodiment of the feed spool holding arm according to the present invention;
FIG. 25 is a cross-sectional view of FIG. 24, taken along line B--B; and
FIG. 26 diagrammatically shows the direction of force of a feed spool holding arm of FIG. 24.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now in detail to the drawings for the purpose of illustrating preferred embodiments of the present invention, the refillable ink ribbon cartridge 1 as shown in FIGS. 1-4 comprises a housing including a casing base 2, a casing top cover 3, a C-shaped rear wall 22, a feed spool side opening 21, a winding spool side wall 23, a front side wall 24 having a front side opening 20, a feed spool member including a feed spool 5, a winding spool member including a winding spool 6 disposed within the housing, and a drive roller 4 in the vicinity of the winding spool 6. The casing top cover 3 includes a feed spool guide channel 32 and a feed spool holding plate 30 having a hole 27 for receiving a semi-global member 31 of the feed spool 5 in the ribbon cartridge 1 through the feed spool guide channel 32 (FIG. 2) and a hook 45 of one end of a pivotal spring 44. Also, guide pins 8, 9, and 10 are supported on the casing base 2, for passing an ink ribbon 7 therethrough from the feed spool 5 to the winding spool 6. The C-shaped rear wall 22 is provided with a winding spool gulf 61 in the vicinity of the winding spool 6 for easily connecting the ink ribbon 7 to the winding spool 6 by the use of a finger.
The feed spool side opening 21 is disposed on the feed spool side of the ribbon cartridge 1 for easily inserting and removing the feed spool 5 into and from the ribbon cartridge 1. The feed spool side opening 21 has a gulf 51 for easily inserting the feed spool 5 having a brand-new ribbon 50 into the ribbon cartridge 1.
As shown in FIGS. 2 and 5, a V-shaped winding spool spring 13 pivotably connected to a fixed pin 11 through a pivotal spring ring 12 disposed at the center thereof. The V-shaped winding spool spring 13 is provided with a lever 28, a lever engagement 14, an arm 17, and a spring arm shaft 18 at the one end thereof for slidably receiving the winding spool 6 through a hub 66 of the winding spool 6 and the lever engagement 14 at the other end thereof for readily engaging a plurality of stoppers 15 and 16 disposed on the outside surface of the casing top cover 3 of the ribbon cartridge 1 (FIG. 1).
The drive roller 4 has a jagged wheel 40 for resisting the used ribbon 60 of the winding spool 6 and maintaining a constant tension on the ink ribbon 60 between the feed spool 5 and the winding spool 6 so that the ribbon 7 from the feed spool 5 has a substantially constant resilient force (FIG. Thus, the stoppers 15 and 16 alternatively give a constant biasing force to the hub 66 of the winding spool 6 for tight positioning against the jagged wheel 40 of the drive roller 4. For example, the lever engagement 14 of the V-shaped winding spool spring 13 is positioned in the stopper 15, the biasing force to the hub 66 of the winding spool 6 is stronger than that when the lever engagement 14 is positioned in the stopper 16. The V-shaped winding spool spring 13 defines an angle of 30° to 45° therebetween (FIGS. 1 and 5).
As shown in FIGS. 1 and 5, the fixed pin 11 supported on the casing base 2 receives the pivotal spring ring 12 of the V-shaped winding spool spring 13. The lever 28 of the V-shaped winding spool spring 13 for locking with the lever engagement 14 thereof is moved in the direction indicated by an arrow from the open position shown in FIG. 5 by releasing the lever 28 from the stoppers 15 and 16 to the closed position as shown in FIG. 1.
Referring in detail to FIGS. 6, 7, 8, 9, and 10, there is illustrated another embodiment of an ink ribbon cartridge 1 according to the present invention. Instead of the semi-global member 31 having a raised position 56 of the feed spool 5 of FIGS. 1 and 9, a head 501 and a tensible neck 502 of a feed spool 500 having the raised portion 56 thereof maintain the position of the feed spool 5 for slidably inserting the feed spool 500 into a head receiver 300 through a guide road 301 disposed on the casing top cover 3. At this time, the raised portion 56 inserts into a slot 25 disposed in the casing base 2 (FIG. 10).
Referring in detail to FIGS. 11, 12, and 13, there is illustrated a further embodiment of an ink ribbon cartridge 1 according to the present invention. The lever 28 of the V-shaped winding spool spring 13 is disposed within a spring housing 33 which duplicates on the casing top cover 3 for horizontally moving the lever 28 between the casing top cover 3 and spring housing 33.
Referring in detail to FIGS. 14 and 15, there are illustrated an additional embodiment of the winding spool member of the ink ribbon cartridge 1 according to the present invention. In the ink ribbon cartridge 1 of FIGS. 1 and 16, instead of the V-shaped winding spool spring 13, first of all, the V-shaped winding spool spring 13 turns over, that is, an arm 121 and a spring arm shaft 122 maintain the position of the arm 17 and the spring arm shaft 18. Second, bending levers 123 and 124 maintain the position of the lever 13 (FIG. 14). In FIG. 15, instead of the L-shaped arm 17 of FIGS. I and 6, bending arms 131, 133, and 136 maintain the position of the lever 28.
FIG. 17 is a perspective view illustrating another embodiment of the winding spool spring 13 (FIG. 14) in the application of the winding spool 6 in accordance with the present invention.
As shown in FIGS. 19 and 20, the winding spool 6 is provided a center pin 512 and a plurality of engagements 511 for mating with a plurality of pins 516 and a center pin receptacle 514 of the semi-global member 31. Therefore, by assembling the semi-global member 31 with the winding spool 6 (FIG. 19), the winding spool 6 can be easily converted to the feed spool 5 (FIG. 20). The semi-global member 31 has a plurality of slots 515, thereby separating the semi-global member 31 from the spool 6.
As shown in FIG. 18A, the ink ribbon 50 has to pass a spring end 45 of a pivotal spring 44 having a spring ring 42 about a fixing pin 41 supported on the casing base 2.
FIG. 18B is a perspective view illustrating another embodiment of the pivotal spring 44 according to the present invention. Instead of the pivotal spring 44, a plastic plate spring 222 maintain the position of the pivotal spring 44 and the plastic plate spring 222 having a spring end 223 is attached to the C-shaped wall 22 at the other end thereof.
FIG. 21 is an exploded perspective view of still another embodiment of the winding spool spring 13 according to the present invention. Instead of the V-shaped spring 13 of FIG. 14, the V-shaped spring 13 is provided with a T-shaped lever 100 including a ring 102 and a handle 101 disposed both horizontal ends and a slot 104 disposed a vertical end thereof, a lever cover 107, and a tensible stopper 115. Therefore, the V-shaped winding spool spring 13 is pivotally fixed with a tubular fixing pin 11 through the spring ring 12 thereof and then the spring end 123 is engaged with the slot 104. The lever cover 107 extends a pin 108 for slidably inserting the lever ring 102, the spring ring 12, and the tubular fixing pin 111 so that the T-shaped lever 100 can be locked to the tensible stopper 115. Accordingly, when the lever handle 101 is released from the tensible stopper 115, the winding spool 6 can be readily taken out from the ink ribbon cartridge 1.
FIG. 22 is an exploded perspective view of yet another embodiment of the winding spool spring 13 according to the present invention. Instead of the T-shaped lever 100 of FIG. 21, a C-shaped end lever 150 maintain the position of the lever 100 and the C-shaped end lever 150 includes a C-shaped end downwardly disposed at one end and a lever handle 154 disposed at the other end thereof. The C-shaped end contains a semi-cylindrical wall 153 for receiving the spring ring 12 and an engagement 152 for tightly receiving the spring end 123. Therefore, the lever handle 154 can be locked to and released from the tensible stopper 115 (FIG. 22).
As shown in FIG. 23, the casing base 2 is provided with a tensible feed spool holding plate 130 having a hole 36 disposed in the center thereof supported on the casing base 2 for slidably receiving the semi-global member 31 of the feed spool 5 through the gulf 51. At this time, the resilient force of the tensible feed spool holding plate 130 is proportioned to the width (X) and length (Y) of the tensible feed spool holding plate 130.
FIGS. 24, 25, and 26 illustrate a further embodiment of a feed spool holding arm 400 according to the present invention. The feed spool holding arm 400 has a U-shaped configuration. A first leg 401, a second leg 402, and a third leg 403 are extended from a first bending point 404, a second bending point 409, and one end 406, respectively. The first leg 401 includes a round end 407 for easily passing the ink ribbon 50 therethrough and an outwardly bending branch 408 for guiding the feed spool 5. The second and third legs 402 and 403 includes circular ends for slidably receiving the feed spool 5, respectively. Thus, the feed spool 5 can be tightly retained by the bending branch 408 and the circular ends 409 and 410 of the first, second, and third legs 401, 402, and 403.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included in the scope of the following claims.
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A refillable ink ribbon cartridge for use in an electronic typewriter which includes a housing, a changeable feed spool member having a semi-global member for slidably inserting into and removing from an aperture of a tensible plate supported on the cartridge through one side opening, a winding spool member having a semi-global head engagement for converting into the feed spool member, a spring arm for easily removing the winding spool member from the cartridge through the other side opening of the cartridge, and a plurality of stoppers for easily controlling the tensibility of winding spool spring, and a jagged wheel, whereby the used ink ribbon cartridge can be reused and maintains a constant tension on an ink ribbon between the feed and winding spools.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to tire of aircraft.
2. Discussion of the Prior Art
When an aircraft touches the ground at landing with a non-revolving wheel, a portion of the periphery of the tire suddenly touches the ground.
While the aircraft still has a relatively high speed of about hundred miles per hour, the periphery of the tire is in rest. At the moment when the tire touches the ground at landing, the ground immediately touches a portion of the periphery of the tire with a relative speed of roughly 100 miles per hour. Since the wheel and the tire have an own mass, they are unable to accelerate in the moment of meeting of tire and ground to the equalness of speed of the aircraft and peripherial speed of the respective tire. Consequently, the tire slips a while on the ground and is at this time subjected to great wear and heating. That shortens the life time of the tire tremendously.
This shows that the commonly used aircraft tires of the prior art have life-time and efficiency problems which require an improvement.
It is the intention of this invention, to provide such required improvement of tires of aircraft.
SUMMARY OF THE INVENTION
It is the object of this invention to provide the wheels of aircraft with tires, which revolve the wheels before actual touch down of the aircraft to a speed which reduces the difference of speeds between the ground and the periphery of the tire for the moment of touch down of the craft.
Another object of the invention is to prevent the slip of the tires on the ground during landing of aircraft.
A still further object of the invention is to prevent the speedy wear off of air craft tires at landing of aircraft.
Still another object of the invention is to revolve and accelerate the wheels of aircraft at landing procedures previous to the actual touching of the ground, without mechanical machinery.
It is also an object of the invention to revolve and accelerate the landing wheels of aircraft exclusively by the relative speed between the aircraft and the surrounding air.
Still another object of the invention is to obtain a revolving of the wheels of the aircraft prior to actual touch of the ground by specific configurations of the tires of the landing wheels.
A portion of the last mentioned object of the invention is, to provide extensions on the tire which have different resistance coefficients on the portions of the tire which are above the axis of the wheel and those portions of the tire which are below the axis of the respective landing wheel.
A preferred object of the invention is to provide the extensions with higher coefficient of resistance on those portions of the respective tire which are at the respective time below the axis of the respective landing wheel.
It is also an object of the invention to provide the mentioned extensions of the tire in such a style that at every angle of rotation the extensions with higher coefficient of resistance are below the axis of the wheel automatically and without the requirement of controllers or of human supervision.
More objects of the invention are, as follows:
Where the wheels of an aircraft, and therefore their tires, are stationary, relative to the aircraft, at touch down on landing ground, there is a large differential in velocity between the points of the tires which make first contact with the landing ground and to the landing ground itself. From the moment the tires make contact with the landing ground they begin to rotate, the rate of rotation increasing very rapidly to that rate appropriate for the particular speed of the aircraft moving on the landing ground, then gradually slowing down as the aircraft is braked. At the moment of touch down, there are considerable impact forces acting on the tires and these forces produce most of the wear and tear suffered by the tires. It was this problem in mind that the present invention was devised.
The present invention broadly consists in an aircraft tire wherein the tire has rotation means such that when the tire is mounted on a wheel of an aircraft and the aircraft is flying with the wheel down so that air flows past the tire, the airflow interacts with the rotation means to produce a net force causing or tending to cause rotation being such as to reduce the impact forces on the tire when the aircraft lands while moving over the landing ground.
Preferably the rotation means comprises a plurality of vanes attached to a side of the tire.
Preferably the vanes are moulded integrally with the tire.
Preferably each vane has a hooked shaped end portion leading to an elongated tail end portion.
Preferably the hook shaped end portion of the vane faces inwardly.
Preferably the tail end portion of the vane is angled outwardly with respect to the tangent to the circle described by the tire radius at the position of the vane.
Preferably the angle is 10 to 20 degrees with respect to the mentioned tangent, most preferably about 15 degrees.
Preferably the tail end portion of any vane terminates on a radial line of the tire and the hooked shaped end portion of the next vane commences substantially from that same radial line or is spaced therefrom by a distance substantially less than the length of the vane.
This invention may also be said broadly to consist in the parts, elements, and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more of said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such as known equivalents are deemed to be incorporated herein as if individually set forth.
The above defines the present invention, a preferred form and preferred forms which will now be described with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a perspective view of an aircraft tire according to the present invention wherein the rotation means comprises a plurality of vanes attached to a side of the tire.
FIG. 2 shows a side view of a portion of the tire showing three vanes in more detail.
FIG. 3 shows a perspective view of a single vane.
FIG. 4 illustrates a cross sectional view through a vane of the invention.
FIGS. 5 and 6 show cross sectional views through another embodiment of a vane of the invention in differently extended locations.
FIGS. 7 and 8 show resistance bodies of the prior art for the evaluation of the coefficients of resistance of the vanes of the invention.
FIG. 9 illustrates a cross sectional view through vanes of the invention on the top- and bottom-portions of a tire with the back ground illustrating in a view from the side the respective portions of the tire and of the aircraft.
FIG. 10 illustrates a calculation form for the calculation of the acceleration of the tire and its final speed of revolution after the tire became objected to the flow of air after the landing gear was extracted from the aircraft.
FIG. 11 shows an example of calculation in the form of FIG. 10.
FIGS. 12 and 13 show calculations for other forward speeds of the aircraft again in the form of FIG. 10 and with equal vanes as in FIG. 11.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As indicated above, FIG. 1 shows a perspective view of a fairly typical aircraft tire 10 of the invention. On one side 12 of the tire, the tire has rotation means which, in the preferred form of the invention, comprises a plurality of vanes 14 attached to the side 12 of the tire. The vanes are preferably made of the same rubber as the tire and are therefore preferably moulded integrally with the tire. In the embodiment shown in FIG. 1, the tire has a single circular array of vanes 14 on its side 12, each vane projecting laterally somewhat from the side of the tire.
Apart from the presence of the vanes 14, the tire 10 can be the same as any conventional aircraft tire. In use, the tires 10, are moulded on wheels of an aircraft. The aircraft can be of the type having a fixed undercarriage gear so that the wheels are permanently down. Alternatively, the aircraft can be of the type having a retractable and extendable undercarriage being lowered to put the wheels down when the aircraft is coming into land.
The number of vanes, and their size, shape and their disposition on the side 12 of each tire 10 are such that as the aircraft fitted with the tires and with its wheels down flies in direction "M" as shown in FIG. 1, the relative air flow past each tire 10 is generally in the opposed direction, direction "A", so as to produce a net force on each tire, causing or tending to cause rotation of the tire in the direction "R".
The object is such that, provided that any brakes associated with the aircraft wheels are released, rotation of the tire in direction "R" will occur. The effect of this is that on touchdown, each tire 10 is alreadly rotating in the appropriate direction "R" so as to reduce the velocity difference between the point of contact 16 of each tire 10 and the ground. By this means, the impact forces on each tire 10 are reduced, and can be considerably reduced, when the aircraft lands.
In the preferred embodiment of the invention shown in FIGS. 1 to 3, the vane 14 has a hook or crescent shaped end portion 18 leading to an elongated tail end portion 20. As best shown in FIG. 2, the hook shaped end portion 18 of each vane faces inwardly. The tail end portion 20 of each vane is preferably angled outwardly with respect to the tangent 22 to the circle described by the tire radius at the position of the vane on the side 12 of the tire. Based on tests conducted so far, the preferred angle is about 15 degrees.
The preferred disposition of each vane relative to the adjacent vanes is best shown in FIG. 2. This preferred disposition has the tail end portion 20 of any one of vane 14 terminate on a radial line 24 with the next vane having its hooked shaped end portion 18 commencing substantially from that same radial line 24 by a small distance which distance is substantially less than the length "L" (see FIG. 3) of each vane. In considering airflow along the radial line 24 towards the tire of FIG. 2, the tail end portion 20 of the vanes tend to present something of a wall to the airflow and much air actually flows over the sides of the vanes rather than passing through the gaps 26 between the vanes. Of course, some airflow will pass through the gaps 26. This is shown in FIG. 1 where "A1" represents such an airflow. The reaction force "F1" on the vanes and hence on the tire is such as to cause the tire to rotate in the wrong direction.
However, in considering the airflow along radial line 24 in a direction away from the tire of FIG. 2, it can be seen that the free ends of the hook shaped end portion 18 of the vanes represents a relatively small obstruction to airflow and the gaps 26 tend to act as funnels funneling airflow therethrough. In FIG. 1, this is shown by airflow "A2" which produces a force "F2" on the vanes and therefore on the tire tending to rotate the tire in the desired direction.
The force "F2" is greater than the force "F1" and therefore the net force is such as to cause rotation of the tire in the desired direction.
A single vane 14 is shown in more detail in FIG. 3. The length "L" of the vane may be about 55 mm and the width "w" may be about 30 mm. The depth of the vane "d", that is its projection from the side 12 of the tire, may be about 8 mm. A typical aircraft tire may have about 40 such vanes.
The above describes a preferred form of the present invention. However, various modifications can be made to the aircraft tire of the present invention without departing from the scope of the invention as has been broadly defined above. For a start, the vanes can have sizes, shapes and dispositions other than those which have been given above by way of example only. More than one circular array of vanes can be provided on a side 12 of the tire. The tire shown in FIG. 1 is suitable for locating on the left-hand side of the aircraft. However, it would not be suitable for the right-hand side of the aircraft if detained in the same orientation nor would it be suitable for the left-hand side of the aircraft if reversed. Therefore, an aircraft tire may have vanes provided on both of its sides so that it does not matter if the tire is used on the left or the right-hand side of the aircraft.
Instead of rotating means being in the form of vanes, they can be provided in the form of channels of appropriate shape and size in one of both sides of an aircraft tire, the air "A" flowing past the tire flowing through the channels in a manner similar to that flowing between the vanes of the preferred construction of tire.
Where the tires, and therefore the wheels, of an aircraft are rotating in an appropriate direction prior to and at point of touchdown, a number of advanages result. The wear on the tire is reduced because of the lack of skidding of the tires on the ground at touchdown. Therefore, the tendency for rubber to be torn from the tire is reduced and the number of landings permissible on the tires before they are replaced is increased.
The reduction of impact forces on the tires also reduces the stress on the undercarriage of the aircraft at touchdown. The drag as the wheels attain landing speed at touchdown is reduced.
ANALYSIS OF THE INVENTION
When a body moves with a forward speed "S" through common air of sea level with an area "A" of the body, the body will cause a resistance according to equation (1):
K=A Cw(ρ/2)S.sup.2 (1)
with "rho"=density of air=about 0.125 Kg s 2 /m,
S=speed in m/s,
A=area in m 2 ,
K=Kg and "Cw"=coefficient of resistance.
FIGS. 7 and 8 show halves of hollow balls in air-streams. FIG. 7 shows the air to flow against the outwards bowed surface of the half ball and the half ball has now the coefficient of resistance of "Cw"=0.33. In FIG. 8 the air blows into the hollow open part of the half ball and the coefficient of resistance is now "Cw"=1.33. These coefficients of resistance are known in the technologies, for example, from Huette I, page 797. Hutte is the german engineering hand book of Ernst publishing Company in Germany.
FIG. 9 shows a schematic which illustrates a portion of the tire of the invention below the aircraft but still above the ground. The body 71 of the aircraft holds on the landing gear structure the axis 72 of the wheel on which the tire of the invention is assembled. Below the tire is the surface 73 of the runway on which the aircraft intends to land. This surface is more remote from the tire than shown in FIG. 9. The portion of the tire which is upwardly located in the Figure is the top portion or upper portion 74 of the tire. The portion of the tire which is below the axis 72 located is the bottom portion or lower portion 75 of the tire. On the top and bottom portions each one single vane or resistance body of the invention is shown. This body is cited by 14 on the bottom portion and by 114 on the top portion of the tire. All vanes or resistance bodies are calculated in this analysis as located with their centers on a periphery which is defined by a radius "Rt" around the axis 72 of the tire.
It will be understood, that, as long as the tire is in rest, which means as long as the does not revolve, the entire tire is subjected to the forward speed of the aircraft 71. This forwards speed is defined as 76="S". However, if the tire revolves anti-clockwise in FIG. 9, the portion of the tire with radius "Rt", and thereby the centers of the resistance bodies 14, 114, become the speed "Vr"=2 Rt pi U
Vr=2RtπU (2)
with U=revolutions per second. The velocity "V" then appears in m/sec.
From FIGS. 4, 7 and 8 it is immediately seen, that the cross sectional areas of the vane or resistance body of FIG. 4 is about similar to the hollow half balls of FIGS. 7 and 8. Not exactly similar, because the vanes or resistance bodies 14,114 are not spherical in FIG. 1, but more close to hollow halfs of cylinders. On the other hand, the inclined tail portions 47 of vanes 14 add efficiencies in the direction of the invention as additions to the coefficients of the half hollow cylinders. Since the actual coefficients of resistance of the vanes are not yet measured, it will be at hand of the above explanations assumed that the coefficients of resistance in flow of the vanes 14,114 are substantially equal to those of FIGS. 7 and 8, respectively. Errors can become corrected during further prosecution and development of the invention. Thus, it should be memorized that the coefficient of resistance of the vane on the top portion of the tire will be "Cwt"=0.3 and the coefficient of resistance of the vane 14 on the bottom portion of the tire will be "Cwb"=1.3 respective to the existing flows of air.
Cwt=0.33 (3)
Cwb=1.3 (4)
The effective areas of the vanes are equal on the top portion and on the bottom portion of the tire. This effective area is the projection of the shape of the vane in the direction of the flow of air against the respective vane.
The sum of mass of the wheel plus tire will be considered to be concentrated along the circle with radius "Rt" of FIG. 9 and this mass is weight/9.81 m/s 2 .
Mass of wheel+tire=Kg(weight)/9.81=Kg mass (5)
It can be seen from FIG. 9 that, when the wheel revolves anticlockwise in the Figure, the relative velocity towards the vane becomes V=S minus Vr.
V=S-Vr (6)
and the air speed towards the vane 114 on the top portion becomes W=S+Vr.
W=S+Vr (7)
If a force acts against a body of a mass "M", the body becomes accelerated in accordance with Newton's law of force. It says:
Force=mass×accelaration, or:F=m a. (8)
From the above it is seen that the resistance of the vane 14 on the bottom portion is:
A·Cwb(ρ/2)V.sup.2 (9)
while the resistance of the vane 114 on the top portion is:
A·Cwt(ρ/2)W.sup.2 (10)
Defining the density of the air as 0.125 and the half of it as 0.0625 it is now easily possible to write a calculation form as it is shown in FIG. 10. In FIG. 11 a calculation of a sample is carried out in the form of FIG. 10. In the form of FIG. 11 the weight of the wheel plus tire is considered to be 100 Kg which brings the sum of mass of 100/9.81=10.19 Kg mass. Further, six effective vanes are considered on the top and bottom portions (three on each side) and the sum of the effective area "A" of these vanes is considered to be 0.06 m 2 . For example, six vanes of area 10×10 cm=0.01 m 2 .
An important novel step in forms 10 and 11 is that at the first calculation the tire is calculated to be in rest. The first vertical column in these forms now defines an intervall of time at which the tire with the wheel becomes accelerated under the forces of the air flows. In the actual calculation of the form of FIG. 11, these intervalls are considered to be 10 seconds. The assumed rough acceleration during the respective time intervall "Δt" (here 10 seconds) is calculated in the forms and the therefrom resulting new velocity "Vr" is then also calculated. The so obtained new sums of speeds "W" and "V" are then used as a start off in the next calculation for the next intervall of time in the respective horizontal line of calculations.
The forward speed "S" of the aircraft is calculated with 40 m/s in FIG. 11, which means with a speed of 144 km per hour.
The calculation in FIG. 11 shows that the tire accelerates fast at early time after start of revolving, while it accelerates slowly later after the start and nears a speed value at which no accelerates appears any more because the resistance on the vane in the top portion becomes equal to that in the bottom portion, due to the higher relative air speed on the vane of the top portion.
However, the result of the calculation also shows that after only one single minute=60 seconds, the tire has already a speed of almost 14 m/s at radius "Rt" which means an even higher speed at the outer face of the tire which will touch the run way at moment of landing. That is 14/40=0.35×100=35 percent of the landing speed of the aircraft. That shows that the invention is very effective and the tire of the invention obtains a much longer life that the aircraft tire without the means of the invention has. The form of FIG. 10 may be used for other outgoing data, especially also for different speeds "S" of the aircraft.
FURTHER DESCRIPTION OF THE PREFERRED EMBODIMENTS
The analysis of the invention has brought to light, that it is, due to the increasing relative speed "W" of the upper portion of the tire, a large effective area "Ab" is desired at the lower portion of the tire, while a smaller area "At" is desired at the upper portion of the tire for the respective vane or resistance body 14,114.
Consequently, the invention obtains a still better effect by the application of FIGS. 4 to 6.
FIG. 4 illustrates one of the samples of the basic structures of the vane of the invention. One portion of the inner face is formed by radius "ri" around line 52, while a portion of the outer face is formed by radius "Ro" around line 51. Both faces with radii Ro and ri meet at the bottom tip face 56. The radii meet the inclined faces which form the inclined tail 47 between the angles "beta"=54 and "alpha"=53 which go from the outer tip face 55. These geometrical data are given for the exact calculation of factors of resistance. For different angle and radii around different points, slightly different coefficients of resistance will appear.
FIGS. 5 and 6 illustrate, that for a most effective embodiment of the invention, the vanes of resistant bodies get inclinable flexible portions, for example, shanks 58 between roots 57 on the tire 49 and a bending portion 59, shanks 60 between bending portions 59 and 61 as well as outer wing portions 63 towards tips 64. The outer portions may be tapered in cross section by taper faces 62.
FIG. 5 shows the vane arrangement partially laterally extended while FIG. 6 illustrates it almost entirely laterally extended with shanks 158, 160, outer wing 162 and bending portions 159, 161 as well as tip face 164.
The outer face of the tire 49 is shown by 48. One sees the distance from the root 57 to tip 64 to be 65 in FIG. 5 while it is 165 between root 57 and tip 164 in FIG. 6. Distance 165 is considerably longer than distance 65 and defines thereby a larger area "A". FIG. 6 shows the vane on the lower portion of the tire with the air blowing from the right in FIG. 6, pressing against bend 159, shanks 158 and 160 as well as against outer wing 162, thereby forcing the vane to obtain its large dimension 165. In FIG. 5 the vane is shown on the top portion of the tire with the wind blowing from the left against the shanks and bend 59 as well as against the outer wing 62. Consequently, the airflow forces the wing of FIG. 5 to obtain its small dimension 65.
The invention aims to materialize wings of FIG. 5 with dimension equal to zero at time of location at the upper portion of the tire and with maximal length of dimension 165 at location of the respective vane at the lower portion of the tire.
If this aim will become obtained, the resistance "Ft" of the calculation form of FIGS. 10 and 11 becomes "zero" because the area "At" becomes "zero". Then, there is no braking force on the tire any more and the tire will accelerate very fast to obtain at the lower portion almost exactly the speed "S" of the aircraft. The tire would then touch onto the ground at the moment of landing without almost no difference in speed between the outer surface of the tire and the ground.
Instead of providing plural shank portions and plural bending portions for a vane it is also possible to use a single shank portion with the root on the tire forming the bending portion.
The features of the invention also reduce the possibility of metal fatigue in the fuselage of the aircraft in the area of the undercarriage and the undercarriage itself.
Another advantage is that the tendency for the tires of the aircraft to aquaplane on wet surfaces is reduced as the tires on rotating wheels tend to cut through surface water rather than slide over the surface, this allowing the tires to make contact with the landing ground sooner. Yet another advantage, is improved comfort to passengers and crew of the aircraft on touchdown. With the aircraft wheels rotating prior to touchdown in the appropriate direction the rough or rumbling vibrations through the aircraft as the wheels make contact with the landing ground is reduced. Where the aircraft wheels are stationary on touchdown they have to accelerate rapidly to achieve landing speed at the point of landing.
Therefore it is believed that the present invention offers significant advantages over existing types of aircraft tire.
The calculations of FIGS. 11 to 13 bring the result that regardless of aircraft speed "W" the tire accelerates each time to about 35 percent of the speed of "W" if the coefficients of resistance are as assumed in the calculations. At higher aircraft speed "W" the wheels accelerate faster but end their acceleration at same ratio of speed relative to the speed of the aircraft. This shows the great importance of election of effective shapes of the means of the invention to obtain the best increase of speed of the by the means of the invention rotated wheels. The coefficients of resistance at upper- and lower- portions of the tire almost exclusively define the rate of "speed-up" to the wheels.
Since the invention is still more in detail described in the present and probably also in future claims, the claims are considered to constitute a portion of the summary of the invention and of the description of the preferred embodiments of the invention.
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This invention introduces a tire for aircraft. The tire of the invention is provided with drive means to revolve the wheel of the aircraft at landing procedure before the aircraft actually touches the ground. The drive means consist of airflow responsive configurations on the tire. Preferably vanes of a specific configuration are formed on the tire to cause a bigger resistance to airflow along the tire at the bottom-most portion of the tire relative to the uppermost portion of the revolving tire. The bigger resistance of that portion of the tire which is closer to the ground forces the tire to revolve. Thereby it is possible to revolve the wheels of the aircraft automatically by the movement of the aircraft through the air and as a result thereof the wheels of the aircraft revolve at the moment of touching the ground with a speed which is substantially equal at the periphery of the tire relative to the speed of the aircraft to the ground. As far as equalness of the mentioned speeds is not fully obtained, the relative speed between the periphery of the tire and the ground at the moment of landing is reduced by the tire of the present invention.
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FIELD OF THE INVENTION
[0001] This invention relates to a novel integrated hydroconversion process for converting heavy hydrocarbon feeds containing vacuum residue and converting and reducing impurities in the straight run and conversion product vacuum gas oil liquids. This is accomplished by utilizing two residue ebullated-bed hydroconversion reaction stages, two vapor-liquid separators, and at least two additional distillate ebullated-bed hydrocracking/hydrotreating reaction stages.
[0002] In a two-stage residue hydroconversion reactor system, the atmospheric or vacuum residue feed and hydrogen react with a catalyst in the first residue hydroconversion stage to produce lighter hydrocarbons. The stage one effluent is thereafter separated in an interstage separator which separates the effluent into a liquid phase and a vapor phase.
[0003] The liquid phase from this interstage separator is then fed to the second residue hydroconversion reaction stage for additional conversion and impurity reduction. The resulting mixed-phase effluent product from this second stage is sent to a second high-pressure separator with the liquid product sent to product separation.
[0004] The overhead vapor from the first stage (interstage separator) and from the second vapor liquid separator contain significant unreacted hydrogen and are thereafter sent to separate distillate ebullated-bed reactors for conversion and hydrotreatment of the diesel and vacuum gas oils contained in these streams. These downstream ebullated-bed hydrogenating/hydrotreating reactors are called distillate ebullated-bed reactors to distinguish them from the upstream system. Additional feedstocks to these distillate ebullated-bed reactors could include straight run vacuum gas oil, cracked material from other processing units, and recovered diesel and VGO from the second-stage residue ebullated-bed hydrocracking product.
BACKGROUND OF THE INVENTION
[0005] Hydrocarbon compounds are useful for a number of purposes. In particular, hydrocarbon compounds are useful, inter alia, as fuels, solvents, degreasers, cleaning agents, and polymer precursors. The most important source of hydrocarbon compounds is petroleum crude oil. Refining of crude oil into separate hydrocarbon compound fractions is a well-known processing technique that can be accomplished by a variety of different methods.
[0006] Crude oils range widely in their composition and physical and chemical properties. Crude oil with a similar mix of physical and chemical characteristics, usually produced from a given reservoir, field or sometimes even a region, constitutes a crude oil “stream.” Most simply, crude oils are classified by their density and sulfur content. Less dense (or “lighter”) crudes generally have a higher share of light hydrocarbons—higher value products—that can be recovered with simple distillation. The denser (“heavier”) crude oils produce a greater share of lower-valued products with simple distillation and require additional processing to produce the desired range of products. Heavy crudes are also characterized by a relatively high viscosity and low API gravity (generally lower than 25°) and high percentage of high boiling components (>975° F.).
[0007] Additionally, some crude oils also have a higher sulfur content, an undesirable characteristic with respect to both processing and product quality. The quality of the crude oil dictates the level of processing and re-processing necessary to achieve the optimal mix of product output.
[0008] In the last two decades, the need to process heavier crude oils has increased. Refined petroleum products generally have higher average hydrogen to carbon ratios on a molecular basis. Therefore, the upgrading of a petroleum refinery hydrocarbon fraction is classified into one of two categories: hydrogen addition and carbon rejection. Hydrogen addition is performed by processes such as hydrotreating and hydrocracking. Carbon rejection processes typically produce a stream of rejected high carbon material which may be a liquid or a solid; e.g., coke.
[0009] To facilitate processing, heavy crudes or their fractions are generally subjected to thermal cracking or hydrocracking to convert the higher boiling fractions to lower boiling fractions, followed by hydrotreating to remove heteroatoms such as sulfur, nitrogen, oxygen and metallic impurities.
[0010] Further information on hydrotreating catalysts, techniques and operating conditions for residue feeds may be obtained by reference to U.S. Pat. Nos. 5,198,100; 4,810,361; 4,810,363; 4,588,709; 4,776,945 and 5,225,383 which are incorporated herein for this teaching.
[0011] Crude petroleums oils with greater amounts of impurities including asphaltenes, metals, organic sulfur and organic nitrogen require more severe processing to remove them. Generally speaking, the more severe the conditions required to treat a given feedstock (e.g. higher temperature and pressures), the greater the cost to build and operate the overall plant.
[0012] Worldwide, fixed-bed reactors are utilized considerably more than ebullated-bed reactors. The fixed-bed system is used for lighter, higher quality feedstocks and is a well understood system. Fixed-bed systems are used mostly for naphtha, mid-distillate, atmospheric and vacuum gas-oils, and atmospheric residua treatment.
[0013] However, as the feedstock becomes heavier, has a greater level of impurities, or requires more severe conversion levels, the fixed-bed system becomes less effective and less efficient. In these cases, the ebullated-bed reactor systems are better suited for residue processing.
[0014] In general, ebullated-bed reactors are utilized to process heavy crude oil feed streams, particularly those feeds with high metals content and high Conradson carbon residue (“CCR”). The ebullated-bed process comprises the passing of concurrently flowing streams of liquids, or slurries of liquids and solids, and gas through a vertically elongated fluidized catalyst bed. The catalyst is fluidized and completely mixed by the upwardly flowing liquid streams. The ebullated-bed process has commercial application in the conversion and upgrading of heavy liquid hydrocarbons and converting coal to synthetic oils.
[0015] The ebullated-bed reactor and related process well-known to those skilled in the art and is generally described in U.S. Pat. No. 25,770 to Johanson, which is incorporated herein by reference. Briefly, a mixture of hydrocarbon liquid and hydrogen is passed upwardly through a bed of catalyst particles at a rate such that the particles are forced into random motion as the liquid and gas pass upwardly through the bed. The catalyst bed motion is controlled by a recycle liquid flow so that at steady state, the bulk of the catalyst does not rise above a definable level in the reactor. Vapors, along with the liquid which is being hydrogenated, pass through the upper level of catalyst particles into a substantially catalyst free zone and are removed from the upper portion of the reactor.
[0016] Ebullated-bed reactors are generally operated at relatively high temperatures and pressures in order to process these heavy feedstocks. Since such operating parameters substantially increase the cost of designing and constructing the reactors, it would therefore be advantageous to have a system wherein the overall design and manufacturing costs were optimized for specific feedstocks or feedstock components. This optimization would result in a lower initial investment and lower annual operating costs.
[0017] Typically, multi-stage ebullated-bed overhead streams processing atmospheric or vacuum residues are combined and sent to additional separation steps including the recovery of light liquids and preparation of a recycle gas which contains any unreacted hydrogen. However, this is not thermally efficient since it requires the streams to be depressurized, cooled down and fractionated, resulting in energy loss.
[0018] Alternatively, the combined separator overheads containing significant unreacted hydrogen could be sent to a fixed-bed or ebullated-bed hydrotreater or hydrocracker to hydroprocess the liquids contained in the high pressure vapor plus any external or recycle distillates or VGO. However, even a small amount of entrained vacuum residue and/or fines would render a fixed-bed incapable of processing this feed. Moreover, if the feedrate is high, and if there are high amounts of external streams also requiring hydroprocessing, a single ebullated-bed reactor may not have sufficient capacity to hydroprocess the streams.
[0019] It would be therefore desirable to have a configuration which effectively integrates the petroleum atmospheric or vacuum residue hydrocracking and the vacuum gas oil hydrotreating/hydrocracking. Moreover, it would be highly desirable to have a configuration that overcomes the flowrate limitations of conventional designs described above. The present invention overcomes such limitations.
[0020] The term “vacuum gas oil” (VGO) as used herein is to be taken as a reference to hydrocarbons or hydrocarbon mixtures which are isolated as distillate streams obtained during the conventional vacuum distillation of a refinery stream, a petroleum stream or a crude oil stream.
[0021] The term “naphtha” as used herein is a reference to hydrocarbons or hydrocarbon mixtures having a boiling point or boiling point range substantially corresponding to that of the naphtha (sometimes referred to as the gasoline) fractions obtained during the conventional atmospheric distillation of crude oil feed. In such a distillation, the following fractions are isolated from the crude oil feed: one or more naphtha fractions boiling in the range of from 90 to 430° F. one or more kerosene fractions boiling in the range of from 390 to 570° F. and one or more diesel fractions boiling in the range of from 350 to 700° F. The boiling point ranges of the various product fractions isolated in any particular refinery will vary with such factors as the characteristics of the crude oil source, refinery local markets, product prices, etc. Reference is made to ASTM standards D-975 and D-3699-83 for further details on kerosene and diesel fuel properties.
[0022] The term “hydrotreating” as used herein refers to a catalytic process wherein a suitable hydrocarbon-based feed stream is contacted with a hydrogen-containing treat gas in the presence of suitable catalysts for removing heteroatoms, such as sulfur and nitrogen and for some hydrogenation of aromatics.
[0023] The term “desulfurization” as used herein refers to a catalytic process wherein a suitable hydrocarbon-based feed stream is contacted with a hydrogen-containing treat gas in the presence of suitable catalysts for removing heteroatoms such as sulfur atoms from the feed stream.
[0024] The term “hydrocracking” as used herein refers to a catalytic process wherein a suitable hydrocarbon-based feed stream is contacted with a hydrogen-containing treat gas in the presence of suitable catalysts for reducing the boiling point and the average molecular weight of the feed stream.
SUMMARY OF THE INVENTION
[0025] The object of this invention is to provide a new integrated petroleum residue hydrocracking and distillate vacuum gas oil hydrotreating/hydrocracking process configuration.
[0026] It is another object of this invention to provide a method for the processing of individual stage overhead vapors from the residue ebullated-bed hydrocracking reactors in separate distillate ebullated-bed reactors to overcome processing limitations at high feedstock throughput rates for conventional designs.
[0027] It is a further object of the invention to provide a unique integrated design which utilizes distillate ebullated-bed reactors for diesel and vacuum gas oil processing so as to alleviate issues relating to solids and vacuum residue carryover, which would normally be of concern for fixed-bed reactors.
[0028] It is yet a further object of the invention to provide the use of separate distillate ebullated-bed reactors to allow for additional processing capacity for streams other than those from the residue conversion step including straight run, cracked and FCC products.
[0029] A novel feature of the invention is the integration of the hydroconversion of heavy atmospheric or vacuum residue product with vacuum gas oil hydrotreating/hydrocracking in an ebullated-bed reactor. In the unique configuration of this invention, the heavy residue from the crude fractionator is sent to a multiple stage atmospheric or vacuum residue conversion process with an interstage separator. The liquid product from the interstage separator between the vacuum residue hydroconversion units is sent to the second-stage vacuum residue ebullated-bed hydroconversion unit for additional processing. The vapor products from the interstage separator and the vapor product from the second stage ebullated-bed hot separator are sent to separate distillate ebullated-bed reactors.
[0030] The straight run vacuum gas oil (“VGO”) products (e.g. those typically boiling in the 650-975° F. range) are sent to a feed drum along with additional VGO feeds, which are pumped to pressure and thereafter equally routed to a separate distillate ebullated-bed unit for processing. Although there are many other possible configurations, the one described below has two residue ebullated-bed units operating in series for processing the heavy residue and two distillate ebullated-bed units operating in parallel for the processing of the separator overhead vapors and external feeds consisting of primarily VGO from multiple sources.
[0031] More particularly, the present invention describes a process for the integration and treatment of multiple types and sources of hydrocarbons comprising:
[0032] A process for the treatment of heavy hydrocarbon feedstream(s) containing vacuum residue comprising:
[0033] a) passing said hydrocarbon feedstream into a first residue hydroconversion reaction stage ebullated-bed reactor to provide an effluent, said hydrocarbon feedstream boiling above 650° F. and having 50%-100% wt material boiling above 975° F.; and
[0034] b) separating said effluent from the first reaction stage ebullated-bed reactor in an interstage separator, where said effluent is separated into a vapor phase and a liquid phase; and
[0035] c) feeding the liquid phase from said interstage separator to a second residue hydroconversion reaction stage ebullated-bed reactor for additional conversion and impurity reduction; and
[0036] d) feeding the vapor phase from said interstage separator to a first downstream distillate ebullated-bed reactor for additional hydroconversion and hydrotreatment; and
[0037] e) processing the effluent from said second residue hydroconversion reaction stage ebullated-bed reactor to a hot, high-pressure separator to provide a liquid phase and a vapor phase from said high-pressure separator; and
[0038] f) feeding said vapor phase from said high-pressure separator to a second downstream distillate ebullated-bed reactor for additional conversion and impurity reduction; and
[0039] g) fractionating the liquid phase from said hot, high-pressure separator to produce naphtha, diesel, VGO, and unconverted residue, and
[0040] h) recovering effluents from first and second distillate ebullated-bed reactors.
[0041] Preferably, the hydrocarbon feedstream contains greater than 60% wt material boiling above 975° F., more preferably greater than 70% or than 80% or than 90%.
[0042] In a preferred embodiment, at least one separate source of materials boiling in the vacuum gas oil range (650-975° F.) which could contain materials boiling in the diesel range (350-650° F.) is also fed to at least one downstream distillate ebullated-bed reactor along with the vapor phase from said interstage separator or hot high-pressure separator of step f).
[0043] Generally, the effluent from the first downstream distillate ebullated-bed reactor and the effluent from the second downstream distillate ebullated-bed are combined and thereafter sent for hydrotreatment and product separation.
[0044] Advantageously, the VGO stream of step g) is thereafter recycled back to the first and/or second distillate ebullated-bed reactors.
[0045] In the process according to the invention, the overall conversion percentage of the hydrocarbon feedstream is preferably greater than 50% wt, and more preferably greater than 80%, or than 90% or than 95%.
BRIEF DESCRIPTION OF THE DRAWINGS
[0046] FIG. 1 is a schematic flowsheet of the integrated process for the hydroconversion of heavy residue and VGO hydrocracking/hydrotreatment.
DETAILED DESCRIPTION OF THE INVENTION
[0047] Crude oil ( 10 ) is first processed through a crude atmospheric fractionator ( 12 ) to create a bottoms stream ( 14 ) boiling above 650° F. and a lighter stream (not shown).
[0048] The bottoms stream ( 14 ) from the crude atmospheric fractionator ( 12 ) is thereafter sent to a vacuum fractionator ( 16 ) to create a residue feed stream ( 18 ) boiling above 975° F. and a vacuum gas oil (VGO) stream ( 20 ) boiling between 650° F. and 975° F. The VGO stream ( 20 ) is fed to a VGO feed drum ( 22 ) along with recovered VGO from downstream separation ( 78 ) and VGO from other processes ( 24 ) to create a VGO feed drum stream ( 28 ) and thereafter sent to a first ( 30 ) and second ( 32 ) distillate ebullated-bed reactors as hereinafter described. These additional VGO streams boil in the heavy diesel and vacuum gas oil range (650-1000° F.). Specifically, these streams can include, but are not limited to, external feeds from straight-run atmospheric or vacuum distillate towers, coker derived liquids, solvent deasphalting DAO, and liquid products recycled from the residue conversion unit.
[0049] The vacuum residue feed stream ( 18 ) is thereafter combined with a hydrogen stream and sent to a first residue ebullated-bed reactor for hydroconversion.
[0050] The effluent from the first residue ebullated-bed reactor ( 42 ) is thereafter sent to an interstage separator ( 44 ) and separated into a vapor phase ( 46 ) and a liquid phase ( 48 ). The interstage separator ( 44 ) is necessitated by the high vacuum residue feedrate as well as the need to minimize the initial investment needed for the plant design.
[0051] The vapor phase ( 46 ) will contain naphtha, diesel, some vacuum gas oil, and unreacted hydrogen. The vapor phase ( 44 ) from the interstage separator is combined with a portion of the VGO feed drum stream ( 28 a ) and sent to a first distillate ebullated-bed reactor ( 30 ) for conversion and treatment of the diesel and vacuum gas oils.
[0052] The liquid phase ( 48 ) from the interstage separator ( 44 ) is sent to a second residue ebullated-bed unit ( 50 ) for further vacuum residue hydroconversion. The effluent from the second vacuum hydroconversion ebullated-bed reactor ( 54 ) is then sent to a hot, high pressure separator ( 56 ).
[0053] The overhead stream ( 60 ) from the hot-high pressure separator ( 56 ) contains product diesel, some VGO, and additional unreacted hydrogen, which are thereafter combined with a portion of the VGO drum feed stream ( 28 b ) and sent to a second distillate ebullated-bed reactor unit ( 32 ) for further hydrogenation of the diesel and hydrogenation and hydrocracking of the vacuum gas oils. It should be noted that additional recycle or make-up hydrogen ( 64 , 65 ) can also be added to the first ( 30 ) and second distillate ebullated-bed reactor ( 32 ).
[0054] This second distillate ebullated-bed reactor ( 32 ) is arranged in parallel with the first distillate ebullated-bed reactor ( 30 ) which receives the overhead from the interstage separator ( 46 ) along with a portion of the VGO drum feed stream ( 28 a ). The product streams from the first and second distillate ebullated-bed reactors are thereafter combined and sent for product separation into naphtha, diesel and unconverted VGO.
[0055] The bottoms stream ( 70 ) from the hot, high-pressure separator ( 56 ) is thereafter sent to a product separator and fractionator ( 72 ) where it is separated into naphtha, diesel, unconverted residue stream, and a recovered VGO stream ( 78 ). The recovered VGO stream ( 78 ) is thereafter recycled back to the VGO feed drum ( 22 ) for further processing through the first ( 30 ) and second distillate ebullated-bed reactors ( 32 ).
[0056] This invention will be further described by the following example, which should not be construed as limiting the scope of the invention.
EXAMPLE 1
[0057] Vacuum residue feedstock is processed in a two-stage in series residue ebullated-bed unit. The feedrate to the plant is relatively high (>50,000 BPSD) and near the limit for a single train plant. The vacuum residue conversion system utilized in the example are residue ebullated-bed reactors. In addition to the vacuum residue feed to the residue ebullated-bed reactors, there are other VGO boiling range feedstocks (straight run, coker VGO and FCC cycle oils), which also require hydrotreatment and it is desirable to coprocess these streams in separate distillate ebullated-bed reactors along with the residue ebullated-bed overhead material which contains product diesel and vacuum gas oils. A summary of the feedstocks for this example is shown in Table 1.
[0058] This high feedrate and the need to minimize initial investment necessitated the use of interstage separation where a separation vessel between the residue ebullated-bed reactors is used to remove the gas and unreacted hydrogen from the first stage effluent. The liquid from the interstage separator is the feed to the second stage residue ebullated-bed reactor. The mixed-phase reactor product from the second stage effluent is separated in a hot high-pressure separator. The liquid from the hot high-pressure separator is the final heavy liquid product which contains full-range conversion liquids and is sent to downstream separation and fractionation.
[0059] In a pre-invention configuration, the two residue ebullated-bed reactor overhead streams would be combined and sent to additional separation steps including recovery of light liquids and preparation of recycle of the unreacted hydrogen. Alternatively, the combined overhead streams could be sent to a fixed-bed or ebullated-bed hydrotreater or hydrocracker to hydroprocess the liquids contained in the high pressure vapor plus any external or recycle distillates or VGO. However, due to the presence of a small amount of entrained vacuum residue and possible inherent or catalyst fines, this material cannot be effectively processed in a fixed-bed reactor system and an ebullated-bed reactor is most appropriate and typically specified. For high capacity situations and where significant quantities of external streams also require hydroprocessing, the flowrate of material to be processed is not possible in a single distillate ebullated-bed reactor. For this example, the C 5 + liquid flowrate to the distillate ebullated-bed system was nearly 68,000 BPSD with inspections summarized in Table 2. This large feedrate cannot be adequately processed in a single distillate ebullated-bed reactor and it is necessary to utilize two reactors. Suitable hydrogenation catalysts for the ebullated-bed reactor include catalysts containing nickel, cobalt, palladium, tungsten, molybdenum and combinations thereof supported on a porous substrate such as silica, alumina, titania, or combinations thereof having a high surface to volume ratio. Typical catalytically active metals utilized are cobalt, molybdenum, nickel and tungsten; however, other metals or compounds could be selected dependent on the application.
[0060] The arrangement of the distillate ebullated-bed reactors and apportioning of feedstocks is a key element of the invention. For a typical arrangement, all of the residue feed could be processed in a two reactor stage in series configuration, preferably the whole effluent from the first reactor passing in the second reactor. For this example however and for many applications, this arrangement was found to be infeasible as a result of the large gas volume and limitations on maintaining a liquid continuous reactor system. Combining the two hot high-pressure separator overheads and then equally splitting a high pressure gas stream to a parallel ebullated-bed reactor arrangement is also not technically feasible.
[0061] The solution presented in this invention is to have a separate distillate ebullated-bed reactor for each overhead material from the residue ebullated-bed conversion unit. The low-pressure external and recycle liquid feeds are combined in a gasoil drum and with two separate pumps, and fed to the two parallel distillate ebullated-bed reactors, and, in an advantageous mode typically equally fed. Since the interstage and hot high-pressure separator overheads comprise only a small portion of the total liquid reactor feeds, the operating conditions and process performance in each reactor are advantageously nearly identical for attaining the same product quality. An advantage of the invention is to allow lower temperatures in the distillate ebullated bed reactors than in the residue ebullated-bed reactors due to gasoil feed, which result both in better conversion of the gaseous distillates from the residue ebullated-bed reactors and in a less expensive overall process. The overall liquid and gas products are combined and sent to final product separation and fractionation. The combined yields and product qualities from the distillate ebullated-bed unit are shown in Table 3.
[0062] The invention may be applied to a wide range of atmospheric/vacuum residue conversion applications including ebullated-bed reactor systems with feed streams including petroleum atmospheric or vacuum residua, coal, lignite, hydrocarbon waste streams, or combinations there of.
[0000]
TABLE 1
Summary of Distillate Ebullated-Bed and Residue
Ebullated-Bed Feedstocks
SR 1
Coker
Vacuum
Derived
FCC 2
FCC
Feed
Residue
SR VGO
VGO
HCO
HLCO 3
Rate, BPSD
50,120
37,500
6,515
3,200
4,400
Gravity,
3.6
13.5
13.3
5.3
11.9
°API
Sulfur, W %
5.96
3.51
1.7
1.02
0.71
Nitrogen,
0.62
1.63
0.26
0.11
0.04
W %
TBP
Distillation,
V %
C 5 -350° F.
350-650° F.
24.5
81.3
650-975° F.
4.6
100.0
100.0
75.5
18.7
975° F.+
95.4
1 Straight Run
2 FCC HCO = Fluid Catalytic Cracker Heavy Cycle Oil
3 FCC HLCO = Fluid Catalytic Cracker Heavy Light Cycle Oil
[0000]
TABLE 2
Liquid Feeds to Distillate Ebullated-Bed Unit
Stage 1
Residue
Ebullated
Stage 2
Recycled
VGO Portion
Bed Ovhd
H-Oil
H-Oil
SR
Coker
of FCC
Feed
C 5 ±
Ovhd C 5 ±
VGO
VGO
VGO
HLCO
Total
Rate, BPSD
4,650
4,902
13,499
37,500
6,515
823
67,889
Gravity, °API
43.2
42.7
18.8
13.5
13.3
7.3
18.0
Sulfur, W %
0.25
0.25
0.67
3.51
1.7
1.13
2.35
Nitrogen, W %
0.13
0.13
0.35
1.63
0.26
0.07
0.20
TBP Distillation, V %
C 5 -350° F.
36.9
35.1
4.3
350-650° F.
50.7
52.8
6.3
650-975° F.
12.4
12.1
100.0
100.0
100.0
100.0
89.4
[0000]
TABLE 3
Net Distillate Ebullated-Bed Reactor Yields and Product Qualities
Yields
W %
V %
Process Performance
H 2 S
2.42
650° F. + CONVERSION,
44.7
W %
NH 3
0.20
Desulfurization, W %
97.2
H 2 O
0.23
Nitrogen Removal, W %
79.3
C 1
0.68
Hydrogen Cons., SCF/BBL
1,110
C 2
0.64
Capacity, BPSD (C 5 + )
67,900
C 3
0.84
Number of Reactors
2
C 4
0.68
1.10
Feed Gravity, °API
18.0
C 5 -350° F.
14.68
19.18
Feed Sulfur, W %
2.35
350-650° F.
31.95
35.21
Feed Nitrogen, W %
0.20
650-975° F.
49.46
51.56
Total
101.78
107.05
Product
Gravity
Qualities
°API
S, WPPM
N, WPPM
C 5 -350° F.
63.9
200
70
350-650° F.
33.2
330
120
650-975° F.
24.3
1,100
760
[0063] The invention described herein has been disclosed in terms of specific embodiments and applications. However, these details are not meant to be limiting and other embodiments, in light of this teaching, would be obvious to persons skilled in the art. Accordingly, it is to be understood that the drawings and descriptions are illustrative of the principles of the invention, and should not be construed to limit the scope thereof.
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This invention relates to a novel integrated hydroconversion process for converting heavy atmospheric or vacuum residue feeds and also converting and reducing impurities in the vacuum gas oil liquid product. This is accomplished by utilizing two residue hydroconversion reaction stages, two vapor-liquid separators, and at least two additional distillate ebullated-bed hydrocracking/hydrotreating reaction stages to provide a high conversion rate of the residue feedstocks.
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CROSS-REFERENCES AND RELATED APPLICATIONS
This application claims the benefit of priority to Chinese Application No. 201510226690.7, filed May 6, 2015, which is a divisional of Chinese Application No. 201510195795.0, entitled “A fused NHase with improved specific activity and stability”, filed Apr. 22, 2015, which is herein incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to the field of genetic engineering, and more particularly relates to a fused NHase with improved specific activity and stability.
Description of the Related Art
Nitrile hydratase (NHase; EC 4.2.1.84) is an enzyme catalyzing the hydration of a broad scope of nitriles to the corresponding amides. The NHase comprises a β-subunit, a α-subunit and a regulatory subunit and it is generally divided into the cobalt-type (Co-NHase) or the iron type (Fe-NHase) depending on the metal ion chelated with the active site.
NHase has been widely used in the industrial production of highly purified acrylamide and nicotinamide, since biotechnology synthesis has advantages of low-cost, low-energy consumption and less pollution compared to traditional chemical synthesis. However, most NHases with high activity are unstable during industrial application. For example, the NHases of Pseudomonas chlororaphils B23 and Rhodococcus sp. N-774 are unstable above 20° C., and the NHase of Rhodococcus rhodochrous J1 is merely stable between 10° C. and 30° C. In addition, it is necessary to maintain low reaction temperature to stabilize the NHases by refrigeration because of the exothermic reaction of nitrile-hydration, which usually causes enormous redundant energy cost. Furthermore, tolerance of NHase to high concentrations of the product is necessary in industrial manufacturing. Therefore, a more stable NHase with high activity and high tolerance is required for industrial manufacturing.
DETAILED DESCRIPTION
To solve the problems described above, the present invention provides a method of improving the specific activity, stability and tolerance of NHase. Usually, the subunits of NHase are separated, and they would be depolymerized at high temperatures which could result in enzyme inactivation. Therefore, the present invention fuses the β- and α-subunits with covalent bonds through molecular approaches, which eliminates the possibility of subunits depolymerization. The resulted fused NHase with improved stability is more suitable for using in the industrial production of acrylamide and the fusion strategy could be applicable for different NHases with separated subunits.
The present invention provides a mutant NHase with improved specific activity and stability. The β- and α-subunits of the mutant NHase are fused in the mutant NHase, and the regulatory subunit is either fused or coexpressed with the fused α- and β-subunits.
In one embodiment of the present invention, the nucleotide sequence of the mutant NHase from 5′ to 3′ is β-subunit gene (B gene), α-subunit gene (A gene), and regulatory subunit gene (P14K gene) fused together.
In one embodiment of the present invention, the mutant NHase is reconstructed from the parent NHase whose nucleotide sequence is SEQ ID NO: 1. And the amino acid sequences of the α-subunit, β-subunit and regulatory subunit of the mutant NHase are the same as those of the parent NHase from Pseudomonas putida NRRL-18668.
In one embodiment of the present invention, the amino acid sequences which encode the β-subunit, α-subunit and regulatory subunit are SEQ ID NO: 2, SEQ ID NO: 3 and SEQ ID NO: 4, respectively.
The B gene and A gene are linked by a linker, and the nucleotide sequence of the linker is SEQ ID NO: 5.
In one embodiment of the present invention, the nucleotide sequence of the mutant NHase is SEQ ID NO.6 or SEQ ID NO.7.
The present invention also provides plasmids containing the amino acid sequences of the mutant NHase above and genetically engineered strains expressing the mutant NHase.
In one embodiment of the present invention, the genetically engineered strain is a recombinant E. coli BL21 (DE3).
The present invention also provides a method of constructing a genetically engineered strain expressing the mutant NHase.
In one embodiment of the present invention, the method of constructing the genetically engineered strain comprises cloning the nucleotide sequence shown in SEQ ID NO: 6 or SEQ ID NO: 7 to the expression plasmid of pET-28a to make a recombinant plasmid and transforming the recombinant plasmid into E. coli BL21(DE3).
The present invention also provides a method of producing NHases by the genetically engineered strain. The recombinant E. coli expressing the mutant NHase was cultivated in 2YT medium (tryptone 16 g/L, yeast extract 10 g/L, NaCl 5 g/L) at 37° C. When the optical density at 600 nm (OD 600 ) of the culture reached 0.8, isopropyl-D-1-thiogalactoside (IPTG) and CoCl 2 .6H 2 O were added to the medium to induce the expression and maturization of NHase. The culture was subsequently incubated at 24° C. for 16 h.
The present invention also provides a method of improving the specific activity and stability of NHase, wherein the NHase is made by fusing the B and A gene together and coexpress the P14K gene, or by fusing the B, A and P14K gene together.
In one embodiment, the present invention provides a method is to fuse the B, A and P14K gene from 5′ to 3′ in the order of “B gene, A gene, P14K gene”, and the B and A gene are connected by a linker whose nucleotide sequence is set forth in SEQ ID NO: 5.
The application of the mutant NHase, especially the application of the mutant NHase in acrylamide production is also under the scope of the present invention.
The mutant NHases obtained by the gene fusion strategy of the present invention exhibited significantly improved specific activity, thermostability and product tolerance than those of the wild type NHase.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 . SDS-PAGE of the wild type NHases and the fused NHases expressed by E. coli . Line 1, molecular weight marker; line 2, the wild type NHases; line 3, the mutant NHase-(BA); line 4, the mutant NHase-(BA)P14K; line 5, the mutant NHase-(BAP14K).
FIG. 2 . Half-time in 50° C. of the wild type NHase and the fused NHases.
FIG. 3 . Product tolerance of the wild type NHase and the fused NHases.
FIG. 4 . The optimal pH of the wild type NHase and the fused NHases.
EXAMPLES
Materials and Methods:
2YT medium: 16 g·L −1 tryptone, 10 g·L −1 yeast extract, 5 g·L −1 NaCl.
The activity of NHase was detected by the method described as follows. The reaction mixture contained 500 μL 200 mM 3-cyanopyridine and 10 μl of the appropriate amount of the enzyme solution. The reaction was performed at 25° C. for 10 min and terminated with the addition of 500 μL of acetonitrile. Then the supernatant was collected by centrifugation and filtered though a 0.22 μm pore-size filter before measured by HPLC. One unit (U) of NHase activity is defined as the amount of enzyme that released 1 μmol nicotinamide per min under these assay conditions.
HPLC conditions: the mobile phase was water-acetonitrile buffer; detection wavelength was 215 nm; the column was C18 column.
Example 1: Construction of the Recombinant E. coli Expressing the Wild Type NHases-BAP14K
Construction of the recombinant E. coli expressing the wild type NHases-BAP14K was carried out by the following steps:
(1) Amplification of the parent NHase gene: Primers were designed according to the published sequence in NCBI to amplify the ABP14K gene encoding the parent NHase from P. Putida . The amino acid sequence of the β-subunit, α-subunit and regulatory subunit of the parent NHases were SEQ ID NO: 2, SEQ ID NO: 3 and SEQ ID NO: 4, respectively.
(2) Construction of recombinant plasmid containing the ABP14K gene: the amplified DNA fragment of step 1 was digested with Nde I and Hind III, and then ligated into the Nde I and Hind III sites of pET-24a to create a recombinant plasmid containing the ABP14K gene. The recombinant plasmid was named pET-24a-ABP14K.
(3) Construction of recombinant plasmid containing the full-length BAP14K gene: pET-24a-ABP14K was used as a template. B gene was amplified by primer pairs B-up (SEQ ID NO: 8) and B-down(BA) (SEQ ID NO: 9), A gene was amplified by primer pairs A-up(BA) (SEQ ID NO: 10) and A-down(AP) (SEQ ID NO: 11), and the P14K gene was amplified by primer pairs P14K-up(AP) (SEQ ID NO: 12) and P-down (SEQ ID NO: 13). The same amount of B, A, P gene were used as templates and the full-length BAP14K gene was amplified by an overlap extension PCR protocol with primer pairs B-up (SEQ ID NO: 8) and P-down (SEQ ID NO: 13). The recombinant plasmid containing the BAP14K gene was named pET-24a-BAP14K, and the NHase expressed by pET-24a-BAP14K was defined as the wild type NHase.
Transformation of pET-24a-BAP14K into E. coli BL21 (DE3): The recombinant plasmid pET-24a-BAP14K was transformed into E. coli BL21 (DE3). The positive transformants expressing the wild type NHase were screened.
Primers used in the present invention were shown in Tab. 1.
TABLE 1
Primers
SEQ
ID
Primer
sequence (5′ to 3′)
NO
B-up
GGAATTC AATGGCATTCACGATACT
8
B-down
CATATCTATATCTCCTTTCACGCTGGCTCCAGGTAGTC
9
(BA)
A-up(BA)
TGAAAGGAGATATAGATATGGGGCAATCACACACGC
10
A-down
CATATCTATATCTCCTTTTAATGAGATGGGGTGGGTT
11
(AP)
P14K-up
TAAAAGGAGATATAGATATGAAAGACGAACGGTTTC
12
(AP)
P-down
CCG TCAAGCCATTGCGGCAACGA
13
B-NdeI-
GGAATTC AATGGCATTCACGATAC
14
up
P-
GCCC TCAAGCCATTGCGGCAACGA
15
HindIII-
down
A-
GCCC TCAATGAGATGGGGTGGGTT
16
HindIII-
down
Linker1-
TACCTGGAGCCAGCG CCAGGT GGGCAATCACACACGCAT
17
up
Linker1-
CGTGTGTGATTGCCC ACCTGG CGCTGGCTCCAGGTAGTC
18
down
Linker2-
CCCACCCCATCTCAT CCAAAT GGAGATATAGATATG
19
up
Linker2-
CATATCTATATCTCC ATTTGG ATGAGATGGGGTGGG
20
down
Note:
restriction sites were in italics and bold; overlapping sequences were underlined.
Example 2: Construction of the Recombinant E. coli Expressing the NHase-(BA)P14K
The recombinant E. coli expressing the NHase-(BA)P14K was constructed by the following steps:
(1) The B and A gene were fused by linker 1 (SEQ ID NO: 5) by primer pairs Linker1-up (SEQ ID NO: 17) and Linker1-down (SEQ ID NO: 18) using pET-24a-BAP14K as a template. The resulted pET-24a-(BA)P14K was used as a template to amplify the (BA)P14K gene by primer pairs B-Nde I-up (SEQ ID NO: 14) and P-Hind III-down (SEQ ID NO: 15). The amplified (BA)P14K fragment was then digested with Nde I and Hind III, ligated into the Nde I and Hind III sites of pET-28a. The resulted recombinant plasmid pET-28a-(BA)P14K could express a fused NHase (nucleotide sequence shown in SEQ ID NO: 6), whose β- and α-subunits were fused together and the regulatory subunit was coexpressed. The NHase expressed by pET-28a-(BA)P14K was defined as NHase-(BA)P14K.
(2) The recombinant plasmid pET-28a-(BA)P14K was transformed into E. coli BL21 (DE3). Positive transformants expressing the NHase-(BA)P14K were screened.
Example 3: Construction of the Recombinant E. coli Expressing the NHase-(BAP14K)
The recombinant E. coli expressing the NHase-(BAP14K) was constructed by the following steps:
Primer pairs Linker2-up (SEQ ID NO: 19) and Linker2-down (SEQ ID NO: 20) were used to connect the A gene and P14K gene and pET-28a-(BA)P14K was the template. The resulted plasmid pET-28a-(BAP14K) contained a fused NHase gene whose B, A, and P14K gene fragments were fused together (nucleotide sequence shown in SEQ ID NO: 7). The NHase expressed by pET-28a-(BAP14K) was defined as NHase-(BAP14K).
The recombinant plasmid pET-28a-(BAP14K) was transformed into E. coli BL21 (DE3). The positive transformants expressing the NHase-(BAP14K) were screened.
Example 4: Expression and Characterization of the NHases
The E. coli recombinants obtained in example 1-3 were used to express the NHases.
The E. coli recombinants were firstly cultivated in 10 ml of liquid 2YT medium containing 50 μg/ml kanamycin at 37° C., then transferred to 500 ml of liquid 2YT medium with 1% inoculation. When OD 600 of the culture reached 0.8, IPTG was added to a final concentration of 0.4 mM to induce NHase expression, and CoCl 2 .6H 2 O was added to a final concentration of 0.05 g/l to obtain mature NHase. The culture was subsequently incubated at 24° C. for 16 h and then the cells were harvested for SDS-PAGE.
Results indicated that the wild type NHase, NHase-(BA)P14K and NHase-(BAP14K) were successfully expressed, as shown in FIG. 1 . The line 3 represented the mutant NHase-(BA) whose β-subunit and α-subunit were just fused in the absence of the regulatory subunit.
The characteristics of the subunits fused NHases:
Specific Activity
Determination of NHases was conducted by the following method. The E. coli recombinants were collected by centrifugation and resuspended with a 0.01M phosphate buffer (pH 7.5) twice before ultrasonic disruption. The enzyme in the supernatant was purified and then the enzyme activity was detected by HPLC.
Compared with 324.8 U/mg of the wild type NHase, the specific activity of NHase-(BA)P14K and NHase-(BAP14K) were 499.2 U/mg and 452.5 U/mg, which were increased by 53.7% and 39.3%, respectively. In addition, the specific activity of NHase-(BA) ( FIG. 1 , line 3) was 69.1 U/mg, indicating that the P14K was also necessary for cobalt incorporation in the fused NHase.
Furthermore, the kinetic parameters (K m , V max , k cat and k cat /K m ) of NHase-(BA)P14K and NHase-(BAP14K) were compared with the wild-type NHase. Results showed that the k cat value of NHase-(BA)P14K (723.4 s −1 ) and NHase-(BAP14K) (676.5 s −1 ) were both approximately 2-fold of the wild-type NHase (335.1 s −1 ), indicating that the fused NHases exhibited faster catalyze rate. In addition, the k cat /K m value of NHase-(BA)P14K (11.8·10 3 s −1 M −1 ) was about 1.5 fold of the wild-type NHase (8.1·10 3 s −1 M −1 ), indicating higher catalytic efficiency of NHase-(BA)P14K.
Thermostability
The thermostability of the NHases was measured by the following steps. First, the eppendorf tube containing the enzyme solution was placed in a metal bath at 50° C. for a while before placed on ice. And then, the tube was placed at 25° C. in the metal bath and 200 mM 3-cyanopyridine (substrate) was added to it. Ten minutes later, acetonitrile was added to terminate the reaction.
As shown in FIG. 2 , the half-life times of NHase-(BA)P14K and NHase-(BAP14K) were 26 min and 18 min, respectively, while that of the wild-type NHase was 9 min. Results suggested that the NHase-(BA)P14K and NHase-(BAP14K) exhibited higher thermostability than the wild-type NHase.
Product Tolerance of the NHases
The product tolerance of the NHases was measured by the following method. The reaction was conducted in 20 mM 3-cyanopyridine (substrate) with and without 0.5 M nicotinamide (product) for 10 min. The reduction of 3-cyanopyridine in each reaction was measured ( FIG. 3 ), and the reduction ratio (the proportion of the reduced 3-cyanopyridine amount in the reaction with and without 0.5 M nicotinamide) was calculated.
Results showed that the consumption of substrate of NHase-(BA)P14K and NHase-(BAP14K) in product containing reaction systems were increased by 26% and 18%, respectively compared with the wild type NHase, and increased by 23% and 15% respectively in reaction systems without product. In addition, the reduction ratios of NHase-(BA)P14K (0.86) and NHase-(BAP14K) (0.83) were higher than that of the wild type (0.80), indicating that the fused NHases exhibited stronger product tolerance than that of the wild type.
The Optimum pH
The enzyme activities of the fused NHases were measured under different pH and compared with the wild type, and the activity under their respective optimum pH was defined as 1(100%). As shown in FIG. 4 , the optimum pH of the three NHases were about 7.5.
These data showed that the specific activity, thermostability and product tolerance of NHase could be significantly increased by fusing the β subunit and the α subunit with the regulatory subunit fused or coexpressed at the same time.
While the present invention has been described in some detail for purposes of clarity and understanding, one skilled in the art will appreciate that various changes in form and detail can be made without departing from the true scope of the invention. All figures, tables, appendices, patents, patent applications and publications, referred to above, are hereby incorporated by reference.
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The present invention provides a fused NHase with improved specific activity and stability, which relates to the field of genetic engineering. This invention provides a method of overexpressing a fused NHase in E. coli and producing a mutant NHase with improved the stability and product tolerance. The invention provides a simple, efficient and safe method of making mutant NHase, and can produce a large amount of soluble NHases in a short period. The present invention makes a contribution to large-scale industrial production and further theoretical study of NHases.
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BACKGROUND OF THE INVENTION
The present invention relates to a spinning machine and more specifically to a ring-type spinning machine for spinning yarns comprised of finite length fibers, preferably carded wool. The machine is provided with a plurality of spinning locations at each of which two textile fiber strands are run together at a joining point after leaving a drawing machine at spaced locations as untwisted fiber strands and are twisted together to form a yarn upon travel to a spindle or the like. A sensor is associated with each spinning location which reacts to a break of one of the two fiber strands by interrupting the spinning of the yarn.
The twisting of the yarn can be produced by conventional means, preferably by means of a spindle which is located coaxially within a spinning ring upon which a runner carried by the yarn travels during winding of the yarn on the spindle. It is also possible to provide other devices for producing the twist and for winding up the yarn such as a rotating spinning head, a wing spindle or the like.
The interruption of the spinning of the yarn after one of the two fiber strands breaks is desirable because the yarn spun after the break in one of the fiber strands, has only half the mass per unit length. In further processing of the yarn, this weak point may easily lead to yarn breaks and low quality goods. Each working location of the spinning machine where yarn is produced is designated hereinafter as a spinning location.
In prior art spinning machines of this type, such as that disclosed in German Utility Model 79 12 423 a sensor is associated with each spinning location and is provided with a yarn guide which is movably supported between two positions on a holder and which is held in balance in the first position and can be moved out of this balanced position to a new position limited by the influence of the yarn passing therethrough. However, when these movement limits are exceeded upon breaking of one of the two fiber strands, a break is produced in the remaining strand travelling to the spindle by the yarn guide pivoting downwardly in a vertical plane by about 180° or horizontally by about 90°. This causes the remaining strand to be diverted by the yarn guide through a sharp acute angle which sooner or later results in the breakage of this remaining strand. There is no guarantee, however, that this break will actually occur because the twisting imparted to this remaining strand by the spindle may extend through the yarn guide clear back to the drawing machine. In addition, even if the remaining strand does indeed break, the period of time before the break occurs can vary greatly and cannot be predicted ahead of time.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to create a new and improved spinning machine of the type described above in which the spinning of the yarn at each spinning location will be reliably interrupted as a result of a break in either of the two fiber strands.
It is a further object of the present invention to provide a new and improved spinning machine which is simple in construction, reliable in operation and cost effective.
The present invention provides a new and improved ring spinning machine for spinning yarns comprised of finite length fibers having a plurality of spinning locations at which two untwisted textile fiber strands are joined together after leaving a drawing machine and form a yarn which is twisted upon travel to a spindle and having a sensor associated at each spinning location which reacts to a break of one of the two fiber strands by interrupting the spinning of the yarn, wherein the sensor senses a characteristic of the yarn which changes in a manner recognizable to the sensor when the yarn is comprised of only one of the two fiber strands so that in consequence of each such change of the yarn characteristic detected by the sensor, the sensor activates an interrupter to interrupt the spinning of the yarn.
The present invention provides a new and improved ring spinning machine for spinning yarns comprised of finite length fibers having a plurality of spinning locations at which two untwisted textile fiber strands are run together at a joining point after leaving a drawing machine at spaced locations and twisted together to form a yarn upon travel to a spindle and having a sensor associated with each spinning location which reacts to a break of one of the two fiber strands by interrupting the spinning of the yarn, wherein a suction device is provided for aspirating fibers discharged from the drawing machine which are not incorporated into the yarn and said sensor reacts to the fibers drawn in by the suction device from the spinning location and causes the spinning of the yarn to be interrupted when the fiber discharge/time sensed by the sensor exceeds a predetermined value indicating a break in one of the fiber strands.
The foregoing solutions make it possible to reliably interrupt the spinning of the yarn from the remaining fiber strand as a consequence of a break in one of the two fiber strands. By utilizing the apparatus according to the present invention, it is possible to interrupt the spinning of the yarn very quickly, preferably immediately after a break in one of the two fiber strands. It is also possible to interrupt the feed of the rovings to the drawing machine to reduce fiber waste.
The sensor provided according to the present invention must sense a characteristic of the yarn which recognizably changes when the yarn is being spun from only one of the two fiber strands. This characteristic can preferably be the approximate mass per unit length of the yarn or the approximate weight per unit length of the yarn, that is the fineness or size of the yarn. The sensing of the yarn fineness can preferably be done by sensing the capacitance but can also be accomplished by an optical sensing arrangement. This is also true of the arrangement utilizing the suction device.
In the operation of the ring spinning machine according to the present invention, the interruption of the spinning of the yarn remaining after a break in one of the two fiber strands can take place in various ways. In one preferred embodiment, the interrupter is a yarn severing device which is electrically activated and disposed adjacent the path of the yarn for severing the yarn. Such a yarn severing device can preferably be a cutting device or a hot wire for burning through the yarn. It is also possible for the interrupter to be in the form of a clamping device which is electrically operated to clamp the yarn to prevent further spinning. Frequently, a relatively long period of time passes before a yarn break is corrected. Since the yarn break is frequently not corrected until after completion of a draw, the broken fiber strand from the drawing machine at the spinning location in question is no longer twisted into the yarn but is aspirated away or in some other manner collected as waste, it is often advantageous to also interrupt the continued delivery of the individual fiber strands from the drawing machine to the spinning location in question after any such fiber strand break. This can be achieved by locating an interrupter upstream of the drawing machine to stop, sever, tear, etc., the rovings fed to the first feed roller pair of the drawing machine. Such an interrupter can be formed as a clamp or a severing device.
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of a preferred embodiment of the invention as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic, partial front view of a spinning location in the ring spinning machine according to a first embodiment.
FIG. 2 is a schematic, side elevation view of a spinning location in a ring spinning machine according to another embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The spinning location 10 of a ring spinning machine as shown in FIG. 1 includes a drawing machine 11 having a plurality of roller pairs for drawing two spaced fiber strands 17,17' running adjacent to each other wherein only the final roll pair 14 is illustrated. The lower roll 15 of the final roll pair 14 can be formed in a manner common in most spinning machines by a cylinder which extends over almost the entire length of the side of the spinning machine. An upper roller 16 is pressed against the lower roller 15 at each spinning location. The two individual fiber strands 17,17' passing through the drawing machine are guided by fiber strand guides (not shown) which are laterally spaced from each other and after leaving the final roll pair 14, the fiber strands merge at a common joining point 19 which is located immediately above a capacitance sensor 21 which includes a yarn guide. The two individual fiber strands leaving the final roll pair 14 are still in the untwisted condition and are considered as fiber strands 22,22' up to the point 19. After the joining point, the strands are twisted together to form a yarn 23. The yarn 23 passes through the capacitance sensor 21 and immediately thereafter, passes through a severing device 24 having two blades. This severing device 24 can be electrically activated and as a result of each activation of its two blades, the yarn 23 will be severed.
As long as the severing device 24 is not activated, the yarn 23 passes through the device without being touched. The yarn then passes through a yarn guide 25 disposed at a distance above a spindle and from there passes to the rotating spindle 26 while forming a ballon. A sleeve 27 is removably located on the spindle 26 and the yarn 23 is wound onto the sleeve to form a skein 29. On the way from the yarn guide 25 to spindle 26 the yarn 23 passes through a runner 30 which travels on ring 31 which coaxially surrounds spindle 26. The ring 31 at each location is carried by member 32 which reciprocates axially of the spindle to form the skein 29.
The capacitance sensor 21 continually takes measurements which are approximately proportional to the mass per unit length of the yarn. This measurement value is fed to a threshold value detector 33, the threshold value of which can be adjusted by means of a threshold value selector 34 which is common to all spinning locations on the machine so that the threshold value of the threshold value detector 33 can be adjusted to the number of the currently spun yarn in such a manner that the signal delivered from the sensor 21 is always lower than the threshold value of the threshold value detector 33. The threshold value detector 33 thus delivers an output signal whenever the mass per unit length of the yarn 23 falls below a predetermined percentage,, such as 20-30% below the set point value. The threshold value detector 33 is thus formed in such a manner that as long as the output signal of the sensor 21 is greater than the threshold value, the threshold value detector 33 delivers no output signal. The detector 33 will deliver an output signal when the signal of the sensor 21 falls below the set threshold value. It is further provided that a value falling below the threshold value is only signaled when this low value is maintained for a predetermined, short period of time, which is choosen in such a manner that it cannot be caused by chance fluctuations of the mass per unit length of the yarn 23. The threshold value detector 33 thus detects any change in yarn size caused by the fact that one of the two fiber strands 22 or 22' is broken, since this results in the mass per unit length of the yarn being reduced by about half. The output signal of the detector 33 which always appears when one of the two fiber strands 22 or 22' is broken is transformed and amplified in an impulse forming stage 36 and is then sent to the severing device 24 to initiate the cutting process so that the yarn 23 is cut by the severing device 24 and the spinning of the yarn is thus interrupted.
In addition to the threshold value detector 33 associated with the illustrated spinning location 10, additional identical threshold value detectors 33 are schematically illustrated in FIG. 1, each of which is associated with another spinning location of the spinning machine. The fact that the threshold values of the detectors 33 can be set in common by means of the central threshold value selector 34 simplifies the adjustment of the threshold values significantly. This type of adjustment is necessary every time the yarn size of the yarn to be spun is changed.
The spinning location 10' illustrated in FIG. 2 is similar to that shown in FIG. 1. The drawing machine 11 in this embodiment has three roller pairs 40, 41 and 14 which draw the two fiber strands 17,17' therethrough in spaced parallel relation. These two fiber strands 17,17' which are not illustrated separately in FIG. 2 since it is a side view, merge at a common joining point 9 after leaving the final roller pair 14. This joining point 19 is formed between the final roller pair 14 and the yarn guide 25 which is arranged coaxially above the spindle 26. The two fiber strands 22,22' leaving the final roller pair 14 as individual fiber strands are twisted together to form the yarn 23 which is wound on the spindle 26.
A suction tube 42 of an aspiration device 43 is disposed a short distance below the final roller pair 14. The aspiration device 43 includes a main suction chamber or channel which extends along the entire length of the machine from which the various suction tubes 42 branch off at each spinning location. Each suction tube 42 has a slot-like suction opening at its free end for aspirating all of the fibers not twisted into the yarn 23.
The suction tube 42 includes a clear section through which the light beam of a photo-optical sensor is directed. As long as both fiber strands 22 and 22' are spun into the yarn 23, only very few fibers will pass individually into the suction tube 42. If, however, one of the two fiber strands 22 or 22' breaks all the fibers of this fiber strand will pass into the suction tube 42 and a relatively heavy fiber stream is then formed within the suction tube which will weaken or even completely interrupt the light beam of the photocell device 45 to such an extent that the photocell device 45 activates an electronic control device 46 electrically connected thereto. The electronic control device 46 will then deliver an electric control signal to a stop device 24, to electrically activate the device. The reaction sensitivity of the control device 46 can be adjusted. The stop device 24' is located upstream of the draw-in roller pair 40 of the drawing machine 11 at a distance therefrom and as illustrated in FIG. 2, is comprised of two cooperating blades which are normally located at a distance from each other. The two rovings which run to the drawing machine 11 at the spinning location 10' pass between the two blades and as soon as the photo-optical device activates the control device 46, the stop device 24 will be activated to cut the two rovings.
The stop device 24' can also be formed in such a manner that it does not cut the two rovings, but rather clamps them to cause a tearing of the rovings or stops them in some other manner. In any case, the cutting, clamping or the like of the two rovings interrupts the spinning of the yarn 23 remaining after the break of one of the two fiber strands after a short time since the supply of the fiber strands to the yarn is halted.
The stop device 24' as shown in FIG. 2 can also be provided in place of or in addition to the interrupter 24 illustrated in FIG. 1 at the spinning location. If it is provided in addition it does not directly interrupt the spinning of the yarn since the interrupter 24 stops the spinning of the yarn earlier than would be possible for the stop device 24'. However, the stop device 24' will eliminate the continued delivery of the broken fiber strands shortly after the stopping of the spinning, thus avoiding unnecessary fiber waste.
The interrupter 24 at the spinning location 10 according to FIG. 1 can also be provided at the spinning location 10' according to FIG. 2 in order to interrupt the spinning of the yarn very quickly after a break in one of the fiber strands. The stop device 24' can then be either eliminated or used in conjunction with the stop device 24.
It is contemplated that various other types of interrupters can be used within the scope of the present invention. The fiber strands drawn and spun on the spinning machine according to the present invention consist of conventional finite-length fibers, preferably relatively long fibers such as carded wool or the like.
While the invention has been particularly shown and described with reference to a preferred embodiments thereof, it will be understood by those in the art that the foregoing and other changes in form and details may be made therein without departing from the spirit and scope of the invention.
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A ring spinning machine for spinning yarns comprised of finite length fibers has a plurality of spinning locations for combining two untwisted textile strands into a yarn to which a twist is imparted prior to winding up of the yarn. A sensor is associated at each spinning location which reacts to a break of one of the two fiber strands and causes an interruption of the spinning of the yarn. The sensor is designed to sense a characteristic of the yarn which changes in a manner recognizable by the sensor when the yarn is only being spun from one of the two fiber strands and an interrupter is provided which acts in response to the signal from the sensor to interrupt the spinning of the yarn upon the detection of a strand break.
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[0001] This application claims the benefit of U.S. Provisional Application No. 60/530,180, filed Dec. 17, 2003.
FIELD OF THE INVENTION
[0002] The present invention relates to an improved process for bleaching Kraft pulp and involves the use of hydrogen peroxide in the early stages of such a process—i.e., before the pulp is treated with chlorine or chlorine containing compounds.
BACKGROUND OF THE INVENTION
[0003] The production of chemical, or Kraft, pulp involves the cooking of wood chips in a digester at elevated temperature and pressure in the presence of suitable chemicals, such as a mixture of sodium hydroxide and sodium sulfide. The unbleached pulp (brownstock) is removed from the digester, washed and bleached. The purpose of bleaching and washing is to remove lignin from the brownstock and to brighten the pulp for subsequent use in paper making operations. The bleaching takes place in a number of successive steps involving the use of chemicals such as elemental chlorine, chlorine dioxide, sodium hypochlorite, ozone and hydrogen peroxide. Generally, chlorine and chlorine containing compounds have been used in the earlier steps followed by ozone, oxygen or hydrogen peroxide used mainly to brighten the pulp.
SUMMARY OF THE INVENTION
[0004] The present invention relates to an improved process in which hydrogen peroxide is used to treat brownstock obtained in a conventional kraft pulping process prior to treatment with chlorine or chlorine containing compounds.
[0005] The method of the present invention uses the hydrogen peroxide in the initial treatment of the brownstock following its removal from the digester.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] In the drawings:
[0007] FIG. 1 shows data from Example 1.
[0008] FIG. 2 shows data from Example 3.
[0009] FIGS. 3 and 4 show data from Example 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] In accordance with the present invention, brownstock from a conventional Kraft pulping operation is treated with hydrogen peroxide prior to treatment with other bleaching agents. When this process is employed, it has been found that the amount of chlorine, chlorine dioxide or other bleaching agents, required in subsequent steps can be reduced without adversely affecting the properties, particularly brightness, of the resulting pulp.
[0011] The treatment of the present invention is preferably conducted by including hydrogen peroxide in the water used in washing the brownstock. The peroxide is used alone as the sole bleaching agent and not in combination with other chemicals.
[0012] The amount of hydrogen peroxide can vary from 0.05 to 2.0% on pulp weight. In general, preferred results are achieved with peroxide in an amount equal to from 0.1 to 0.8% on pulp weight.
[0013] In addition to treatment of brownstock, the present invention can be used to treat recycle pulp such as that obtained in the recycling of newspapers. Here again the recycle pulp is treated with hydrogen peroxide followed by treatment with chlorine or chlorine containing compounds.
[0014] The process of the present invention results in pulp having a brightness equal to that obtained in the conventional process while using less chlorine or chlorine containing compounds. It can be conducted in conventional equipment so no capital investment is required and does not require the addition of alkaline chemicals since the brownstock is already alkaline.
[0015] In order to describe the invention in more detail, the following examples are set forth:
[0016] As is known to those skilled in the art “kappa” relates to the lignin content of the pulp and “brightness” relates to the whiteness of paper made from the pulp.
EXAMPLE 1
[0017] A softwood pulp was produced in a digester. After a few stages of washing, the pulp was stored in a high-density storage tank. The pulp kappa number before peroxide treatment was about 30 for several hours prior to the point where peroxide addition was started as shown on FIG. 1 .
[0018] Hydrogen peroxide was added to the high-density tank at the rate of 10 pounds/ton (0.5% on weight of pulp). Pulp stayed in the tank for approximately two hours at a temperature of 140 degrees Fahrenheit and a pH of 10.5. No caustic was added to the pulp.
[0019] The pulp kappa as recorded by the analyzer was about 22 after the peroxide treatment. The pulp was discharged from the tank, washed with additional water and fed to the bleach plant. A reduction of about 20 pounds/ton pulp as equivalent chlorine was noted in the bleach plant. A reduction of about 8 pounds/ton of caustic was also realized in the bleach plant. Pulp quality was maintained and a slight increase in the final pulp brightness was achieved. The kappa and chemical demand as total equivalent chlorine (TEC) are shown in FIG. 1 . As can be seen, during the period when peroxide was added at 10 pounds/ton the TEC was reduced. TEC was also reduced when the peroxide was added at 5 pounds/ton. Further reduction in caustic (% NaOH) it also shown in FIG. 1 .
EXAMPLE 2
[0020] Hardwood pulp was produced in a digester. After a few stages of washing, the pulp was stored in a high-density storage tank. The pulp kappa number before peroxide treatment was about 15 (14.7).
[0021] Hydrogen peroxide was added to the high-density tank at the rate of 2 pounds/ton (Example 2-1) (0.1% on weight of pulp) and 6 pounds/ton (Example 2-2) (0.3% on weight of pulp). Pulp stayed in the tank for one hour at a temperature of 140 degrees Fahrenheit and a pH of 10.5. No caustic was added to the pulp.
[0022] The pulp was discharged from the tank, washed with additional washer and fed to the bleach plant. The pulp kappa after the peroxide treatment was about 13. A reduction of about 4 pounds/ton pulp of chlorine dioxide (Example 2-1) and about 10 pounds/ton pulp of chlorine dioxide (Example 2-2) was noted in the bleach plant. About 2 pounds/ton caustic was also reduced from the bleach plant in (Example 2-2). Pulp quality and brightness were maintained. The data is shown in the following Table where the results of Example 2-1 and 2-2 are compared to a control in which no hydrogen peroxide was used.
TABLE Control 2-1 2-2 H 2 O 2 to HD (lbs./ton) 0.0 2.0 6.0 Decker Kappa 14.7 13.6 13.2 Decker Brightness 33.1 32.4 35.1 Bleach Plant: D100 ClO 2 (lbs./ton) 39.3 35.1 28.9 EOP kappa 2.2 2.2 2.3 EOP caustic (lbs./ton) 26.3 26.3 25.6 EOP Brightness 76.0 76.2 75.0 D1 ClO 2 (lbs./ton) 13.5 13.4 13.4 D1 Brightness 89.4 88.9 89.2
EXAMPLE 3
[0023] A softwood pulp was produced in a digester. After a few stages of washing, the pulp was stored in a high-density storage tank. The pulp kappa number before peroxide treatment was about 26.
[0024] Hydrogen peroxide was added to the high-density tank at the rate of 8 pounds/ton (0.4% on weight of pulp). Pulp stayed in the tank for two hours at a temperature of 140 degrees Fahrenheit and a pH of 10.0. No caustic was added to the pulp.
[0025] The pulp was discharged from the tank and fed to the bleach plant. A reduction of about 10pounds/ton pulp chlorine dioxide was noted in the bleach plant. About 4 pounds/ton caustic was also reduced in the bleach plant. Pulp quality was maintained and an increase in the final pulp brightness was achieved. FIG. 2 shows the reduction in chlorine dioxide from about 45 pounds/ton pulp when the hydrogen peroxide was first added to 40 pounds/ton or less over time.
EXAMPLE 4
[0026] Softwood pulp of kappa 28.5 was collected from a pulp mill and evaluated in the lab. Two levels of hydrogen peroxide, 0.2 and 0.4% based on the weight of the pulp, were added to the pulp. A base line experiment was also conducted without any hydrogen peroxide. No caustic was added.
[0027] Pulp was kept in bags at 140 degrees Fahrenheit for two hours. The pulp consistency was 12%.
[0028] The pulp was taken out of the bags, washed and the brightness and kappa number determined. A drop in kappa number and an increase in pulp brightness were noted. The effect was greater for the higher amount of hydrogen peroxide. The results are shown in FIGS. 3 and 4 .
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An improved process for bleaching Kraft pulp is disclosed. The improved process involves the use of hydrogen peroxide to treat brownstock before treatment with chlorine or chlorine containing compounds. The process may also be used to treat recycle pulp.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is to an ozonator, which is a type of chemical reactor apparatus.
2. Description of the Prior Art
Ozone (O 3 ) is a gas and was discovered in the mid-nineteenth century but its widespread use has only been after the 1950's and is used for environmental pollutant control. Ozonators have become popular in commercial use for rectifying man-made pollution. Ozone is a three atom allotrope of oxygen and is second only to fluorine in electro-negative oxidation potential. Although a natural ingredient of the earth's atmosphere it has become widely used to improve water quality. Ozone is an extremely efficacious oxidant which does not persist as a residual element in air and water treatment.
The widespread use of swimming pools as back yard recreational means and in municipal recreational associations has given rise to the making of the water used therein safe for swimming. In recent years chlorine pellets and the like have been used as the cost has been low and the test for concentration has been relatively simple. Chlorine and similar chemicals has been less than satisfactory in pools as this chemical addition has now become rather expensive and said chlorine has often adversely affected the eyes and skin of many swimmers. The rubber and like materials used in swim suits and pool equipment have also been adversely affected by these chemicals with discoloration and deterioration as a result. As and of itself chlorine-like pellets and like components are very dangerous and require careful handling and safe storage away from children and pets.
For many years ozone has been recognized as an outstanding bacteriacide and virus deactivant. Ozone is most economically produced by creating a "corona discharge." This occurs when electrons flow at sufficiently high potential through a gas such as air. In household air the addition of small amounts of ozone freshens the air and removes unwanted odors. Ozone is widely used to remove odors from waste dumps and to purify or alter stack gasses. An investigation and/or evaluation will indicate to what extent the addition of ozone to the air will control bacteria count and odors.
The production of ozone is shown in many prior U.S. Pat. Nos. among which are 599,455 as issued Feb. 22, 1893 and 744,096 as issued Nov. 17, 1903 to OTTO. These patents show "corona discharge" and motor driven components. They do not show adjustability for corona discharge or an air driven rotor. LINDER has U.S. Pat. Nos. 951,443 which issued on Mar. 8, 1910 and 969,547 which issued on Sept. 6, 1910. These also showed power rotated spark generator components. LINDERMANN disclosed a fixed ozone generator in U.S. Pat. No. 1,363,000 issued Dec. 21, 1920. DALY disclosed a water purifier in U.S. Pat. No. 1,865,433 issued on July 5, 1932. HARTMAN patented an ozone generator utilizing air moved by a fan in U.S. Pat. No. 1,991,668 issued Feb. 19, 1935.
More recent and incidentally much more complicated and expensive generators are shown in BLAIR, U.S. Pat. Nos. 3,365,383 as issued Jan. 23, 1968; ARFF, 4,049,552 as issued Sept. 20, 1977; GNEUPEL, 4,159,971 as issued in July 3, 1979; STOPKA, 4,176,061 issued Nov. 27, 1979; HUTTER, 4,101,783 as issued July 18, 1978; and SAYLOR, 4,314,995 as issued July 29, 1980. These patents and others as far as is known do not disclose a cylindrical generator with a rotor which brings atmospheric air into the ozone generation chamber. This chamber of applicant's invention utilizes the inflow of air to move metal blades in way of electrodes or conductors so that high voltage sparks can produce ozone. The rotating blades enable and insure that deterioration of the potential conductor ends does not occur.
SUMMARY OF THE INVENTION
This invention may be summarized, at least in part, with reference to its objects. It is an object of this invention to provide, and it does provide, an ozone generator in which atmospheric air is fed to an ozone generating chamber and this inflow of air impinges upon blades of a rotatable member. Said blades have conducting means that are rotated to bring their edges in way of adjustably spaced multi-conductors so that the desired corona discharge is produced with no appreciable burning of the edges.
It is a further object of this invention to provide, and it does provide, an ozone generator having metal screen blades carried by anti-friction bearings of jewel or the like pivots, these blades are carried by and with a conductor shaft which carries one side of a high voltage potential. The other side of this high voltage potential is fed to a metal screen disposed next to an outer support in which are mounted adjustable screws. These screws are adjusted so as to space and provide a gap for corona discharge. The circuit providing the rotation of the blade carrying member also may include a timer.
In brief, this summary of the invention pertains to an ozone generator in which incoming air is used to drive and rotate blades of a windmill or like device used therewith. These blades each have a conducting capability extending from a center shaft to the outer edges. These blade ends or edges are spaced from the ends of conducting screws, said screws engage a screen carried around the rotor blades. These screws are connected to one of the legs of the high voltage potential. The rotating blades are preferably a metal screen but may be metal embedded in plastic. The screen members forming the blades are of conducting metal and are attached to the shaft. Said shaft is also an electrical conductor with high voltage fed to the ends of the blades. Air is fed into the chamber by a positive pump or a fan or by negative pressure created when fluid flow is made through a filter and thence to a swimming pool or other body of water. It is to be noted that electrical codes require that a primary supply voltage be conventionally "ground fault protected" and in all installations such protection is contemplated.
As shown, a cylindrical member carries a plurality of adjustable metal screws whose shanks each are engaged in a close mesh screen acting as a conductor. This screen is preferably inside of the cylinder member. Each screw is adjusted to provide a determined spark spacing so that the desired corona discharge can be made. In one embodiment it is to be noted that the high voltage is also connected to a electro-static precipitator for removing dust from air passing through the ozone generator. The precipitator is used with the ozone generator for purification of the air into the room or house and for removal of undesirable odors such as from a kitchen, basement or bedroom. The high voltage is anticipated to be from six to fifteen thousand volts with a very low amperage consuming less than fifty or sixty watts. The air pump requires very low amperage at one hundred ten volts and a fan is also shown in another embodiment. The sparks developed for and in the corona discharge make or produce heat and the movement of air through the cylindrical chamber and the rotational movement of the blades past the ends of the adjusting screws during ozone generation produces a desired cooling effect.
In addition to the above summary the following disclosure is detailed to insure adequacy and aid in understanding of the invention. This disclosure, however, is not intended to cover each new inventive concept no matter how it may later be disguised by variations in form or additions of further improvements. For this reason there has been chosen specific embodiments of ozone generators utilizing air flow for rotating the blades and showing a preferred means for using the generating apparatus for swimming pools and the like and for purifying the air. These specific embodiments have been chosen for the purposes of illustration and description as shown in the accompanying drawings wherein:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 represents a somewhat diagrammatic, isometric view showing ozone producing apparatus in which ozone is produced by a corona discharge of high voltage, and also showing a circuit diagram for the operation of said ozone producing apparatus;
FIG. 2 represents a sectional side view, partly diagrammatic, and showing an ozone generator in which the rotor portion is driven by air moved by a fan, this generator also showing a circuit diagram for the operation of this ozone producing apparatus;
FIG. 3 represents a sectional view in an enlarged scale and showing the arrangement of components for and of the ozone generator of FIG. 1;
FIG. 4 represents a diagrammatic sectional side view of a negative pressure producing apparatus which may be used with fluid flow under pressure;
FIG. 5 represents a fragmentary, sectional, side view of apparatus that may be added to the ozone generator of FIG. 2 to produce electrostatic precipitation of dust particles in the air, and
FIG. 6 represents an alternate, partial circuit diagram showing the high voltage circuit of FIG. 1 arranged to produce high voltage with a minimum of associated electrical apparatus and producing said voltage with a minimum cost.
In the drawings to be more fully described below it is contemplated that at least the high voltage transformer and conductors will be housed in an equipment container so that any potential or voltage current leak will be positively contained. This box or container has not been shown since any shape, configuration and composition of material is merely a matter of preference and selection.
In the following description and in the claims various details are identified by specific names for convenience. These names are intended to be generic in their application. Corresponding reference characters refer to like members throughout the several figures of the drawings.
The drawings accompanying, and forming part of, this specification disclose details of construction for the purpose of explanation but structural details may be modified without departure from the concept and principles of the invention and the invention may be incorporated in other structural forms than shown.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Embodiment as seen in FIG. 1
Referring next to the drawings and in particular to FIG. 1, the ozone generator includes a cylindrical housing 10 which is preferably of plastic or other non-electrical conducting material. Adjacent the inner wall of this cylinder and inwardly of the ends thereof is a conducting screen 12 that provides one distributation means for high voltage electricity. In the side walls of this cylindrical housing are formed a plurality of threaded apertures in which adjusting screws 14 are mounted. The shank of each screw is threaded through a threaded aperture and passes through the screen to engage said screen and provide an electrical conducting path to the inner ends of each screw. Screen 12 is conventionally of metal such as stainless steel and is of a mesh that is sufficiently close that the shank of each screw firmly engages the screen to provide a positive conductor. Of course, the screen 12 may be eliminated with a conductor lead provided to each adjustable screw.
A rotatable conductor for the other leg of the high voltage includes a shaft 16 which is preferably an extrusion of metal and is adapted to receive and retain blade members 18. Preferably these blade members are of screen-type metal and as shown are four in number. Each blade is preferably slightly curved to increase the ability of each blade to rotate under the influence of a directed air stream. A lower end of shaft 16 is supported and carried by a bearing, a jewel journal or the like 19 in and by a disk 20 which is secured in the lower end of the cylindrical housing. The upper end of this same shaft 16 has a reduced portion 21 carried in a bearing or jewel or the like 22. This bearing is carried and supported by an upper disk 24. This reduced portion conventionally extends above the upper supporting disk 24 and is rotatably connected to a spring contact member 26 which may be a carbon block or cup contact and from thence to a flexible lead 28 extending to the wall of the cylindrical chamber 10.
In the depicted circuit for supplying high voltage to the generator many components are identified and are used in the apparatus wherein full and variable control is desired. This circuit may be reduced for economic reasons as in FIG. 6. A conductor 30 extends from a high voltage side of a transformer 32. This conductor is connected to spring contact member 26. The other side of transformer 32 (ground) is connected by a conductor 34 (usually flexible) to the screen or grid 12. A timer 35 is depicted as actuated by the flow of current in low voltage A.C. lines 36 and 37 and leading to adjustable transformer 38. This transformer is used to bring the high voltage transformer 32 into actuation and the output from the high voltage transformer to the ozone generating apparatus is from six to fifteen thousand volts. The low voltage transformer output also is shown with a timed closed control switch 39 which is actuated with and by the timer 35. Switch 40 is actuated to feed low voltage to conductors 42 and 43. A fuse 44 is also shown in one lead or conductor to protect the circuit in case of overload. The closing of switch 40 also provides a flow of current to an input air pump 45 and as depicted an output pump 46.
From air pump 45 the output is fed through conductors 48 and 50 to inlet nozzles 52 and 54 where pressurized air is caused to be directed by said impinging nozzles so as to direct the blast of air onto the blades 18 to provide a rotation of the assembly of the bladed conductor. Two nozzles 52 and 54 are shown but as few as one or as many as several may be used to direct the influent flow of air to induce rotation of the bladed apparatus. This rotated assembly, when carrying a high voltage, provides a corona discharge of sparks passing to the ends of the screws 14. The screw ends are adjusted in and out so the spark space is about one-half inch from each other and the rotation of this conductor varies from less than a hundred to as much as two hundred r.p.m. This speed is not critical and many factors determine the rotational speed including friction, air velocity, size of impinging nozzles, closeness of screen mesh and others. The ozone produced in the cylinder is drawn through collector 56 and thence through a conductor 58 to pump 46 and thence through flexible conductors not shown to the bottom of the swimming pool or like body of water to be treated. It is to be noted that ozone is also very beneficial to aerate water in ponds having fish.
Embodiment of FIG. 2
Referring next to FIG. 2, there is shown an alternate construction of the ozone generator of FIG. 1. The cylinder 10, screen 12 and screws 14 are like that above. Rather than air pump 46 and nozzles 52 and 54 the air within the chamber is moved by a fan 60 and the rotating conductor has angled blades 62 which are canted so as to induce rotation by the directing of air thereagainst and thereby. These blades are carried by attaching means provided by shaft 64. A jewel or bearing 19 as in FIG. 1 is secured to and carried by a perforated disk 66. This disk may also be a screen material of non-conducting material. Fan 60 is carried by support means 68 disposed to allow the free passage of air thereby.
The upper end of this shaft 64 is carried by and supported by a jewel or bearing 22 as in FIG. 1 above. A disk-like support means 68 is provided and is perforated or a screen that allows the passage of ozone carrying air. The upper end of this shaft 64 extends through the jewel or bearing and is engaged by a carbon block or contact 69. This block is carried by a spring member 26 (FIG. 1) so that conduction of high voltage for the conductor to the shaft end is made. This construction is very conventional. The produced air-bearing ozone exits from the top or bottom of the cylinder 10, as depicted, and by the directional rotation of the fan 60. The high voltage produced by transformer 32 receives the conventional A.C. and may also have a duration timing device, not shown, that establishes the duration of ozone produced by a confined area. The timer may be utilized to insure that excess ozone is not present or produced.
Enlarged Sectional View as in FIG. 3
In FIG. 3 is shown an enlarged sectional view of the apparatus of FIG. 1 showing the construction that is used for a controlled volume of ozone. The cylindrical member 10 has a conducting screen 12 adjacent to and held by the wall of the cylindrical member 10. Adjusting screws 14 have their shanks mounted in threaded apertures in this cylindrical member. These shanks are in contact with and conduct interiorally the high voltage carried by the conductive screen 12. Screen-type metal blades 70 provide members which are secured to extending rib portions 71 of a shaft 72 which preferably is an extrusion. Bolts and nuts 74 and 75 secure the blades to this shaft portion. These blades are preferably made of screen-type metal and are spaced so that the outer edges may pass by the inner ends of screws 14 to provide the spark or corona discharge. High voltage is passed or conducted across the space therebetween. The inlet nozzles 52 and 54 are disposed tangentially to cause the inflow of air to impinge upon these blades and cause the shaft mounted assembly to turn. The produced ozone is withdrawn from the chamber through a conductor 58 carried and mounted in the lower disk 20 (FIG. 1).
Apparatus of FIG. 4
In FIG. 4 there is shown a connection whereby ozone produced in the cylindrical member 10 may be fed into a water conductor 80. Ozone is fed into the interior of this reduced pressure producing member 82 through a conductor 84 and is drawn into and mixes with the water in the conductor 80. Ozone and air, as a mixture, is fed into the area of reduced pressure (venturi tube) so that a suction of the product is fed into the flow of water or fluid. Although this is an apparatus that can be used in the feeding of ozone into the fluid flow in said conductor 80, it is to be noted that where the pipe may be filled with water a check valve, not shown, may be inserted in the conductor line 84 so that any water or fluid as a backfeed is prevented from reaching the high voltage section.
Dust Precipitator as in FIG. 5
In FIG. 5 it is to be realized that the apparatus of FIG. 2 for producing ozone is altered so as to also remove dust from the atmosphere by additions to the apparatus which includes a lower filter 90. Said filter 90 is carried within housing 110 and an electrostatic field is provided and electrical conductors 92 and 94 are shown as connected to a source of high voltage and half-wave rectifiers 96 and 97 provide positive and negative current flow to insure removing unwanted particles of dust. In this field the particles of dust are charged and collected on an upper filter 98. Electrostatic precipitators for collecting dust are well known and the high voltage as provided in the ozone producing apparatus may also be used for dust precipitators. The particles of dust are electrostatically charged and are collected on screens by electrostatic precipitation which is more-or-less conventional and well known. A thermal protector and sensor are preferably provided in said added apparatus so as to detect excessive heat and prevent fire.
Circuit of FIG. 6
In FIG. 6 there is shown the circuit of FIGS. 1 and 2 as altered to require an absolute minimum of electrical components. The A.C. of conventional voltage is fed to switch 40 as above. A fuse 44 and the high voltage transformer 32 are as above described. The leads or conductors 42 and 43 may power pumps 45 and 46 as in FIG. 1 or may power fan 60 as in FIG. 2. This "bare bones" circuit is shown since it is contemplated that such an electrical circuit probably will be used in commercial applications where the components producing the high voltage and ozone will be in a safety enclosure and that all necessary adjustments and assembly are made at the factory or repair shop.
General Use
It is to be realized that the apparatus as shown is useful in both swimming pools, ponds or tanks and utilizes a high voltage electrical flow to rotating apparatus in which blades have conducting means extending to their tips. These blades and the apparatus associated therewith are moved at selected speeds. The corona discharge or spark passing from the tips of these blades to the ends of the adjusting screws enable the length and frequency of these sparks to be produced without burning of the conducting ends or tips of the blades.
The above described ozone generators, since they use high voltage, are preferably housed in a safety enclosure. This enclosure is contemplated to have a safety switch or disconnect if and when the enclosure is opened to inspect and/or repair and adjust the generator. A fuse is shown in the circuit and is adapted to "blow" when excessive amperage is drawn by the generator and associated apparatus. A time delay may or may not be used since the inflow of air through the jets causes the rotor assembly to turn under the influence of the influent stream of produced air. Electrical codes do not allow any electrical current within a given distance of a swimming pool. Usually the specified distance is about ten feet except for underwater lightening to which this invention does not pertain. To conform to this distance code a long length of plastic tubing can and is used to carry the produced ozone to said pool. This can be accomplished since the ozone is always a pressurized gas moved by the pump so said ozone can always be delivered through almost any desired length of tubing. The output end of this length of tubing is conventionally weighted and may have a commercial member such as Flexi-Mist (TM Blue Ribbon Pet Products) air stone mounted at the end of said tubing to disperse the ozone. The ozone produced can also be fed into the intake of a swimming pool pump used with a filter system.
It is to be noted that the screws 14 are the preferred electrical conductors but this is not to preclude the use of metal, rod-like members slidable in receiving means formed or provided in the tubular or cylindrical member 10. The conducting screen 12 is preferably disposed adjacent the inner diameter of member 10 but the conductor from the high voltage transformer 36 need not be to a screen 12 but may be a grid of conductors. The blades 18 are depicted as of screen-type mesh and of conducting metal but may be of plastic with wire or metal conductors extending to the outer edge by attaching means. The shaft 16 may be of non-conducting plastic with conducting wires affixed thereto and connected to conductors in the blades.
A carbon block or contact 69 is shown and is readily available but other contacting and current carrying means are known and contemplated. Fan 60 is a conventional bladed member rotated with and by readily available A.C. but other air propelling means may be provided including a squirrel cage blower. The filtering of the air fed to the ozone producing apparatus is only shown as an additional benefit to the apparatus. It is readily acknowledged that the apparatus must be tested and approved by all regulatory agencies. The ozone producing apparatus, when used with an outdoor pool, contemplates the generating of a volume of ozone for a period of time and poses no potential problem as excess ozone is dispelled in the atmosphere. In a building or house either for a pool, sauna, or an air purifier, the in and out transfer of atmosphere providing seal effectiveness of the building is a consideration. A positive timer is contemplated so that produced ozone does not exceed the acceptable limits established by regulatory agencies.
Terms such as "left," "right," "up," "down," "bottom," "top," "front," "back," "in," "out" and the like are applicable to the embodiments shown and described in conjunction with the drawings. These terms are merely for the purposes of description and do not necessarily apply to the position in which the ozone producing apparatus may be constructed or used.
While particular embodiments of the generating apparatus have been shown and described it is to be understood the invention is not limited thereto and protection is sought to the broadest extent the prior art allows.
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The apparatus for producing a desired quantity of ozone uses a flow of air in which a corona discharge utilizes high voltage to produce sparks. This apparatus includes a source of high voltage and the spark is produced when metal or conducting edge portions of the blades are moved in way of spaced conductors carried in a tubular confine. The blades are carried as an assembly which may be rotated by a flow of air. The flow of air and the turning of the assembly maintains the blades in a cooled condition so that unwanted burning of the edges of the blades does not occur. The corona discharged ozone may be used in swimming pools, or as an air purifier or dust eliminator. The ozone, when used in a closed building, will utilize a timer so an excess of ozone is not produced. The rotating of the bladed member is preferably by the flow of air, said volume of air flow regulates the speed of rotation.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to copending U.S. provisional application entitled, “MAMMALIAN CELL LINES SPECIFICALLY DEFICIENT IN O-LINKED GLYCOSYLATION,” having Ser. No. 60/455,365, filed Mar. 17, 2003, which is entirely incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] The U.S. government has a paid-up license in this disclosure and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of DK46403 awarded by the National Institutes of Health (NIH) of the U.S.
TECHNICAL FIELD
[0003] The present disclosure is generally related to providing a means for studying N- and O-linked glycosylation and providing a mammalian cell host capable of producing novel glycoproteins. More particularly, this disclosure is related to genetically modifying a cell line to express UDP-galactose 4-epimerase (GALE) capable of interconverting UDP-galactose (UDP-gal) and UDP-glucose (UDP-glc), but essentially incapable of interconverting UDP-N-acetylgalactosamine (UDP-galNAc) and UDP-N-acetylglucosamine (UDP-glcNAc).
BACKGROUND
[0004] Galactosemia is a rare genetic metabolic disorder. Symptoms of galactosemia are exhibited by elevated blood galactose levels, which may result in mental deficiencies and the formation of cataracts, among other complications, and, if untreated, ultimately death. Most of these symptoms can be avoided with early detection of the disease in children. Relief is given by simply restricting galactose from the diet. Because of the lack of certain enzymes, galactokinase (GALK), galactose- 1 -phosphate uridyl transferease (GALT), or UDP-galactose 4-epimerase (GALE), the body is unable to break down galactose, which then builds up, together with its by-products, and becomes toxic. GALE is the third enzyme in the metabolism of dietary galactose and the key enzyme in de novo synthesis of galactose and its metabolites from glucose. Human GALE catalyzes reversible reactions between UDP-gal and UDP-glc and between UDP-galNAc and UDP-glcNAc. A deficiency of this enzyme results in epimerase deficiency galactosemia, a variant form of galactosemia with clinical severity that ranges from apparantly benign to potentially lethal.
[0005] Human GALE catalyzes, as mentioned above, the interconversion of UDP-gal and UDP-glc and the interconversion of UDP-galNAc and UDP-glcNAc. It is known that by interconverting UDP-gal and UDP-glc, GALE activity serves as an important regulator of these metabolite pools, which in turn serve as substrate pools of glucose and galactose for the addition to growing sugar chains for both N-linked and O-linked glycosylation and lipid-linked sugars. It is also known that UDP-galNAc is the obligate first sugar donor for all O-linked glycosylation reactions in mammals. By inhibiting the UDP-galNAc/UDP-glcNAc interconversion, but not UDP-gal/UDP-glc interconversion, glycosylation of N-linked sites can proceed as normal. Glycosylation sites on proteins are classified into two groups—as either N-linked or O-linked. Some glycoproteins carry only N-linked sugars, some carry only O-linked sugars, and many carry both. More than half of all eukaryotic proteins carry covalently attached oligosaccharide or polysaccharide chains.
[0006] In N-linked glycoproteins, the glycans are usually attached through N-acetylglucosamine or N-acetylgalactosamine to the side chain amino group in an asparagine residue. In O-linked glycoproteins, glycans are usually attached through an O-glycosidic bond between N-acetylgalactosamine and the hydroxyl group of a threonine or serine residue. Important N-linked glycans are found in ovalbumin and the immunoglobulins. Every immunoglobulin has carbohydrate attached to the constant domain of each heavy chain. Part of the recognition of immunoglobulins is due to the sequence of the oligosaccharide chains of the glycans.
[0007] A very important further use of N-linked oligosaccharides is in intracellular targeting in eukaryotic organisms. Proteins destined for certain organelles or for excretion from the cell are marked specifically by oligosaccharides during post translational processing to ensure they arrive at their proper destinations.
[0008] Important O-linked glycans appear to function in intracellular targeting and molecular and cellular identification. One example is found in the blood group antigens. Also, mucins, which are found extensively in salivary secretions, contain many short O-linked glycans. These glycoproteins increase the viscosity of the fluids in which they are dissolved.
[0009] The bacterial counterpart form of GALE, in particular that from Escherchia coli ( E. coli ) (WTeGALE), can only interconvert UDP-Gal and UDP-Glc. As discussed above, when the UDP-galNAc and UDP-glcNAc interconversion is absent, and in the absence of environmental sources of UDP-galNAc, glycosylation proceeds via the N-linked pathway only.
[0010] Clone ldlD cells are a CHO-derived line originally isolated from a screen for mutants defective in the endocytosis of low density lipoprotein (LDL) as described by Krieger, M. et al. J. Mol.Biol. 150:167-184 (1981). Subsequent studies demonstrated that the LDL receptor defect in these cells was part of a pleiotropic defect in the addition of sugars to glycolipids and glycoproteins, including the LDL receptor, and that these defects all resulted from a loss of GALE activity. Kingsley et al. Cell 44: 749-759(1986); Kingsley et al. The New Eng. J. of Med. 314: 1257-1258(1986). Further, studies by Krieger et al.(1986) and Krieger et al. Methods in Cell Biology 32: 57-84(1989) have demonstrated that the LDL receptor defect, like other glycoprotein and glycolipid defects in ldlD cells, was “environmentally reversible,” meaning that both glycosylation and function could be restored by the addition of low levels of both galactose and galNAc to the culture medium, thereby enabling cellular production of UDP-gal and UDP-galNAc via the sugar salvage pathway. Addition of either gal or galNAc alone enabled only partial glycosylation of the LDL receptor, presumably because, while UDP-gal serves as a galactose donor for the growth of both N- and O-linked sugar chains, UDP-galNAc is the obligate first sugar donor for all O-linked glycosylation in mammals Krieger et al.(1989). Considering that no truly GALE-null patients have been identified, and no GALE mouse knock-out is yet available, ldlD represents the only mammalian cell line currently available that is completely deficient in GALE activity.
[0011] Although for over a decade the ldlD cell system has provided a valuable tool for the study of both N- and O-linked glycoproteins in mammalian cells (Krieger et al.(1989)), a fundamental problem has remained—namely that because ldlD cells lack epimerase activity, galactose is not only necessary for their production of UDPgal, it is also toxic to them. Indeed, it was reported that ldlD cells exposed to concentrations of galactose greater than 75 microMolar (μM) will experience toxicity, although wild-type CHO cells demonstrate no apparent toxicity from exposure to galactose levels as high as 10 milliMolar (mM). Krieger et al.(1989). While short-term experiments involving low levels of galactose/galNAc addition are feasible, the biochemical phenotype observed is nonetheless a composite of corrected glycosylation defects superimposed upon metabolic abnormalities resulting from impaired metabolism of galactose. As such, these cells may serve as a useful model system representing epimerase deficiency galactosemia in its most extreme theoretical form, but they cannot support clean dissection of the cellular phenotypes reflecting impaired glycosylation, from those that result from impaired Leloir metabolism of galactose.
[0012] Tunicamycin is a known antibiotic that inhibits the synthesis of all N-linked glycoproteins by blocking the transfer of N-acetylglucosamine moiety to dolichol phosphate. The treatment of various cell lines with tunicamycin has permitted the study of glycosylation as it proceeds solely via O-linked glycosylation. There currently exists no counterpart to tunicamycin and no clean mechanism whereby O-linked glycosylation is specifically inhibited to permit the study of N-linked glycosylation in the absence of O-linked glycosylation.
[0013] Thus, a heretofore unaddressed need exists in the industry to address the aforementioned deficiencies and/or inadequacies.
SUMMARY
[0014] This disclosure provides an isolated polynucleotide comprising a polynucleotide selected from: a polynucleotide sequence set forth in SEQ ID NO: 1(C307YhGALE) or a degenerate variant of the SEQ ID NO: 1; a polynucleotide sequence at least 90% identical to the polynucleotide sequence set forth in SEQ ID NO: 1; a polynucleotide sequence at least 75% identical to the polynucleotide sequence set forth in SEQ ID NO: 1; and a polynucleotide sequence at least 50% identical to the polynucleotide sequence set forth in SEQ IDNo: 1
[0015] Briefly described, SEQ ID NO: 1 is human GALE (hGALE) having an adenine substituted for guanine, changing a TGT codon at residue 307 (encoding cysteine) to a TAT codon (encoding tyrosine) which is identified as C307Y.
[0016] The polypeptide of the present disclosure is selected from: an amino acid sequence set forth in SEQ ID NO: 2 (C307YhGALE), or conservatively modified variants thereof; an amino acid sequence that is at least 90% identical to SEQ ID NO: 2; an amino acid sequence that is at least 75% identical to SEQ ID NO: 2; and an amino acid sequence that is at least 50% identical to SEQ ID NO: 2. SEQ ID NO: 2 corresponds to wild type hGALE except a tyrosine residue has been substituted for cysteine at position 307. This single amino acid substitution results in a substantial decrease in the ability of hGALE to interconvert UDP-galNAc and UDP-glcNAc while still maintaining the ability to interconvert UDPgal and UDPglc. It will be appreciated that the substitution of other bulky amino acids, such as phenylalanine, tryptophan or histidine in place of tyrosine as described above may also accomplish the desired results.
[0017] The present disclosure further provides a vector comprising the polynucleotide as described above where the vector is preferably pPIC3.5K.
[0018] The present disclosure further provides a host cell comprising a vector comprising the polynucleotide described above where the host cell can be Pichia pastoris, Saccharomyces cerevisiae, Schizosaccharomyces pombe, or Escherichia coli. The host cell is preferably Pichia pastoris.
[0019] The present disclosure further provides a process for producing a polypeptide comprising culturing a host cell, preferably Pichia pastoris, under conditions sufficient for the production of the polypeptide where the polypeptide has the characteristics that the polypeptide is capable of UDP-gal/UDP-glc interconversion and substantially incapable of UDP-galNAc/UDP-glcNAc interconversion. The polypeptide is selected from: an amino acid sequence set forth in SEQ ID NO: 2 (C307YhGALE) or conservatively modified variants thereof; an amino acid sequence that is at least 90% identical to SEQ ID NO: 2; an amino acid sequence that is at least 75% identical to SEQ ID NO: 2; and an amino acid sequence that is at least 50% identical to SEQ ID NO:2.
[0020] The present disclosure further provides a cell line transfected with an expression vector comprising a polynucleotide SEQ ID NO: 1 (C307YhGALE) or a degenerate variant of the SEQ ID NO: 1; a polynucleotide sequence at least 90% identical to the polynucleotide sequence set forth in SEQ ID NO: 1; a polynucleotide sequence at least 75% identical to the polynucleotide sequence set forth in SEQ ID NO: 1; and a polynucleotide sequence at least 50% identical to the polynucleotide sequence set forth in SEQ ID No: 1, encoding a polypeptide having the characteristics that the polypeptide is capable of UDP-gal/UDP-glc interconversion and substantially incapable of UDP-galNAc/UDP-glcNAc interconversion. The polypeptide is selected from: an amino acid sequence set forth in SEQ ID NO: 2 (C307YhGALE), or conservatively modified variants thereof; an amino acid sequence that is at least 90% identical to SEQ ID NO: 2; an amino acid sequence that is at least 75% identical to SEQ ID NO: 2; and an amino acid sequence that is at least 50% identical to SEQ ID NO: 2. The expression vector of the cell line is preferably pCDNA3. The cell line is GALE deficient, preferably ldlD.
[0021] The present disclosure further provides a vector comprising an isolated polynucleotide selected from: a polynucleotide sequence set forth in SEQ ID NO: 3 (WTeGALE), or a degenerate variant of the SEQ ID NO: 3; a polynucleotide sequence at least 90% identical to the polynucleotide sequence set forth in SEQ ID NO: 3; a polynucleotide sequence at least 75% identical to the polynucleotide sequence set forth in SEQ ID NO: 3; and a polynucleotide sequence at least 50% identical to the polynucleotide sequence set forth in SEQ ID NO: 3. The vector is preferably pPIC3.5K.
[0022] The present disclosure further provides a process for producing a polypeptide comprising culturing a host cell, where the host cell can be Pichia pastoris, Saccharomyces cerevisiae, Schizosaccharomyces pombe, or Escherichia coli, preferably Pichia pastoris, under conditions sufficient for the production of the polypeptide where the polypeptide has the characteristics that the polypeptide is capable of UDP-gal/UDP-glc interconversion and substantially incapable of UDP-galNAc/UDP-glcNAc interconversion. The polypeptide is selected from: an amino acid sequence set forth in SEQ ID NO: 4 (WTeGALE), or conservatively modified variants thereof; an amino acid sequence that is at least 90% identical to SEQ ID NO: 4; an amino acid sequence that is at least 75% identical to SEQ ID NO: 4; and an amino acid sequence that is at least 50% identical to SEQ ID NO: 4.
[0023] The present disclosure further provides a cell line transfected with an expression vector comprising a polynucleotide SEQ ID NO: 3 (WTeGALE) or a degenerate variant of the SEQ ID NO: 3; a polynucleotide sequence at least 90% identical to the polynucleotide sequence set forth in SEQ ID NO: 3; a polynucleotide sequence at least 75% identical to the polynucleotide sequence set forth in SEQ ID NO: 3; and a polynucleotide sequence at least 50% identical to the polynucleotide sequence set forth in SEQ ID No: 3, encoding a polypeptide having the characteristics that the polypeptide is capable of UDP-gaVUDP-glc interconversion and substantially incapable of UDP-galNAc/UDP-glcNAc interconversion. The polypeptide is selected from: an amino acid sequence set forth in SEQ ID NO: 4 (WTeGALE), or conservatively modified variants thereof; an amino acid sequence that is at least 90% identical to SEQ ID NO: 4; an amino acid sequence that is at least 75% identical to SEQ ID NO: 4; and an amino acid sequence that is at least 50% identical to SEQ ID NO: 4. The expression vector of the cell line is preferably pCDNA3. The cell line is GALE deficient, preferably ldlD.
[0024] The present disclosure further provides a method of culturing a GALE deficient cell line transfected with either a polynucleotide selected from: a polynucleotide sequence set forth in SEQ ID NO: 1 (C307YhGALE) or a degenerate variant of the SEQ ID No: 1; a polynucleotide sequence at least 90% identical to the polynucleotide sequence set forth in SEQ ID NO: 1, a polynucleotide sequence at least 75% identical to the polynucleotide sequence set forth in SEQ ID No: 1, and a polynucleotide sequence at least 50% identical to the polynucleotide sequence set forth in SEQ ID NO: 1 or a polynucleotide selected from: a polynucleotide sequence set forth in SEQ ID NO: 3 (WTeGALE), or a degenerate variant of the SEQ ID NO: 3; a polynucleotide sequence at least 90% identical to the polynucleotide sequence set forth in SEQ ID NO: 3; a polynucleotide sequence at least 75% identical to the polynucleotide sequence set forth in SEQ ID NO: 3; and a polynucleotide sequence at least 50% identical to the polynucleotide sequence set forth in SEQ ID NO: 3 in the absence of galactose to produce glycoproteins having intact N-linked modifications with substantially no O-linked modifications.
[0025] Other systems, methods, features, and advantages of the present disclosure will be or will become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Many aspects of the 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.
[0027] FIG. 1 is a comparative illustration of epimerase activity in the purified enzymes wild type human GALE (WThGALE), wild-type E. coli GALE (WTeGALE), and the mutant human enzyme C307YhGALE, with regard to both UDP-gal/UDP-glc interconversion and UDP-galNAc/UDP-glcNAc interconversion.
[0028] FIG. 2 is a western blot showing that C307YhGALE (4OkDa band evident in lane 4) can be stably expressed in ldlD cells.
[0029] FIG. 3 demonstrates that C307YhGALE expressed in ldlD cells is active with regard to UDP-gal/UDP-glc interconversion.
[0030] FIG. 4 is a western blot showing that WTeGALE can be stably expressed in ldlD cells (40 kDa band evident in lane 4).
[0031] FIG. 5 demonstrates that WTeGALE expressed in ldlD cells is active with regard to UDP-gal/UDP-glc interconversion.
[0032] FIG. 6 demonstrates that C307Y hGALE and WTeGALE in ldlD cells are not significantly active with regard to UDP-galNAc/UDP-glcNAc interconversion, although the WThGALE enzyme in these cells is very active with regard to this reaction.
DETAILED DESCRIPTION
[0033] Polynucleotides, polypeptides, host cells, cell lines and corresponding methods that can be used to study glycosylation or to prepare glycoproteins with novel glycosylation patterns as disclosed.
[0034] Prior to setting forth embodiments of the disclosure in detail, it may be helpful to first define the following terms
[0035] The term “affinity tag” is used herein to denote a polypeptide segment that can be attached to a second polypeptide (making a fusion protein) to provide for detection of the fusion protein using a monoclonal antibody that recognizes the affinity tag, or purification of the fusion protein using an affinity column of immobilized antibody or other specific ligand (nickel, GST, etc.). In principal, any peptide or protein for which an antibody or other specific binding agent is available can be used as an affinity tag. Affinity tags include HA (a 9 amino acid sequence, derived from the hemagglutinin sequence (tyr-pro-tyr-asp-val-pro-asp-tyr ala), poly-histidine tract (hexahistidine), protein A (Nilsson, et al., EMBO J, 4:1075, 1985; Nilsson, et al., Methods Enzymol., 198:3, 1991), glutathione S transferase (Smith, et al., Gene, 67:31, 1988), Glu-Glu affinity tag, substance P, Flag™ peptide (Hopp, et al., Biotechnology, 6:1204-10, 1988), streptavidin binding peptide, or other antigenic epitope or binding domain. See, in general, Ford, et al., Protein Expression and Purification, 2: 95-107, 1991. DNAs encoding affinity tags are available from commercial suppliers (e.g., Pharmacia Biotech, Piscataway, N.J.).
[0036] “Polynucleotide” generally refers to any polyribonucleotide or polydeoxribonucleotide, which may be unmodified ribonucleic acid (RNA) or deoxyribonucleic acid (DNA) or modified RNA or DNA. “Polynucleotides” include, without limitation, single- and double-stranded DNA, DNA that is a mixture of single- and double-stranded regions, single- and double-stranded RNA, and RNA that is a mixture of single- and double-stranded regions, hybrid molecules comprising DNA and RNA that may be single-stranded or, more typically, double-stranded or a mixture of single- and double-stranded regions. In addition, “polynucleotide” refers to triple-stranded regions comprising RNA or DNA or both RNA and DNA. The term “polynucleotide” also includes DNAs or RNAs containing one or more modified bases and DNAs or RNAs with backbones modified for stability or for other reasons. “Modified” bases include, for example, tritylated bases and unusual bases such as inosine. A variety of modifications may be made to DNA and RNA; thus, “polynucleotide“embraces chemically, enzymatically, or metabolically modified forms of polynucleotides as typically found in nature, as well as the chemical forms of DNA and RNA characteristic of viruses and cells. “Polynucleotide” also embraces relatively short polynucleotides, often referred to as oligonucleotides. “Polypeptide” refers to any peptide or protein comprising two or more amino acids joined to each other by peptide bonds or modified peptide bonds, (i.e., peptide isosteres). “Polypeptide” refers to both short chains, commonly referred to as peptides, oligopeptides, or oligomers, and to longer chains, generally referred to as proteins. “Polypeptides” may contain amino acids other than the 20 gene-encoded amino acids. “Polypeptides” include amino acid sequences modified either by natural processes, such as post-translational processing, or by chemical modification techniques, which are well known in the art. Such modifications are described in basic texts and in more detailed monographs, as well as in a voluminous research literature.
[0037] Modifications may occur anywhere in a polypeptide, including the peptide backbone, the amino acid side-chains and the amino or carboxyl termini. It will be appreciated that the same type of modification may be present to the same or varying degrees at several sites in a given polypeptide. Also, a given polypeptide may contain many types of modifications. Polypeptides may be branched as a result of ubiquitination, and they may be cyclic, with or without branching. Cyclic, branched, and branched cyclic polypeptides may result from post-translational natural processes, or may be made by synthetic methods. Modifications include acetylation, acylation, ADP-ribosylation, amidation, covalent attachment of flavin, covalent attachment of a heme moiety, covalent attachment of a nucleotide or nucleotide derivative, covalent attachment of a lipid or lipid derivative, covalent attachment of phosphotidylinositol, cross-linking, cyclization, disulfide bond formation, demethylation, formation of covalent cross-links, formation of cystine, formation of pyroglutamate, formylation, gamma-carboxylation, glycosylation, GPI anchor formation, hydroxylation, iodination, methylation, myristoylation, oxidation, proteolytic processing, phosphorylation, prenylation, racemization, selenoylation, sulfation, transfer-RNA mediated addition of amino acids to proteins such as arginylation, and ubiquitination (Proteins—Structure and Molecular Properties, 2nd Ed., T. E. Creighton, W. H. Freeman and Company, New York, 1993; Wold, F., Post-translational Protein Modifications: Perspectives and Prospects, pgs. 1-12 in Post-translational Covalent Modification of Proteins, B. C. Johnson, Ed., Academic Press, New York, 1983; Seifter, et al., Meth Enzymol, 182: 626-646, 1990, and Rattan, et al., Ann NY Acad. Sci., 663:48-62, 1992).
[0038] “Variant” refers to a polynucleotide or polypeptide that differs from a reference polynucleotide or polypeptide, but retains essential properties. A typical variant of a polynucleotide differs in nucleotide sequence from another, reference polynucleotide. Changes in the nucleotide sequence of the variant may or may not alter the amino acid sequence of a polypeptide encoded by the reference polynucleotide. Nucleotide changes may result in amino acid substitutions, additions, deletions, fusions, and truncations in the polypeptide encoded by the reference sequence, as discussed below.
[0039] A typical variant of a polypeptide differs in amino acid sequence from another, reference polypeptide. Generally, differences are limited so that the sequences of the reference polypeptide and the variant are closely similar overall and, in many regions, identical. A variant and reference polypeptide may differ in amino acid sequence by one or more substitutions, additions, and deletions in any combination. A substituted or inserted amino acid residue may or may not be one encoded by the genetic code. A variant of a polynucleotide or polypeptide may be naturally occurring such as an allelic variant, or it may be a variant that is not known to occur naturally. Non-naturally occurring variants of polynucleotides and polypeptides may be made by mutagenesis techniques or by direct synthesis.
[0040] “Identity,” as known in the art, is a relationship between two or more polypeptide sequences or two or more polynucleotide sequences, as determined by comparing the sequences. In the art, “identity” also means the degree of sequence relatedness between polypeptide or polynucleotide sequences, as the case may be, as determined by the match between strings of such sequences. “Identity” and “similarity” can be readily calculated by known methods, including, but not limited to, those described in ( Computational Molecular Biology, Lesk, A. M., Ed., Oxford University Press, New York, 1988; Biocomputing: Informatics and Genome Projects, Smith, D. W., Ed., Academic Press, New York, 1993; Computer Analysis of Sequence Data Part I, Griffin, A. M., and Griffin, H. G., Eds., Humana Press, New Jersey, 1994; Sequence Analysis in Molecular Biology, von Heinje, G., Academic Press, 1987; and Sequence Analysis Primer, Gribskov, M. and Devereux, J., Eds., M Stockton Press, New York, 1991; and Carillo, H., and Lipman, D., SIAM J Applied Math., 48: 1073 (1988).
[0041] Preferred methods to determine identity are designed to give the largest match between the sequences tested. Methods to determine identity and similarity are codified in publicly available computer programs. The percent identity between two sequences can be determined by using analysis software (i.e., Sequence Analysis Software Package of the Genetics Computer Group, Madison Wis.) that incorporates the Needelman and Wunsch, ( J. Mol. Biol., 48: 443-453, 1970) algorithm (e.g., NBLAST, and XBLAST). The default parameters are used to determine the identity for the polynucleotides and polypeptides of the present disclosure.
[0042] By way of example, a polynucleotide sequence of the present disclosure may be identical to the reference sequence of SEQ ID NO: 1, that is be 100% identical, or it may include up to a certain integer number of nucleotide alterations as compared to the reference sequence. Such alterations are selected from the group including at least one nucleotide deletion, substitution, including transition and transversion, or insertion, and wherein said alterations may occur at the 5′ or 3′ terminal positions of the reference nucleotide sequence or anywhere between those terminal positions, interspersed either individually among the nucleotides in the reference sequence or in one or more contiguous groups within the reference sequence. The number of nucleotide alterations is determined by multiplying the total number of nucleotides in the reference nucleotide by the numerical percent of the respective percent identity (divided by 100) and subtracting that product from said total number of nucleotides in the reference nucleotide. Alterations of a polynucleotide sequence encoding the polypeptide may alter the polypeptide encoded by the polynucleotide following such alterations.
[0043] Similarly, a polypeptide sequence of the present disclosure may be identical to the reference sequence of SEQ ID NO: 2, that is be 100% identical, or it may include up to a certain integer number of amino acid alterations as compared to the reference sequence such that the % identity is less than 100%. Such alterations are selected from the group including of at least one amino acid deletion, substitution, including conservative and non-conservative substitution, or insertion, and wherein said alterations may occur at the amino- or carboxy-terninal positions of the reference polypeptide sequence or anywhere between those terminal positions, interspersed either individually among the amino acids in the reference sequence or in one or more contiguous groups within the reference sequence. The number of amino acid alterations for.a given % identity is determined by multiplying the total number of amino acids in the reference polypeptide by the numerical percent of the respective percent identity (divided by 100) and then subtracting that product from said total number of amino acids in the reference polypeptide.
[0044] The terms “amino-terminal” and “carboxyl-terrninal” are used herein to denote positions within polypeptides. Where the context allows, these terms are used with reference to a particular sequence or portion of a polypeptide to denote proximity or relative position. For example, a certain sequence positioned carboxyl-terminal to a reference sequence within a polypeptide is located proximal to the carboxyl terminus of the reference sequence, but is not necessarily at the carboxyl terminus of the complete polypeptide.
[0045] The term “degenerate nucleotide sequence” denotes a sequence of nucleotides that includes one or more degenerate codons (as compared to a reference polynucleotide molecule that encodes a polypeptide). Degenerate codons contain different triplets of nucleotides, but encode the same amino acid residue (e.g., GAU and GAC triplets each encode Asp).
[0046] The term “expression vector” is used to denote a DNA molecule, linear or circular, which includes a segment encoding a polypeptide of interest operably linked to additional segments that provide for its transcription and translation. Such additional segments include promoter and terminator sequences, and may also include one or more origins of replication, one or more selectable markers, an enhancer, a polyadenylation signal, etc. Expression vectors are generally derived from yeast or bacterial genomic or plasmid DNA, or viral DNA, or may contain elements of both.
[0047] The term “isolated”, when applied to a polynucleotide, denotes that the polynucleotide has been removed from its natural genetic milieu and is thus free of other extraneous or unwanted coding sequences, and is in a form suitable for use within genetically engineered protein production systems. Such isolated molecules are those that are separated from their natural environment and include cDNA and genomic clones. Isolated polynucleotide molecules of the present disclosure are free of other polynucleotides with which they are ordinarily associated, but may include naturally occurring 5′ and 3′ untranslated regions such as promoters and terminators. The identification of associated regions will be evident to one of ordinary skill in the art (Dynan, et al., Nature, 316: 774-78, 1985).
[0048] An “isolated” polypeptide or protein is a polypeptide or protein that is found in a condition other than its native environment, such as apart from blood and animal tissue. In a preferred form, the isolated polypeptide is substantially free of other polypeptides, particularly other polypeptides of animal origin. It is preferred to provide the polypeptides in a highly purified form, i.e. greater than 95% pure, more preferably greater than 99% pure. When used in this context, the term “isolated” does not exclude the presence of the same polypeptide in alternative physical forms, such as dimers or alternatively glycosylated or derivatized forms.
[0049] The term “operably linked”, when referring to DNA segments, indicates that the segments are arranged so that they function in concert for their intended purposes (e.g., transcription initiates in the promoter and proceeds through the coding segment to the terminator).
[0050] The term “promoter” is used herein for its art-recognized meaning to denote a portion of a gene containing DNA sequences that provide for the binding of RNA polymerase and initiation of transcription. Promoter sequences are commonly, but not always, found in the 5′ non-coding regions of genes.
[0051] The term “modulate” and “modulation” denote adjustment or regulation of the activity of a compound or the interaction between one or more compounds.
[0052] The term “phenotype” means a property of an organism that can be detected, which is usually produced by interaction of an organism's genotype and environment.
[0053] The term “open reading frame” means the amino acid sequence encoded between translation initiation and termination codons of a coding sequence.
[0054] The term “codon” means a specific triplet of mononucleotides in the DNA chain. Codons correspond to specific amino acids (as defined by the transfer RNAs) or to start and stop of translation by the ribosome.
[0055] The term “wild-type” means that the nucleic acid fragment does not include any deleterious mutations. A “wild-type” protein means that the protein is active at a level of activity found in nature and includes the amino acid sequence found in nature.
[0056] The term “chimeric protein” means that the protein comprises regions which are wild-type and regions which are mutated. It may also mean that the protein comprises wild-type regions from one protein and wild-type regions from another protein.
[0057] The term “mutation” means a change in the sequence of a wild-type nucleic acid sequence or a change in the sequence of a polypeptide. Such mutation may be a point mutation such as a transition or a transversion. The mutation may be a deletion, an insertion, a substitition or a duplication.
[0058] In the polypeptide notation used herein, the lefthand direction is the amino terminal direction and the righthand direction is the carboxy-terminal direction, in accordance with standard usage and convention. Similarly, unless specified otherwise, the lefthand end of single-stranded polynucleotide sequences is the 5′ end; the lefthand direction of double-stranded polynucleotide sequences contains the 5′ end of the top strand, and the 3′ end of the bottom strand.
[0059] The term “agent” is used herein to denote a chemical compound, a mixture of chemical compounds, an array of spatially localized compounds (e.g., a VLSIPS peptide array, polynucleotide array, and/or combinatorial small molecule array), a biological macromolecule, a bacteriophage peptide display library, a bacteriophage antibody (e.g., scFv) display library, a polysome peptide display library, or an extract made from biological materials such as bacteria, plants, fungi, or animal (particularly mammalian) cells or tissues.
[0060] All publications, including but not limited to patents and patent applications, cited in this specification are herein incorporated by reference as if each individual publication were specifically and individually indicated to be incorporated by reference herein as though fully set forth.
[0061] As indicated above, embodiments of the present disclosure include polypeptides and polynucleotides that encode the polypeptides. Embodiments of the polypeptide are designated “GALE polypeptides”, while embodiments of the polynucleotides are designated “GALE polynucleotides.” One GALE polynucleotide sequence is set forth in SEQ ID NO: 1 (C307YhGALE) and the corresponding GALE polypepetide amino acid sequence is set forth in SEQ ID NO: 2. A second GALE polynucleotide sequence is set forth in SEQ ID NO: 3 (WTeGALE) and the corresponding GALE polypeptide sequence is set forth in SEQ ID NO: 4.
[0062] As discussed above, embodiments of the present disclosure provide GALE polynucleotides, including DNA and RNA molecules that encode the GALE polypeptides. Those skilled in the art will readily recognize that, in view of the degeneracy of the genetic code, considerable sequence variation is possible among these polynucleotide molecules. SEQ ID NO: 1 and SEQ ID NO: 3 are degenerate polynucleotide sequences that encompass polynucleotides that encode the GALE polypeptides of SEQ ID NO: 2 and SEQ ID NO: 4. The degeneracy of nucleic acid is well known in the art and as such degenerate polynucleotides of SEQ ID NO: 1 and SEQ ID NO.3 are included within the scope of the present disclosure.
[0063] Table 1 sets forth the three letter symbols and the one letter symbols for the amino acids as well as possible codons that can be associated with the amino acids.
TABLE 1 THREE ONE LETTER SYNONYMOUS LETTER CODE CODE CODONS Cys C TGC TGT Ser S AGC AGT TCA TCC TCG TCT Thr T ACA ACC ACG ACT Pro P CCA CCC CCG CCT Ala A GCA GCC GCG GCT Gly G GGA GGC GGG GGT Asn N AAC AAT Asp D GAC GAT Glu E GAA GAG Gln Q CAA CAG His H CAC CAT Arg R AGA AGG CGA CGC CGG CGT Lys K AAA AAG Met M ATG Ile I ATA ATC ATT Leu L CTA CTC CTG CTT TTA TTG Val V GTA GTC GTG GTT Phe F TTC TTT Tyr Y TAC TAT Trp W TGG Asn-Asp B Glu-Gln Z Any X
[0064] One of ordinary skill in the art will appreciate that some ambiguity is introduced in determining a degenerate codon. Other nucleic acid sequences that encode the same protein sequence are considered equivalents. Thus, some polynucleotides encompassed by the degenerate sequence may encode variant amino acid sequences, but one of ordinary skill in the art can easily identify such variant sequences by reference to the amino acid sequences of SEQ ID NO: 2 and SEQ ID NO: 4.
[0065] Variant GALE polynucleotides that encode polypeptides that can be used as defined above are within the scope of the embodiments of the present disclosure. More specifically, variant GALE polynucleotides that encode polypeptides which exhibit at least about 50%, about 75%, about 85%, and preferably about 90%, of the activity of GALE polypeptides encoded by the variant GALE polynucleotides are within the scope of the embodiments of the present disclosure.
[0066] For any GALE polypeptide, including variants and fusion proteins, one of ordinary skill in the art can readily generate a fully degenerate polynucleotide sequence encoding that variant using the information set forth in Table 1. Moreover, those of skill in the art can use standard software to devise GALE variants (i.e., polynucleotides and polypeptides) based upon the polynucleotide and amino acid sequences described herein.
[0067] As indicated above, GALE polynucleotides and isolated GALE polynucleotides of the present disclosure can include DNA and RNA molecules. Methods for preparing DNA and RNA are well known in the art. In general, RNA is isolated from a tissue or cell that produces GALE RNA. Such tissues and cells can be identified by Northern blotting (Thomas, Proc. Natl. Acad. Sci. USA, 77: 5201, 1980). An exemplary source being human liver tissue. Total RNA can be prepared using guanidine HCI extraction followed by isolation by centrifugation in a CsCl gradient (Chirgwin, et al., Biochemistry, 18:,52-94, 1979). Complementary DNA (CDNA) can be prepared from the RNA using known methods. In the alternative, genomic DNA can be isolated. Polynucleotides encoding GALE polypeptides are then identified and isolated by hybridization or PCR, for example.
[0068] GALE polynucleotides can also be synthesized using techniques widely known in the art. (Glick, et al., Molecular Biotechnology, Principles & Applications of Recombinant DNA, (ASM Press, Washington, D.C. 1994); Itakura, et al., Annu. Rev. Biochem., 53: 323-56, 1984 and Climie, et al., Proc. Natl. Acad. Sci. USA, 87: 633-7, 1990.
[0069] Embodiments of the present disclosure also provide for GALE polypeptides and isolated GALE polypeptides that are substantially homologous to the GALE polypeptides of SEQ ID NO: 2 and SEQ ID NO: 4. The term “substantially homologous” is used herein to denote polypeptides having about 50%, about 75%, about 85%, and preferably about 90% sequence identity to the sequence shown in SEQ ID NO: 2 and SEQ ID NO: 3. Percent sequence identity is determined by conventional methods as discussed above. In addition, embodiments of the present disclosure include polynucleotides that encode homologous polypeptides.
[0070] In general, homologous polypeptides are characterized as having one or more amino acid substitutions, deletions, and/or additions. These changes are preferably of a minor nature, that is conservative amino acid substitutions and other substitutions that do not significantly affect the activity of the polypeptide; small substitutions, typically of one to about six amino acids; and small amino- or carboxyl-terminal extensions, such as an amino-terminal methionine residue, a small linker peptide of up to about 2-6 residues, or an affinity tag. Homologous polypeptides comprising affinity tags can further comprise a proteolytic cleavage site between the homologous polypeptide and the affinity tag.
[0071] In addition, embodiments of the present disclosure include polynucleotides that encode polypeptides having one or more “conservative amino acid substitutions,“compared with the GALE polypeptides of SEQ ID NO: 2 and SEQ ID NO: 4. Conservative amino acid substitutions can be based upon the chemical properties of the amino acids. That is, variants can be obtained that contain one or more amino acid substitutions of SEQ ID NO: 2 and SEQ ID NO: 4, in which an alkyl amino acid is substituted for an alkyl amino acid in a GALE polypeptide, an aromatic amino acid is substituted for an aromatic amino acid in a GALE polypeptide, a sulfur-containing amino acid is substituted for a sulfur-containing amino acid in a GALE polypeptide, a hydroxy-containing amino acid is substituted for a hydroxy-containing amino acid in a GALE polypeptide, an acidic amino acid is substituted for an acidic amino acid in a GALE polypeptide, a basic amino acid is substituted for a basic amino acid in a GALE polypeptide, or a dibasic monocarboxylic amino acid is substituted for a dibasic monocarboxylic amino acid in a GALE polypeptide.
[0072] Among the common amino acids, for example, a “conservative amino acid substitution” is illustrated by a substitution among amino acids within each of the following groups: (1) glycine, alanine, valine, leucine, and isoleucine, (2) phenylalanine, tyrosine, and tryptophan, (3) serine and threonine, (4) aspartate and glutamate, (5) glutamine and asparagine, and (6) lysine, arginine and histidine. Other conservative amino acid substitutions are provided in Table 2.
TABLE 2 CHARACTETISTIC AMINO ACID Basic: arginine lysine histidine Acidic: glutamic acid aspartic acid Polar: glutamine asparagine Hydrophobic: leucine isoleucine valine Aromatic: phenylalanine tryptophan tyrosine Small: glycine alanine serine threonine methionine
[0073] Conservative amino acid changes in GALE polypeptides can be introduced by substituting nucleotides for the nucleotides recited in SEQ ID NO: 1 and SEQ ID NO: 3. Such “conservative amino acid” variants can be obtained, for example, by oligonucleotide-directed mutagenesis, linker-scanning mutagenesis, mutagenesis using the polymerase chain reaction, and the like (McPherson (Ed.), Directed Mutagenesis: A Practical Approach (IRL Press 1991)). The ability of such variants to treat conditions as well as other properties of the wild-type protein can be determined using standard methods. Alternatively, variant GALE polypeptides can be identified by the ability to bind specifically to anti-GALE antibodies.
[0074] GALE polypeptides having conservative amino acid variants can also comprise non-naturally occurring amino acid residues. Non-naturally occurring amino acids include, without limitation, trans-3-methylproline, 2,4-methanoproline, cis-4-hydroxyproline, trans-4-hydroxyproline, N-methyl-glycine, allo-threonine, methylthreonine, hydroxy-ethylcysteine, hydroxyethylhomocysteine, nitro-glutamine, homoglutamine, pipecolic acid, thiazolidine carboxylic acid, dehydroproline, 3- and 4-methylproline, 3,3-dimethylproline, tert-leucine, norvaline, 2-azaphenyl-alanine, 3-azaphenylalanine, 4-azaphenylalanine, and 4-fluorophenylalanine. Several methods are known in the art for incorporating non-naturally occurring amino acid residues into proteins. For example, an in vitro system can be employed wherein nonsense mutations are suppressed using chemically aminoacylated suppressor tRNAs. Methods for synthesizing amino acids and aminoacylating tRNA are known in the art. Transcription and translation of plasmids containing nonsense mutations is carried out in a cell-free system comprising an E. coli S30 extract and commercially available enzymes and other reagents. Proteins are purified by chromatography. (Robertson, et al., J. Am. Chem. Soc., 113: 2722, 1991; Ellman, et al., Methods Enzymol., 202: 301, 1991; Chung, et al., Science, 259: 806-9, 1993; and Chung, et al., Proc. Natl. Acad. Sci. USA, 90: 10145-9, 1993). In a second method, translation is carried out in Xenopus oocytes by microinjection of mutated mRNA and chemically aminoacylated suppressor tRNAs (Turcatti, et al., J. Biol. Chem., 271: 19991-8, 1996). Within a third method, E. coli cells are cultured in the absence of a natural amino acid that is to be replaced (e.g., phenylalanine) and in the presence of the desired non-naturally occurring amino acid(s) (e.g., 2-azaphenylalanine, 3-azaphenylalanine, 4-azaphenylalanine, or 4-fluorophenylalanine). The non-naturally occurring amino acid is incorporated into the protein in place of its natural counterpart. (Koide, et al., Biochem., 33: 7470-6, 1994). Naturally occurring amino acid residues can be converted to non-naturally occurring species by in vitro chemical modification. Chemical modification can be combined with site-directed mutagenesis to further expand the range of substitutions (Wynn, et al., Protein Sci., 2: 395-403, 1993).
[0075] Essential amino acids in the polypeptides of the present disclosure can be identified according to procedures known in the art, such as site-directed mutagenesis or alanine-scanning mutagenesis (Cunningham, et al., Science, 244: 1081-5, 1989; Bass, et al., Proc. Natl. Acad. Sci. USA, 88: 4498-502, 1991). In the latter technique, single alanine mutations are introduced at every residue in the molecule, and the resultant mutant molecules are tested for biological activity as disclosed below to identify amino acid residues that are critical to the activity of the molecule. (Hilton, et al., J. Biol. Chem., 271: 4699-708, 1996). Sites of ligand-receptor interaction can also be determined by physical analysis of structure, as determined by such techniques as nuclear magnetic resonance, crystallography, electron diffraction or photoaffinity labeling, in conjunction with mutation of putative contact site amino acids. (de Vos, et al., Science, 255: 306-12, 1992; Smith, et al., J. Mol. Biol., 224: 899-904, 1992; Wlodaver, et al., FEBS Lett., 309: 59-64, 1992). The identities of essential amino acids can also be inferred from analysis of homologies with related nuclear membrane bound proteins.
[0076] Multiple amino acid substitutions can be made and tested using known methods of mutagenesis and screening, such as those disclosed by Reidhaar-Olson and Sauer ( Science, 241: 53-7, 1988) or Bowie and Sauer ( Proc. Natl. Acad. Sci. USA, 86: 2152-6, 1989). Briefly, these authors disclose methods for simultaneously randomizing two or more positions in a polypeptide, selecting for functional polypeptide, and then sequencing the mutagenized polypeptides to determine the spectrum of allowable substitutions at each position. Other methods that can be used include phage display (Lowman, et al., Biochem., 30: 10832-7, 1991; Ladner, et al., U.S. Pat. No. 5,223,409) and region-directed mutagenesis (Derbyshire, et al., Gene, 46:145, 1986; Ner, et al., DNA, 7:127, 1988).
[0077] Variants of the disclosed GALE polypeptides can be generated through DNA shuffling. (Stemmer, Nature, 370: 389-91, 1994 and Stemmer, Proc. Natl. Acad. Sci. USA, 91: 10747-51, 1994). Briefly, variant polypeptides are generated by in vitro homologous recombination by random fragmentation of a parent DNA followed by reassembly using PCR, resulting in randomly introduced point mutations. This technique can be modified by using a family of parent DNAs, such as allelic variants or genes from different species, to introduce additional variability into the process. Selection or screening for the desired activity, followed by additional iterations of mutagenesis and assay provides for rapid “evolution” of sequences by selecting for desirable mutations while simultaneously selecting against detrimental changes.
[0078] Mutagenesis methods can be combined with high-throughput, automated screening methods to detect activity of cloned, mutagenized polypeptides in host cells. Preferred assays in this regard include cell proliferation assays and biosensor-based ligand-binding assays. Mutagenized DNA molecules that encode active polypeptides can be recovered from the host cells and rapidly sequenced using modern equipment. These methods allow the rapid determination of the importance of individual amino acid residues in a polypeptide of interest, and can be applied to polypeptides of unknown structure.
[0079] Using the methods discussed herein, one of ordinary skill in the art can identify and/or prepare a variety of GALE polypeptide fragments or variants of SEQ ID NO: 2 of SEQ ID NO: 4 that retain the functional properties of the GALE polypeptides. Such polypeptides may also include additional polypeptide segments as generally disclosed herein.
[0080] For any GALE polypeptide, including variants and fusion proteins, one of ordinary skill in the art can readily generate a degenerate polynucleotide sequence encoding that variant using the information set forth in Table 1 above as well as what is known in the art.
[0081] As used herein, a fusion protein consists essentially of a first portion and a second portion joined by a peptide bond. In one embodiment the first portion includes a polypeptide comprising a sequence of amino acid residues that is at least about 50%, about 75%, about 85%, and preferably about 90% identical in amino acid sequence to SEQ ID NO: 2 or SEQ ID NO: 4 and the second portion is any other heterologous non GALE polypeptide. The other polypeptide may be one that does not inhibit the function of the GALE polypeptide, such as a signal peptide to facilitate secretion of the fusion protein or an affinity tag.
[0082] The GALE polypeptides of the present disclosure, including full-length polypeptides, biologically active fragments, and fusion polypeptides, can be produced in genetically engineered host cells according to conventional techniques. Suitable host cells are those cell types that can be transformed or transfected with exogenous DNA and grown in culture, and include bacteria, fungal cells, and cultured higher eukaryotic cells. Eukaryotic cells, particularly cultured cells of multicellular organisms, are preferred. Techniques for manipulating cloned DNA molecules and introducing exogenous DNA into a variety of host cells. (Sambrook et al., Molecular Cloning: A Laboratory Manual, 2nd Ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., 1989, and Ausubel, et al., Eds., Current Protocols in Molecular Biology, John Wiley and Sons, Inc., N.Y., 1987).
[0083] In general, GALE polynucleotide sequences encoding GALE polypeptides are operably linked to other genetic elements required for its expression, generally including a transcription promoter and terminator, within an expression vector. The vector also commonly contains one or more selectable markers and one or more origins of replication, although those skilled in the art will recognize that within certain systems selectable markers may be provided on separate vectors, and replication of the exogenous DNA may be provided by integration into the host cell genome. Selection of promoters, terminators, selectable markers, vectors and other elements is a matter of routine design within the level of ordinary skill in the art. Many such elements are described in the literature and are available through commercial suppliers.
[0084] It is preferred to purify the GALE polypeptides of the present disclosure to about 80% purity, more preferably to about 90% purity, even more preferably about 95% purity, and particularly preferred is a pharmaceutically pure state, that is greater than 99.9% pure with respect to contaminating macromolecules, particularly other proteins and nucleic acids, and free of infectious and pyrogenic agents. Preferably, a purified polypeptide is substantially free of other polypeptides, particularly other polypeptides of animal origin.
[0085] Expressed recombinant GALE polypeptides (or fusion GALE polypeptides) can be purified using fractionation and/or conventional purification methods and media. Ammonium sulfate precipitation and acid or chaotrope extraction may be used for fractionation of samples. Exemplary purification steps may include hydroxyapatite, size exclusion, FPLC and reverse-phase high performance liquid chromatography. Suitable chromatographic media include derivatized dextrans, agarose, cellulose, polyacrylamide, specialty silicas, and the like. PEI, DEAE, QAE and Q derivatives are preferred. Exemplary chromatographic media include those media derivatized with phenyl, butyl, or octyl groups, such as Phenyl-Sepharose FF (Pharmacia), Toyopearl butyl 650 (Toso Haas, Montgomeryville, Pa.), Octyl-Sepharose (Pharmacia) and the like; or polyacrylic resins, such as Amberchrom CG 71 (Toso Haas) and the like. Suitable solid supports include glass beads, silica-based resins, cellulosic resins, agarose beads, cross-linked agarose beads, polystyrene beads, cross-linked polyacrylamide resins and the like that are insoluble under the conditions in which they are to be used. These supports may be modified with reactive groups that allow attachment of proteins by amino groups, carboxyl groups, sulfhydryl groups, hydroxyl groups and/or carbohydrate moieties. Examples of coupling chemistries include cyanogen bromide activation, N-hydroxysuccinimide activation, epoxide activation, sulfhydryl activation, hydrazide activation, and carboxyl and amino derivatives for carbodiimide coupling chemistries. These and other solid media are well known and widely used in the art, and are available from commercial suppliers. Methods for binding receptor polypeptides to support media are well known in the art. Selection of a particular method is a matter of routine design and is determined in part by the properties of the chosen support. (Affinity Chromatography: Principles & Methods, Pharmacia LKB Biotechnology, Uppsala, Sweden, 1988).
[0086] The GALE polypeptides of the present disclosure can be isolated by exploitation of their binding properties. For example, immobilized metal ion adsorption (IMAC) chromatography can be used to purify histidine-rich proteins, including those comprising polyhistidine tags. Briefly, a gel is first charged with divalent metal ions to form a chelate (Sulkowski, Trends in Biochem., 3: 1-7, 1985). Histidine-rich proteins will be adsorbed to this matrix with differing affinities, depending upon the metal ion used, and will be eluted by competitive elution, lowering the pH, or use of strong chelating agents. Other methods of purification include purification of glycosylated proteins by lectin affinity chromatography and ion exchange chromatography ( Methods in Enzymol., 182, M. Deutscher, (Ed.), Acad. Press, San Diego, 1990, pp.529-39). Within additional embodiments of the disclosure, a fusion of the polypeptide of interest and an affinity tag (e.g., Gly-Gly tag) may be constructed to facilitate purification.
[0087] GALE polypeptides or fragments thereof may also be prepared through chemical synthesis according to methods known in the art, including exclusive solid phase synthesis, partial solid phase methods, fragment condensation or classical solution synthesis. (Merrifield, J. Am. Chem. Soc., 85: 2149, 1963).
[0088] Using methods known in the art, GALE polypeptides may be prepared as monomers or multimers and may be post-translationally modified or unmodified.
EXAMPLE 1
[0089] Preparation and Expression of SEQ ID NO: 1 (C307y h GALE): Site-directed PCR mutagenesis was performed on the WThGALE cDNA sequence using the following primers: SEQ ID NO: 5-hEPIMFC307Y, 5′-GGTGATGTGGCAGCCTATTACGCCAACCCC-3′ and SEQ ID NO: 6-hEPIMRC307Y, 5′-GCTGGGGTTGGCGTAATAGGCTGCCACATCACC-3′. Following mutagenesis, dideoxy sequencing was performed to confirm mutation and remaining wild-type sequence. The mutations of interest were introduced into the high copy number Pichia pastoris expression vector pPIC3.5K (Invitrogen), which already contained WThGALE sequence, by gap repair in the bacterial strain XL-1 blue, and again confirmed by sequencing. It will be appreciated that other host cells and expression vectors may be utilized. Plasmids were then introduced into the methylotrophic yeast, Pichia pastoris for protein overexpression. Plasmids were linearized and integrated in multiple copy into the Pichia strain, GS115, using a spheroplasting kit (Invitrogen). Cells were screened and selected on G418 (U.S. Biological) for the highest expressing colonies. Expression was confirmed by western blot analysis as previously described in Wohlers et al. Am. J. Hum. Gen. 64:462-470(1999). Clones demonstrating the highest level of hGALE expression were then expanded, cultured, and induced for expression with methanol in a New Brunswick Scientific Bioflo 3000 fermenter. Cells were lysed by agitation with glass beads in breaking buffer (50 mM sodium phosphate pH 7.4, 1 mM PMSF, 1 mM EDTA and 5% glycerol) using a Beadbeater (Biospec). Cell lysates were collected and the soluble portion retrieved by centrifuging spinning at 4° C. in a high-speed centrifuge (Sorvall) until the supernatant was clear. The wild-type and C307Y mutant epimerases were purified and crystallized precisely as previously described (Thoden, 1996).
EXAMPLE2
[0090] In Vitro Assays for UDP-Gal: Aliquots of each purified enzyme from Example lwere stored in 50% glycerol with 4 mM NAD+ in liquid nitrogen, while crude extracts were stored at −80° C. until needed. All crude extracts were passed through Micro biospin 30 columns (Biorad) before being assayed for enzyme activity. Assays to determine the level of GALE activity with respect to UDP-Gal were performed essentially as previously described in Thoden et al. J Biol Chem Jul 26; 277(30):27528-34 (2002). Enzymatic conversion from substrate to product was detected either by radioactive assay or by carbohydrate analysis on HPLC; results from the HPLC assays were determined to be comparable to those seen for the radioactive assay (data not shown). For radioactive assay, conversion of UDP-Gal to UDP-Glc was measured in a 12.5-μl reaction containing 2.5 μl of premix (0.05 μCi of UDP-[ 14 C]Gal (Amersham Biosciences), 2 nM cold UDP-Gal, 0.2 mM glycine buffer, pH 8.7), 2.5 μl of 20 mM NAD+, and 7.5 μl of purified protein diluted in Johnston buffer (20 mM HEPES/KOH, pH 7.5, 1 mM dithiothreitol, and 0.3 mg of bovine serum albumin/ml). Appropriate amounts of protein were used in each reaction in order to stay within the predetermined linear range of the assay. Reactions were incubated at 37° C for 30 min and were stopped by boiling at 100° C. for 10 min. Following high speed centrifugation for 15 min in a microcentrifuge, 10 μl of the sample was spotted onto a prewashed PEI-Cellulose TLC plate (Baker). After thorough drying, the plate was run for 16-24 h in a solvent containing 1.5 mM Na 2 B 4 O 7 , 5 mM H 3 BO 3 , and 25% ethylene glycol. After running, plates were air-dried before being exposed to storage phosphor screens (Amersham Biosciences) overnight. Images were visualized with a Typhoon 9200 variable mode imager and quantified using ImageQuant software (both from Amersham Biosciences). Percent conversion was determined by dividing the product signal by the total signal and multiplying by 100. For detection by HPLC, the above assay protocol was used, with minor modifications. C 14-labeled UDP-galactose was removed from the premix, and the corresponding volume replaced by water. The assay proceeded through the 30 min incubation described above, and was then stopped by addition of 2.5 volumes of ice cold 100% methanol. After brief vortex mixing, samples were spun on high speed for 10 min at 4° C. Supernatant was collected, and dried under vacuum with low heat. Resultant pellets were resuspended in 250μl ddH 2 O, and the suspension added to an 0.2 μM nylon micro-spin filter tube (Alltech), and spun for approximately 5 min at 4000g. A 15 μl aliquot was then analyzed by HPLC.
[0091] In Vitro Assay for UDP-GalNAc: The radioactive method for detecting conversion of UDP-GalNAc to UDP-GIcNAc was performed essentially as described above for UDP-Gal, with the following assay components per 25 μl of reaction: 8.75 μl of premix (0.04 μCi of UDP-[ 14 C]GalNAc (ICN), 1.89 mM cold UDP-GalNAc, 28.6 mM pyruvate, 286 mM glycine, pH 8.7, 5 μl of 20 mM NAD), and 11.25 μl of protein diluted in Johnston buffer. Appropriate amounts of protein were used in each reaction to stay within the predetermined linear range of the assay. Assays were performed as for UDP-Gal, with a TLC run-time of 10 h and quantified as described for UDP-Gal.
[0092] For analysis by HPLC, protein samples were diluted with glycine buffer (100 mM glycine, pH 8.7) to a final volume of 7.5 μl. For each reaction, 2.5 μl of 20 mM NAD+, and 2.5 il of premix (3.3 mM UDP-GalNAc, and 500 mM glycine, pH 8.7) were added, for a final reaction volume of 12.5 μl. Assay mixtures were incubated at 37° C. for 30 min before stopping by addition of 2.5 volumes of ice-cold 100% methanol. Samples were vortexed, spun and dried as for UDP-Gal HPLC assays, and resuspended in 750 μl ddH 2 O. The suspension was added to an 0.2 μm nylon micro-spin filter tube, and spun for approximately 2.5 min at 4000 g. An aliquot of 20 μl was then analyzed by HPLC.
[0093] HPLC Analysis of Carbohydrates: Carbohydrate detection by HPLC was based on the methods of Smits (1998) and de Koning (1992). HPLC analysis was carried out on a DX600 HPLC system (Dionex, Sunnyvale, CA) consisting of a Dionex AS50 autosampler, a Dionex GP50 gradient pump, and a Dionex ED50 electrochemical detector. Carbohydrates were separated on a CarboPac PA10 column, 250×4 mm, with a CarboPac PA10 guard column, 50×4 mm, placed before the analysis column, and a borate trap placed after. It was noted that elimination of the borate trap led to better separation of UDP-sugars from NAD; therefore, the trap was removed for all UDP-GalNAc analyses. For UDP-Gal assays 15 μl was injected into a 25 μl injection loop, while for UDP-GalNAc assays, the injection volume was 20 μl. Samples were maintained at 4° C. in the autosampler tray and the HPLC analysis was carried out at room temperature.
[0094] The following mobile phase buffers were used for HPLC analysis: buffer A, 15 mM NaOH, and buffer B, 50 mM NaOH/1 M NaAC. To prevent carbonate contamination of the analysis column, a 50% NaOH solution (Fisher) containing less than 0.04% sodium carbonate was used. Buffers were degassed with He and then maintained under an He atmosphere. UDP-Gal and UDP-Glc were separated using a high salt isocratic procedure with a flow rate of 1 mmin: 30% buffer A and 70% buffer B for 20 min. UDP-GalNAc and UDP-GlcNAc were separated using an isocratic procedure with a flow rate of 0.75 ml/min: 45% buffer A and 55% buffer B for 40 min.
[0095] The ED50 detector consisted of a gold electrode and a pH-Ag/AgCl reference electrode for signal detection by integrated amperometry. The following waveform potential-time sequence was used: 0.1 V (0 to 0.20 s), with integration at 0.1 V (0.20 to 0.40 s), followed by a decrease to −2.0 V (0.41 to 0.42 s), increase to 0.6 V (0.43 s), decrease to −0.10 V (0.44 to 0.50 s). Carbohydrates were quantified using PeakNet software version 6.4 (Dionex) and based on integration of peak areas with comparison to standards. For evaluation of UDP-hexoses, the following standard solution (1×) was used: 10 μM UDP-GalNAc, 10 μM UDP-GlcNAc, 100 μM UDP-Gal, and 100 μM UDP-Glc.
[0096] As shown in FIG. 1 , the in vitro activity assays were performed to determine the ability of each purified enzyme, wild type human GALE (WThGALE), wild-type E. coli GALE (WTeGALE) and the mutant human enzyme C307YhGALE, to epimerize the substrates, UDP-gal and UDP-galNAc. These recombinant proteins were all expressed in and purified from Pichia Pastoris. As demonstrated, WT eGALE has no ability to interconvert UDP-GalNAc and UDP-GlcNAc, while WT hGALE can interconvert both UDP-Gal /UDP-Glc, and UDP-GalNAc /UDP-GlcNAc well. The C307Y hGALE protein maintains wildtype levels of UDP-Gal activity, while UDP-GalNAc activity is reduced to 2.30% of that seen in WT hGALE.
EXAMPLE 3
[0097] Construction of Vectors:
[0098] GALE vectors: All GALE alleles were introduced into the CMV promoter-driven mammalian expression vector, pCDNA3 (Invitrogen), which contains a G418 resistance gene for selection of stable cell lines. The allele sequences contained a HA affinity tag for monitoring the stable expression of the GALE protein in cells. In order to obtain a level of GALE expression, which is comparable to endogenous levels seen in CHO-KI cells, it was necessary to remove the CMV promoter in some vectors, and replace it with the weaker mouse Galactose-1-Phosphate Uridylyltransferase (mGALT) promoter. The mGALT promoter sequence was obtained by PCR-amplification of the promoter sequence from crude mouse genomic DNA. The primers used to create the mGALT sequence contained the restriction enzyme sequences Mlu I and Hind III for ease of sub-cloning: mGALTproMlulfl, 5′-CGCGACGCGTATCCGTGGCGGGACGAATGGACACAGCAAC-3′ (SEQ ID NO: 7) and mGALTproHind3rl, 5′-CGCGAAGCTTATCGGCTCCGCTATGCGACGTGAGGCC-3′ (SEQ NO: 8). The PCR product was subcloned into the pCDNA3 vector, replacing the CMV promoter, and finally subjected to dideoxy sequencing to ensure correct sequence.
EXAMPLE 4
[0099] Transfection and isolation ofstable clones containing SEQ ID NO: 1 (C307Y h GALE): ldlD cells were transfected with the mammalian expression vector, pCDNA3 (Invitrogen), encoding an HA-tagged allele of C307Y hGALE, and subcloned by standard recombinant techniques and using standard protocols for the lipofection reagents Lipofectamine 2000 or Lipofectamine (both by Invitrogen). Cells were re-plated at <1:10 in selective media containing G418 (U.S. Biologicals). After approximately 14d of drug selection, individual clones were isolated and purified by further exposure to selective drugs. Stable expression of GALE alleles in said clones was confirmed by western blot analysis targeting the HA-tag, and by activity assays.
[0100] Cell culture methods: ldlD cells, and the parent cell line, CHO-KI were maintained under standard protocols (trypsin-EDTA harvesting) and conditions (5% CO 2 , 37° C.) in a monolayer culture in Ham's F-12 media (containing 100 U/ml Penicillin, 100 pg/ml streptomycin, 2 mM glutamine, and 5% (v/v) fetal bovine serum (FBS)). For experiments, cells were EDTA-trypsin harvested, and washed with media before being counted and plated at the appropriate densities. In experiments studying glycosylation or galactose sensitivity, it is necessary to avoid the use of serum containing large amounts of glycoproteins from which Gal and GalNAc can be scavenged (Krieger, 1989). For this reason, 5% FBS in these experiments must be replaced by one of the following: (i) direct plating into 1-3% NCLPDS; (ii) plating into 1-3% NCLPDS for Id, followed by the replacement of this media with ITS+ medium (0.625 mg/ml insulin, 0.625 mg/ml transferring, 0.625 ug/ml selenium, 0.535 mg/ml linoleic acid, and 0.125 g/ml BSA), or an equivalent culture medium containing less glycoproteins/glycolipids than 5% FBS to allow expression of the phenotype (Krieger et al. 1986).
[0101] Preparation of lipoprotein-deficient serum: Newborn calf lipoprotein-deficient serum (NCLPDS) was made according to the method described by Goldstein, and modified by Krieger et al.(1986). Whole newborn calf serum (Invitrogen) was adjusted to a final density of 1.215 g/ml with solid Potassium Bromide (Sigma). The serum was then centrifuged for 36 hr at 4° C. and 59,000 RPM in a 60 Ti Beckman rotor. The resulting bottom layer (deficient in lipoproteins) was separated from the lipoprotein-containing fraction. The lipoprotein-deficient fraction was dialyzed at 4° C. against a total of 30 L of 150 mM NaCl for 72hr, changing dialyzing liquid 5 times. The lipoprotein-deficient serum was sterilized with a 0.45 μM Millipore filter and adjusted to a protein concentration of 60 mg/ml by dilution with 150 mM NaCl. This procedure results in a total serum cholesterol content, which is <5% of that found in the initial whole serum.
[0102] Western Blot Analyses: Western blot analyses were performed as described previously(Lang, Li, Black-Brewster, and Fridovich-Keil, Nucleic Acids Research 29: 2567-2574 (2001). HA-tagged GALE protein alleles were detected using the 12CA5 monoclonal antibody (mAb, Roche) at a final concentration of 0.8 μg/ml followed by HRP-conjugated donkey anti-mouse secondary antibody (Covance), diluted 1:5000. Signals were detected by chemiluminescence. Immediately before incubation, 1.5μl of 30% (w/w) H 2 O 2 were added to 10 ml of a working solution (1.25 mM luminol, 0.2 mM p-coumaric acid, and 100 mM Tris-HCL, pH 8.5). The resultant solution was added to the nitrocellulose blot, and incubated for 2 minutes before exposure to film.
[0103] It has been demonstrated that IdiD cells transfected with C307YhGALE do express C307YhGALE. Protein extracts from ldlD cells, IdiD stably expressing WThGALE, and ldlD stably expressing C307YGALE were subjected to SDS-PAGE, and analyzed by western blot. Both the C307YhGALE and hGALE proteins contained an HA tag. The results, demonstrating expression of both 40 kDa epimerase proteins, are shown in FIG. 2 . Each lane contains 50 ug protein. GALE enzyme is represented by a band at 40 kDa. Lane 1 , marker; lane 2 , IdiD cells; lane 3 , positive control (ldlD cells transfected w/HA-tagged WT human GALE); lane 4, ldlD cells transfected with C307Y human GALE.
[0104] It was further demonstrated that the C307YhGALE expressed in ldlD cells is active. Protein extracts from ldlD cells, CHO cells and ldlD cells stably expressing C307YhGALE driven by the CMV promoter were subjected to in vitro UDP-gal activity assays. CHO cells were used as a positive control and ldlD cells were used as a negative control. The results are shown in FIG. 3 .
[0105] Finally, while C307YhGALE expressed in ldlD cells is active with respect to UDP-Gal, the activity with respect to UDP-GalNAc is reduced to levels close to those seen in ldld cells expressing backbone alone, as demonstrated in FIG. 6 . In this experiment, ldlD cells expressing WThGALE were used as a positive control, and ldlD cells expressing backbone alone were used as a negative control. Without the ability to produce UDP-GalNAc endogenously from UDP-GlcNAc, these cells will be dramatically reduced in their capacity to synthesize 0-glycans without the addition of exogenous sugars, while the ability to synthesize N-glycans will be maintained.
EXAMPLE 5
[0106] Transfection and isolation of stable clones containing SEQ ID NO: 3 (WTeGALE): ldlD cells were transfected with the mammalian expression vector, pCDNA3 (Invitrogen), encoding an HA-tagged allele of otherwise WTeGALE, which had been amplified from E. coli genomic DNA, and subcloned by standard recombinant techniques and using standard protocols for the lipofection reagents Lipofectamine 2000 or Lipofectamine (both by Invitrogen). Cells were re-plated at <1:10 in selective media containing G418 (U.S. Biologicals). After approximately 14d of drug selection, individual clones were isolated and purified by further exposure to selective drugs. Stable expression of GALE alleles in said clones was confirmed by western blot analysis targeting the HA-tag, and by activity assays.
[0107] Cell culture methods: As described in Example 4 above.
[0108] Preparation of lipoprotein-deficient serum: As described in Example 4 above.
[0109] Western Blot Analyses: Western blot analyses were performed as described previously (Lang, Li, Black-Brewster, and Fridovich-Keil, Nucleic Acids Research 29: 2567-2574 (2001). HA-tagged GALE protein alleles are detected using the 12CA5 monoclonal antibody (mAb, Roche) at a final concentration of 0.8 μg/ml followed by HRP-conjugated donkey anti-mouse secondary antibody (Covance), diluted 1:5000. Signals were detected by chemiluminescence. Immediately before incubation, 1.5μl of 30% (w/w) H 2 O 2 were added to 10 ml of a working solution (1.25 mM luminol, 0.2 mM p-coumaric acid, and 100 mM Tris-HCL, pH 8.5). The resultant solution was added to the nitrocellulose blot, and incubated for 2 minutes before exposure to film.
[0110] It has been demonstrated that ldlD cells transfected with WTeGALE do express WTeGALE. Protein extracts from ldlD cells, ldlD stably expressing WThGALE, and ldlD stably expressing WTeGALE were subjected to SDS-PAGE, and analyzed by western blot. Both the eGALE and hGALE proteins contained an HA tag. The results are shown in FIG. 4 . Each lane contains 50 ug protein. GALE enzyme is represented by a band at 4OkDa. Lane 1 , marker; lane 2 , ldlD cells; lane 3 , positive control (ldlD cells transfected w/HA-tagged WT human GALE); lane 4 , ldlD cells transfected with WT E. coli GALE.
[0111] It was further demonstrated that the WTeGALE expressed in ldlD cells is active. Protein extracts from ldlD cells, or ldlD cells stably expressing WTeGALE driven by the CMV promoter were subjected to in vitro UDP-gal activity assays. CHO cells were used as a positive control and ldlD cells were used as a negative control. The results are shown in FIG. 5 .
[0112] Finally, while C307YhGALE expressed in ldlD cells is active with respect to UDP-Gal, the activity with respect to UDP-GalNAc is reduced to levels close to those seen in IdiD cells expressing backbone alone, as demonstrated in FIG. 6 . In this experiment, ldlD cells expressing WThGALE were used as a positive control, and ldlD cells expressing backbone alone were used as a negative control. Without the ability to produce UDP-GalNAc endogenously from UDP-GlcNAc, these cells will be dramatically reduced in their capacity to synthesize O-glycans without the addition of exogenous sugars, while the ability to synthesize N-glycans will be maintained.
[0113] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations, and are merely set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) of the disclosure without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and the present disclosure and protected by the following claims.
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Genetically modified cell lines that express a UDP-galactose 4-epimerase (GALE) capable of interconverting UDP-galactose (UDP-gal) and UDP-glucose (UDP-glc), but essentially incapable of interconverting UDP-N-acetylgalactosamine (UDP-galNAc) and UDP-N-acetylglucosamine (UDP-glcNAc).
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RELATED APPLICATIONS
[0001] This application claims priority to BE 2007/0050 filed Feb. 7, 2007.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention pertains to an artificial turf and to the yarns required therefore. The object of the present invention is to provide a new type of artificial turf comprising a combination of straight and curly monofilament yarns. The thus obtained artificial turf provides, on the one hand, the look of natural grass, and on the other hand, the known use of a well-known infill layer by filling for example sand and/or rubber particles for enhancing the elasticity of the surface of the artificial turf becomes superfluous.
[0004] 2. Description of the Related Art
[0005] Many patent applications describe yarns for the manufacture of synthetic turfs made of a variety of materials and combinations thereof. Often, combinations are presented of polyethylene, polypropylene, or block copolymers thereof. Further to the use of these materials, the use of polyamide 6 (nylon) is also known, for instance from the Japanese patent application JP-A-3.279.419.
[0006] Apart from the choice of material, many structural shapes of yarns are known, among others straight monofill, fibrillated or monofill curled yarns.
SUMMARY OF THE INVENTION
[0007] The present invention provides a specific combination of structural shape and material for the yarns as a result of which tufts are formed which do not need infill material. Therefore, especially the application and the maintenance of such synthetic turfs is simplified. Also, recycling possibilities are strongly increased as a result of which these synthetic turfs are more environment-friendly.
[0008] The present invention is related to yarns, tufted on a carrier material. It is generally known that several yarns twisted or twined together are tufted in a carrier material. In this way standing tufts are formed, wherein each individual tuft is composed of a multiple of filaments.
[0009] The invention relates mainly to a tufted artificial turf comprising a flexible, water-permeable support fabric, provided with tufts, wherein each tuft comprises partly of straight monofilament yarn and partly of curly monofilament yarn, characterised in that said tufts are manufactured from a compound yarn composed from said straight monofilament yarn twined together with the curly monofilament yarn.
[0010] According to the invention the support fabric comprises a flexible way water-permeable plastic material, preferably a laminate of a UV-stabilised tuft fabric from polypropylene, provided with a latex backing. The specific weight of this laminate amounts preferably between 800 and 1500 g/m 2 , and more preferably between 1100 and 1400 g/m 2 .
[0011] The artificial turf according to the invention comprises tufts, manufactured from a compound yarn, i.e. from straight monofilament yarn and curly monofilament yarn, wherein the straight and curly monofilament yarns are twined together such that the curly monofilament yarn is nested around the straight monofilament yarn, wherein the curly monofilament yarn provides partly stability and partly elasticity to the straight monofilament yarn. Because of this, an infill with for example sand or rubber particles is superfluous.
[0012] In a preferred embodiment of the artificial turf according to the invention, the curly and straight monofilament yarns of said composed yarn are extruded from polyamide, for example polyamide 6, polyamide 6.6 and polyamide 6.12, and more preferably polyamide 6.
[0013] In a further preferred embodiment, both the straight monofilament yarn and the curly monofilament yarn of said composed yarn each comprise preferably of 4 to 12 individual filaments, more preferably of 6 to 10 individual filaments, and most preferably of 8 individual filaments.
[0014] The thickness and width of the filaments are such that they resemble individual blades of grass; the width of the individual filaments preferably ranges between 0.5 and 2 millimetre, more preferably between 0.75 and 1.5 millimetre, and is most preferably equal to approximately 0.9 millimetre.
[0015] The thickness of the individual filaments is not only important to achieve the look of natural grass, but also to achieve the desired properties of elasticity. The individual filaments usually have a thickness between 50 μm and 200 μm, more preferably between 100 μm and 150 μm and most preferably, it amount to approximately 140 μm.
[0016] The yarn number of the individual filaments of the straight monofilament yarn usually ranges between 500 and 2000 dtex, more preferably between 750 and 1500 dtex, and is most preferably equal to approximately 1000 dtex. Whereas the yarn number of the individual filaments of the curly monofilament yarn usually ranges between 300 and 1500 dtex, more preferably between 500 and 1000 dtex, and most preferably is equal to approximately 750 dtex. The total dtex value per tuft preferably ranges between 12,000 and 16,000, and more preferably between approximately 13,000 and 15,000, and is most preferably equal to approximately 14,000 dtex.
[0017] In a further preferred embodiment of the invention, the individual filaments are manufactured in several shades, wherein the straight monofilament yarn preferably comprises 2 to 6 dark green and 2 to 6 olive green filaments, more preferably 3 to 5 dark green and 3 to 5 olive green, and most preferably 4 dark green and 4 olive green filaments. The curly monofilament yarn preferably comprises 1 to 3 beige and 3 to 9 light green filaments, more preferably 1.5 to 4.5 beige and 2.5 to 7.5 light green, and most preferably 2 beige and 6 light green filaments.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0018] The curly monofilament yarn is generally manufactured from a straight monofilament yarn that is subjected to one or more heat treatments. This treatment may take place as from the extrusion of the yarn and/or during the processing step and/or on the finished carpet. Preferably, the final curling and crimping is obtained after a heat treatment during the coating of the tuft fabric with a stabilizing agent, such as for example latex, as a result of which also the tufts become firmly attached in the tuft fabric. In its finished form the support fabric comprises a laminate of a tuft fabric with an additional layer of a stabilizing agent, preferably a latex, applied onto it.
[0019] According to present the invention, the manufacturing of curly monofilament yarn by means of a heat treatment can be performed in 3 different ways, i.e. by means of a heat treatment of the monofilament yarn directly after extrusion and before the tufting process, by means of a heat treatment during the application of the adhesion material (latex) on the tuft fabric, or by means of a combination of both aforementioned heat treatments. In a preferred embodiment the straight monofilament yarn is subjected to a first heat treatment which takes place before the tufting process such that an initial curling arises. Subsequently, the straight and partly curly monofilament yarn is tufted in line on a tuft fabric, after which a latex backing is applied to the back of aforementioned tuft fabric by means of a second heat treatment. The application of the latex backing and the associated heat treatment completes on the one hand the curling and ensures on the other hand an optimum fixing of the tufts in the tuft fabric. After aforementioned heat treatment(s), the curly monofilament has a shrinkage of at least 60% and more preferably of at least 50%. Therefore, the rest height of the curly yarn ranges between ⅕ to ⅗, preferably ⅓ to ⅗ and most preferably approximately ½ of the length of the straight monofilament yarn in the tuft. This height ratio on the support fabric ensures that a good elasticity and bonding strength to the artificial turf are obtained such that an infill becomes superfluous.
[0020] Both aforementioned monofilament yarns are subsequently twined together to form one yarn and this with a speed of approximately 30 turns per running meter wherein the curly monofilament yarn is nested around the straight monofilament yarn. The finally obtained composed yarn has a yarn number which usually ranges between 10,000 dtex and 20,000 dtex, preferably between 12,000 and 16,000, more preferably between 13,000 and 15,000 and is most preferably approximately 14,000 dtex.
[0021] Preferably, the filaments in a tuft all have the same length between 3 and 5 cm, more preferably between 3.5 cm and 4.5 cm and most preferably approximately between 3.7 and 3.9 cm. The curly filaments in their curly state have a length ranging between 40 and 60% with respect to the initial length. In general, the shrinkage is obtained by a heat treatment.
[0022] The invention is further illustrated by means of the examples below which illustrate some preferred embodiments of the invention.
Example 1
[0023] The compound yarn comprises 8 filaments curly monofilament yarn of polyamide 6 (nylon) with a compound dtex value of 6000 (8 filaments of each 750 dtex per filament) with a width of 0.9 mm, a thickness of 140 μm and a height of 38 mm in elongated form and a height of approximately 24 mm in curly form with 8 filaments straight monofilament (diamond structure) with a dtex value of 8000, a width of 0.9 mm and also a thickness of 140 μm. These yarns are twined together and subsequently this composed yarn is linearly tufted with approximately 140 stitches per running meter with a needle distance of 5/16″, and a pile height of 38 mm such that a pile weight was obtained of approximately 2200 g/m 2 . The support material comprises a polypropylene tuft fabric which is UV-stabilised with a specific weight of approximately 164 g/m 2 provided with a latex backing with 1000 g/m 2 .
[0024] The obtained artificial turf have the following properties:
[0000]
Colour stability
Scale 7 (DIN 54004)
UV-Stability
>6,000 u (DIN 53387)
Water permeability
6.10 −4 m/sec
Flame retardancy
Class 1 (DIN 51960)
Pile anchoring
>30 N
Chlorine resistance
4-5 (DIN 54019)
Resistance to seawater
4-5 (DIN 54007)
Example 2
[0025] In a similar manner a number of other artificial turfs were tufted. Table I below gives the individual data for each type of filament.
[0000]
Ex 2
Ex 3
Ex 4
Ex 5
Ex 6
Ex 7
Ex 8
Ex 9
Curly PA monofilament
number
8
10
6
6
6
4
8
8
dtex (per fil)
740
600
1300
1100
1200
1500
800
750
length straight (mm)
40
42
38
39
45
40
38
46
length (curly)
25
20
18
17
21
16
15
19
width (mm)
0.6
0.8
1.4
0.9
1
0.95
0.85
0.6
thickness (μm)
150
85
100
140
130
175
100
140
Straight PA monofilament
number
8
6
10
8
12
12
10
8
dtex (by fil)
1000
1200
600
1500
1100
1000
1300
1200
length
40
42
38
42
48
38
38
46
width (mm)
0.8
0.9
0.5
1
0.9
0.8
1
0.7
thickness (μm)
140
140
150
170
130
135
140
180
[0026] The thus obtained composed yarns are tufted on a tuft fabric and provided with a water permeable backing, for example made of latex.
[0027] It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention.
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A tufted artificial turf having a flexible, water-permeable support fabric provided with tufts is disclosed. The tufts include parts of straight monofilament yarn and parts of curly monofilament yarn and are manufactured from a compound yarn formed by twining together the straight monofilament yarn with the curly monofilament yarn.
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BACKGROUND OF THE INVENTION
The present invention relates to a method for preparing an amorphous polymer chain in elastomers by a novel technique differing from conventional ones and to a method for preparing an elastomer having excellent mechanical strength as well as rubber elasticity. Generally, elastomers (rubber elastic bodies) are substances which can be obtained by chemically or physically bonding a part of linear polymeric substance (raw rubber: raw material rubber) whose molecules are active in rotational movement at room temperature. Typical elastomers include natural rubber, a part of which is crosslinked with sulfur, peroxides, or the like. A natural rubber derived elastomer is a polymeric compound comprising monomer components arranged with stereoregularity and is amorphous in a normal state but it is highly oriented to behave like a crystallized polymer when excessive deformation is applied thereto and, hence, is an ideal elastomer that has a sufficient resistance to wear and a sufficient strength.
According to the prior art, various elastomers with synthetic amorphous polymer chains have been designed or prepared by processes including the following:
First, there are cited homopolymers such as isoprene rubber (IR), butadiene rubber (BR), and chloroprene rubber (CR). The crystallizability of these polymers depend largely on their micro structures. Here, note that IR is a polymer of isoprene which is a polymerization unit of natural rubbers (NR) and designed to have high properties similar to natural rubbers by selectively increasing cis-1,4- bonds to the level observed in natural rubbers. BR is known to be a polymer whose crystallizability can be controlled by precisely controlling the micro structures such as cis-1,4-, trans-1,4-, -1,2- or -1,3-addition. Also, CR is a crystallizable polymer which comprises mainly a trans-1,4- structure.
Second, there are cited random copolymers such as styrene/butadiene rubber (SBR) and ethylene/propylene rubber (EPR), which are made amorphous by random copolymerization using as one of comonomers a monomer capable of forming a homopolymer having a low glass transition temperature (Tg), for example, butadiene, ethylene, etc.
Third, there are cited alternate copolymers such as tetrafluoroethylene/propylene rubber which are made amorphous by alternate copolymerization to vary the length of the unit structure constituting the polymer.
Fourth, there is cited graft or block copolymers such as block SBR, in which two units, i.e., a rubber component and a resin component, are arranged in the form of a main chain and a graft attached thereto or of blocks linked to each other to thereby render the resulting polymer amorphous.
Fifth, there are cited modified polymers such as chlorosulfonated polyethylene rubber (CSM) and chlorinated polyethylene (CM), in which the corresponding crystallizable homopolymer (e.g., homopolymer of ethylene) having a low Tg is modified to render the resulting polymer noncrystallized or amorphous.
Sixth, there are cited copolymers of a liquid or low crystallizability oligomer having reactive groups on the terminals of the molecule with a chain extender capable of reacting with the terminals. This approach is used typically in the preparation of millable polyurethanes.
As described above, in order to prepare acceptable amorphous polymer chains having vivid molecular motility, it has conventionally been considered necessary to reduce intermolecular force and minimize steric hindrance for the rotation of molecules and, hence, the above described amorphous polymer chains have been designed and prepared. Accordingly, conventional methods for designing amorphous polymer chains include: (1) arranging the double bonds in the polymer chain stereoregularly; (2) randomly or alternately copolymerizing a plurality of monomers having different properties such as structural unit length and showing crystallizability when converted into homopolymer to thereby decrease the crystallizability and render the polymer amorphous; (3) graft or block copolymerizing a plurality of monomers containing at least one monomer to be made amorphous to render the polymer amorphous as a whole; (4) making the polymer amorphous by chemically modifying a homopolymer which shows crystallizability, and; (5) polymerizing an amorphous oligomer.
In addition, there have been known amorphous polymer chains having two or more of the above described features in combination. For example, in the case of CR, in order to cope with the need for continued use at low temperatures, there have been used those polymers having a decreased crystallizability by copolymerization with one or more other monomers (cf. German Patent Publication DE-A-2,235,811).
Along with recent diversification of industry, a wide variety of elastomers having various functions have been demanded and conventional elastomers have become difficult to cope with such demand. More particularly, there has been awaited development of high performance elastomers having simultaneously those characteristics which have conventionally been considered contradictory to each other. To meet with such needs, the above described conventional approaches have been unsuccessful.
For example, suppose that it is intended to prepare polymer chains having reversal property that they crystallize when stretched while they become amorphous when relaxed. Then, it is necessary to prepare amorphous polymer chains which have structural regularity. However, it has been difficult to perform fine or precise control or adjustment of the polymer arrangement to the extent as desired by the above described conventional methods.
For example, it has been considered that such a high performance elastomer can be prepared using a catalyst such as metallocene or the like with simultaneously controlling stereoregularity, comonomer composition, and molecular weight distribution. However, the monomers which can be used are limited to olefins so that it is difficult to high performance elastomers having desired characteristics.
SUMMARY OF THE INVENTION
Generally, an object of the present invention is to provide a method for preparing an amorphous polymer chain which enables one to manufacture on an industrial scale high performance or high function elastomers that have been difficult to make by conventional methods by a combination of simple processes such as ring opening polymerization, polyaddition, polycondensation and the like.
Specifically, the present invention provides a method for preparing an amorphous polymer chain in an elastomer comprising: forming a crystallizable oligomer having a repeating unit comprising regularly arranged monomer units having first and second ends and reacting said repeating unit at both ends thereof to effect extension of its chain length; selecting the kind of said monomer units to be introduced into said repeating unit; selecting the number of said monomer units in said oligomer; selecting a molecular weight distribution of said repeating unit comprising said monomer units; selecting a linkage unit comprising a compound which reacts with the ends of said repeating units and inhibits crystallization of said repeating unit after the reaction, thereby controlling crystallizability of said polymer chain.
The method of the present invention permits the preparation of elastomers using polymers that have previously not been used because of their high crystallizability, by selecting the number of the monomer units in the oligomer and the molecular weight distribution of the repeating unit in the oligomer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram illustrating temperature dependence of ball rebound.
FIG. 2 is a diagram illustrating results of DSC measurement of Sample 4.
FIG. 3 is a diagram illustrating results of DSC measurement of Comparative Sample 11.
FIG. 4 is a diagram illustrating results of DSC measurement of Sample 5.
FIG. 5 is a diagram illustrating results of DSC measurement of Comparative Sample 12.
FIG. 6 is a diagram illustrating results of DSC measurement of natural rubber.
FIG. 7 is a diagram illustrating results of WAXD measurement of Example 3.
FIG. 8 is a diagram illustrating results of WAXD measurement of Comparative Example 7.
FIG. 9 is a diagram illustrating results of WAXD measurement of Example 4.
FIG. 10 is a diagram illustrating results of WAXD measurement of Comparative Example 8.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention, in contrast to the conventional design concept of controlling stereoregularity of polymer chains, forms a polymer chain having monomer units and a linkage unit connecting the units and controls the manner of how to combine these or arrangement, the number of repetition of the monomer units, and the molecular weight distribution of the monomer units, thereby making it possible to design amorphous polymer chains having monomer compositions that have conventionally been considered unusable because of their too strong crystallizability. In addition, the preparation method of the present invention can be practiced by using very simple methods such as ring opening polymerization and polyaddition or polycondensation, so that upon industrial scale production, the range in which raw materials for the preparation are selected can be broadened and freedom of design can be increased considerably.
More specifically, appropriate selection of the number of repetition of monomer units and molecular weight distribution of the crystallizable oligomer allows the oligomer portion to be prevented from being crystallized due to an influence by the linkage unit connecting to the oligomer portion. As a result, the monomer compositions that have heretofore been considered unusable because of occurrence of too strong a crystallization can also be used in the present invention. That is, according to the method of the present invention, high melting point oligomers that have hitherto not been introduced into amorphous polymer chains without difficulty can be incorporated thereinto.
Here, the crystallizable oligomer means an oligomer having a melting point, and it is desirable to use high melting oligomers having preferably a melting point of 20° C. or more, more preferably 30° C. or more.
Further, the monomer unit comprises a single monomer or a plurality of monomers and a predetermined number of the monomer unit(s) forms a diol unit. Generally, the diol unit and the end(s) thereof constitutes an oligomer. The oligomer may be a combination of a plurality of the linked monomer units, or diol units, linked at both ends thereof. More specifically, an example of the oligomer is poly-ε-caprolactone polyol represented by general formula (I) below. In this case, the above described R 1 (OH) 2 is used as the polymerization initiator, and the monomer unit is the e-caprolactone unit embraced by and m and n indicate the number of ε-caprolactone units. ##STR1##
Furthermore, the linkage unit may be arranged on at least one of the ends of the monomer unit. However, it is preferred that the linkage unit is arranged at both ends of the monomer unit so that the oligomer portion can be prevented from crystallization efficiently. The noncrystalline or amorphous polymer chain thus prepared must have a glass transition temperature of -20° C. or below in order for it to be useful for preparing elastomers. Preferably, the oligomer is a dicarboxylic acid and the compound which reacts with the oligomer is a diamine so that the linkage unit is an amide linkage.
According to the preparation of the present invention, controlling the molecular structure itself of the amorphous polymer chain comprising a crystal portion, results in controlling the crystallizability and amorphousness of the amorphous polymer chain so that it is possible to prepare high performance or high function elastomers which are prevented from crystallization under normal deformation conditions but develops crystallizability or behaves similarly to a crystallized polymer when deformed excessively to increase mechanical strength.
Note that polyurethanes comprising a polycaprolactone based polyol having a narrow molecular weight distribution is disclosed in, for example, Examined Published Japanese Patent Application (Kokoku) No. 39007/1988. This is intended to develop polyurethanes having improved recovery of elasticity. Polyols having narrow molecular weight distributions are disclosed in Examined Published Japanese Patent Application (Kokoku) No. 56251/1991, Unexamined Published Japanese Patent Application (Kokai) No. 292083/1995, and Unexamined Published Japanese Patent Application (Kokai) No. 196623/1988, respectively. They are intended to provide new polyols.
However, to the present inventor's knowledge, there has been no idea that control of, for example, the molecular weight and molecular weight distribution of polyols to be within an appropriate range before they are reacted with diisocyanate, the resulting polyols have a controlled crystallizability.
The present invention is based on the discovery that, in polyols, presence of molecules having a molecular weight more than a predetermined value, results in crystallization as a whole, while increasing the number of molecules having a molecular weight not larger than a predetermined molecular weight results in a lack of a definite glass transition temperature, Tg, of the elastomer. This also depreciates the elastomeric behavior of the final elastomer.
The preparation method of the present invention is achieved by designing the polymer chain such that the molecular weight distribution of the oligomers having crystallizability is controlled to small values and the oligomers are connected to each other through a suitable linkage unit. In order to arrange and connect the oligomer and linkage unit with regularity, it is desirable that the molecular structure be designed so that such structure can be realized by polyaddition or polycondensation.
More specifically, explanation will be made taking an example in which a polyol is used as the oligomer, and a urethane linkage unit is used as the linkage unit. As the polyol, there can be used those which have not been used for the purpose because of having crystallizability, for example, poly-ε-caprolactone based diols. In addition, the system is designed so that when the polyol having a controlled, narrowed molecular weight distribution is reacted with a diisocyanate, the crystallization of the polyol should be prevented by an influence by the polyurethane linkage unit originated from the diisocyanate. For example, when the polyol is to be used which contains as a major component the poly-ε-caprolactone based diol represented by formula (I) above, use of the average number of the caprolactone units in the poly-e-caprolactone based diol of 3 to 6 and the molecular weight distribution, Mw/Mn, of 1.5 or below for the caprolactone unit of the poly-ε-caprolactone based diol prevents the crystallization of the poly-e-caprolactone unit. If the average number of the caprolactone units is 7 or more, there appear portions where the crystallization is not prevented by the urethane linkage units. On the other hand, if there are two or less caprolactone units, the glass transition temperature of the polymer chain exceeds -20° C. so that they are unsuitable for use in elastomers.
The poly-ε-caprolactone based diol is prepared by the reaction between the ε-caprolactone monomer and the polymerization initiator. Those represented by formula (I) are prepared using R 1 (OH) 2 as a polymerization initiator.
The polymerization initiator is not limited particularly and any compounds may be used as far as they have one or more active hydrogen atoms and form one or more diols after ring-open polymerization. Diols and diamines can be used for the purpose. Such an initiator give an influence on the crystallizability of the poly-e-caprolactone unit as described above. Therefore, in the case where R 1 is a straight chain hydrocarbon, for example, the above described average number of the caprolactone unit must be controlled to 3 to 6. For example, when R 1 is derived from an initiator having high steric hindrance such as an aromatic ring, an aliphatic ring, etc., and, hence, has a great influence on the crystallizability of the poly-ε-caprolactone unit, the average number of the caprolactone units may be controlled to 4 to 8. That is, in the method of the present invention, the average number of the caprolactone units is controlled to a predetermined number depending on the type of the polymerization initiator.
Examples of the short chain initiators which can be used in the present invention include straight chain glycols having 2 to 12 carbon atoms in the main chain thereof, such as ethylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol; diols having a side chain and having up to 12 carbon atoms, such as neopentyl glycol and 3-methyl-1,5-pentanediol; diols having an unsaturated group and having up to 12 carbon atoms, such as 3-allyloxy-1,2-propanediol; and diols having an aromatic ring and having up to 20 carbon atoms, such as 1,4-bis(hydroxyethoxy)benzene and p-xylene glycol; alicyclic diols such as cyclohexanediol and cyclohexanemethanol; and the like. These short chain initiators may be used singly or two or more of them may be used in combination.
For preparing poly-ε-caprolactone based polyols which are used in the present invention, selection of catalysts as well as ε-caprolactone and polymerization initiator is important. As the catalyst which can control the molecular weight distribution of polyol to narrow ranges, there can preferably be used metal compound catalysts containing halogens or organic acid radicals, for example, tin dihalides such as chloride, bromide, iodide, etc. and the tin based catalyst represented by formula (II) below. ##STR2## wherein R 2 is a hydrogen atom, an alkyl group, or an aryl group; and X is a hydroxyl group, an alkoxide group or a halogen atom other than fluoride.
In preparing the poly-ε-caprolactone based polyols with a narrow molecular weight distribution, which are used advantageously in the present invention, it is preferred to polymerize the corresponding ε-caprolactone monomers at low temperatures as low as, preferably, 130° C. or below using the tin based catalyst represented by formula (II) above, for example, monobutyltin oxide or tin halides excepting tin fluoride. In this manner, use of monobutyltin oxide or tin halides (excluding fluoride) can give rise to a mono-disperse poly-ε-caprolactones having a molecular weight distribution within the range of 1.0 to 1.3 even at temperatures within the range of 100 to 200° C. without crystallization according as the polymerization reaction proceeds, thus allowing practicing the reaction in the absence of solvents. On the contrary, the technique described in Unexamined Published Japanese Patent Application (Kokai) No. 196623/1988 polymerizes lactone by ring opening polymerization reaction with an inorganic acid catalyst at a temperature of 100° C. or lower instead of 100° C. to 200° C. used in the preceding techniques to give highly mono-dispersed acetone polymers having a molecular weight distribution within the range of 1.0 to 1.2. In the case of bulk polymerization reactions at such low temperatures, crystallization tends to occur according as the polymerization reaction proceeds so that it has been recommended to perform the reaction in the presence of inert organic solvents such as benzene and toluene. However, this requires an additional step of removing or recovering solvents from the reaction mixture after completion of the reaction, which could be a bar to perform the reaction on an industrial scale.
In the present invention, the above described specified poly-ε-caprolactone based diol, which is a long chain polyol, is used as a main component of the polyol and in addition thereto a long chain polyol and chain extenders generally used can be employed in amounts within the range where the object of the present invention is not harmed. As the generally used long chain polyols, there can be used either polyester polyols or polyether polyols, or blends copolymerization products or partially modified products therefrom. Examples of the chain extenders include straight chain glycols having 2 to 12 carbon atoms in the main chain, such as ethylene glycol, thiodiethanol, propylene glycol, and butylene glycol; diols having an aromatic ring and having up to 20 carbon atoms, such as 1,4-bis(hydroxyethoxy)benzene and p-xylene glycol and hydrogenated products thereof. Additionally, triols such as trimethylol; or stearyl alcohol, hydroxyethyl acrylate and the like can also be used.
In the case where the polyurethane obtained by the method of the present invention is crosslinked with sulfur, a compound having an unsaturated bond is used as a part of the polymerization initiator or chain extender in accordance with conventional manner.
Such a diol can be reacted with a suitable diisocyanate to form an amorphous polymer chain. Preferred diisocyantes include at least one member selected from the group consisting of 2,6-toluene diisocyanate (TDI), 4,4'diphenylmethane diisocyanate (MDI), p-phenylene diisocyante (PPDI), 1,5-napthalene diisocyanate (NDI), and 3,3-dimethyldiphenyl-4,4'-diisocyanate (TODI). Such an amorphous polymer chain can be converted to a millable polyurethane. The amorphous polymer chain can be converted to a millable polyurethane by crosslinking the amorphous polymer chain, as it is or after introduction of suitable crosslinking sites therein, with sulfur, peroxides, metal salts, and the like.
In this case, the polyurethane is adjusted such that its crystallization is prevented under normal deformation conditions whereas under excessive deformation, it develops crystallizability. Accordingly, the millable polyurethane thus obtained has excellent mechanical strength and wear resistance.
As described above, the preparation method of the present invention, as compared with the conventional design, makes it possible to use a wide variety of raw materials and, hence, has flexibility in use or general purpose properties. The present invention makes it possible to design the polymer chain using even those oligomers that have conventionally been paid no attention because of excessive crystallizability for designing elastomers, thus enhancing freedom in design considerably.
Further, according to the preparation method of the present invention, the above-described oligomer portion have two phases which changes one from another reversibly, i.e., an elastic state or phase where the oligomer shows rubber elasticity under normal use conditions because the oligomer has a limited crystallizability and an orientation crystallization state or phase where the oligomer develops crystallizability due to excessive deformation. Therefore, according to the present invention, the crystallizability of the polymer chain can be adjusted precisely. One of the factors for such a precise adjustment of the crystallizability is, for example, the above-described selection of R 1 for polymerization initiator. In the selection of R 1 in the polymerization initiator, for reversible development of crystallizability, it is desirable to use straight chain glycols having 2 to 6 carbon atoms, but contains no alkyl side chains such as a methyl group. Particularly, among the cyclic compounds, those having attached to the 1,4-positions thereof the linkage unit to the lactone directly or indirectly shows ideal reversibility. Example of such a compound include p-xylene glycol, 1,4-bis(hydroxyethoxy)benzene (BHEB), and the like.
The amorphous polymer chains designed by the method of the present invention can be converted to an elastomer by crosslinking them as they are or after introduction therein of suitable crosslinking sites with sulfur, peroxides, metal salts, and the like.
The amorphous polymer chains designed by the method of the present invention can be used as a soft segment for preparing a thermoplastic elastomer as well as for use as raw rubber as described above, and further as a soft segment for preparing castable or thermoplastic polyurethane elastomers. Thermoplastic polyurethane elastomers can be prepared with such a soft segment and a hard segment.
EXAMPLES
Hereafter, the present invention will be described in greater detail by an example which explains how to produce the amorphous polymer chain in a millable polyurethane elastomer.
First, as the monomer unit for the repeating unit which constitutes the amorphous polymer chain of a polyurethane elastomer, there was selected ε-caprolactone used as a starting compound for preparing a castable high strength polyurethane. This caprolactone, upon ring opening polymerization reaction with R 1 (OH) 2 , a polymerization initiator, and a catalyst, formed a crystallizable oligomer having an e-caprolactone unit and a hydroxyl group on each end thereof. In this amorphous polymer chain, the crystallizability of the repeating unit comprising ε-caprolactone is inhibited by polyurethane linkage unit derived from a diisocyanate and R 1 derived from the polymerization initiator.
Therefore, physical properties of various millable polyurethanes were investigated in accordance with the following procedures.
Investigation for the Selection of the Number of Monomer units
To begin with, ethylene glycol was selected as a polymerization initiator, and a poly-ε-caprolactone based diol was produced by setting the molecular distributions to about 1.4 and about 2.2, respectively, the average number of monomer units to values varying within the range of 2.5 to 8.5.
Here, the group of Samples 1 to 7 (hereafter, referred to as Group A) had a molecular weight distribution as narrow as about 1.4 while the group of Samples 8 to 14 (hereafter, referred to as Group B) had a molecular weight distribution of about 2.2, which value was, within the range usually used in the conventional techniques. Table 1 shows the amount of catalyst and reaction temperature used in each reaction, the designed and calculated values of the number of ε-caprolactone units, designed and measured values of average molecular weight, and molecular weight distribution (Mw/Mn).
Here, the average molecular weights were determined by measuring the hydroxyl number of polyols according to JIS K1557-6.4 and calculating by the following equation: Molecular Weight=56.1×N×1000/Hydroxyl Number where N is the number of functional groups in the polymerization initiator.
Further, the molecular weight distribution was determined by gel chromatography (GPC) under the following conditions:
______________________________________Apparatus: LC-3A, SHIMAZU SEISAKUSHO; Solvent: Tetrahydrofuran (1 ml/min.) Temperature: 50° C. Column: Shodex KF801 1 tube KF8025 1 tube KF804 1 tube Detector: RID-6A, SHIMAZU SEISAKUSHO______________________________________
TABLE 1__________________________________________________________________________ Ini. ε-CL CAT R.Temp NCl AMW AMW NClSample K. P. P. K. (ppm) ° C. Dd. Dd. Md. Cd. Mw/Mn__________________________________________________________________________A 1 EG 62 570 SnCl.sub.2 5 150 2.5 632 616 2.4 1.4 2 EG 62 684 SnCl.sub.2 5 150 3 746 810 3.3 1.4 3 EG 62 912 SnCl.sub.2 5 150 4 974 999 4.1 1.3 4 EG 62 1140 SnCl.sub.2 5 150 5 1202 1163 4.8 1.4 5 EG 62 1368 SnCl.sub.2 5 150 6 1430 1480 6.2 1.3 6 EG 62 1596 SnCl.sub.2 5 150 7 1658 1647 7.0 1.4 7 EG 62 1938 SnCl.sub.2 5 150 8.5 2000 1991 8.5 1.4 B 8 EG 62 570 TBT 10 170 2.5 632 641 2.5 2.3 9 EG 62 684 TBT 10 170 3 746 792 3.2 2.2 10 EG 62 912 TBT 10 170 4 974 974 4.0 2.1 11 EG 62 1140 TBT 10 170 5 1202 1184 4.9 2.3 12 EG 62 1368 TBT 10 170 6 1430 1460 6.1 2.1 13 EG 62 1596 TBT 10 170 7 1658 1699 7.2 2.2 14 EG 62 1938 TBT 10 170 8.5 2000 1991 8.5 2.3__________________________________________________________________________ Ini.: Initiator, K.; Kinds, P.: Parts, CL; caprolactone, P.: Parts CAT: Catalyst, K.: Kinds R.Temp: Room Temperature NCl(Dd.):Designed values of the number of caprolactone units, AMW(Dd.):Designed values of average molecular weight AMW(Md.):Measured values of average molecular weight NCl(Cd.):Calculated values of the number of caprolactone units
Each of the poly-ε-caprolactone based polyols and equimolar amount of 4,4'-diphenylmethane diisocyanate (MDI) were reacted at 100° C. for 5 hours to obtain various millable polyurethanes.
In order to evaluate the properties of the millable polyurethanes thus obtained as an amorphous polymer chain their glass transition temperature, Tg, and the stability during storage at low temperatures was examined. The stability during storage at low temperatures was judged from their flexibility after standing at temperatures of -15° C., 5° C. and 25° C. for 3 days. Table 2 shows the results obtained.
As a result, it was found that in both group A having a narrower molecular weight distribution and group B having a broader molecular weight distribution, the crystallizability of the polyurethanes increased with an increased average number of e-caprolactone units. Group A had a wider temperature range than group B at which the amorphous state can be maintained.
TABLE 2______________________________________ Properties of GUM Ini. NCl Tg (Prop. after 3 days)Sample K. (Dd.) Mw/Mn ° C. -15° C. 5° C. 25° C.______________________________________A 1 EG 2.4 1.4 -10 Am Am Am 2 EG 3.3 1.4 -24 Am Am Am 3 EG 4.1 1.3 -33 Am Am Am 4 EG 4.8 1.4 -37 Cry Am Am 5 EG 6.2 1.3 -41 Cry Cry Am 6 EG 7.0 1.4 -45 Cry Cry Cry 7 EG 8.5 1.4 -48 Cry Cry Cry B 8 EG 2.5 2.3 -12 Am Am Am 9 EG 3.2 2.2 -24 Am Am Am 10 EG 4.0 2.1 -34 Cry Am Am 11 EG 4.9 2.3 -38 Cry Cry Am 12 EG 6.1 2.1 -42 Cry Cry Cry 13 EG 7.2 2.2 -46 Cry Cry Cry 14 EG 8.5 2.3 -48 Cry Cry Cry______________________________________ Ini.: Initiator, K.: Kinds, P.: Parts, Tg: Glass transition temperature NCl(Dd.): Designed values of the number of caprolactone units, Properties of GUM: Properties of polyurethane Prop. After 3 days: Properties after standing at each temp. for 3 days Am: Amorphous Cry: Crystallization
Further, to 100 parts by weight of each of the millable polyurethanes produced as described above was added 1.5 parts by weight of dicumyl peroxide (NIPPON FATS & OIL; PERCUMYL D (trade name)) and the mixture was kneaded in an open roll and press-molded at 160° C. for 20 minutes to obtain various crosslinked elastomers. These crosslinked elastomers were measured for hardness (Hs: JIS A scale) according to JIS K6253, ball rebound (Rb: %) according to JIS K6255 (based on ISO 4662), tensile strength (Tb: MPa) and elongation (Eb: %) according to JIS K6251 (based on ISO 37), tear strength using a notched, an angled test piece (Tr: N/mm) according to JIS K6252 (based on ISO 34). Table 3 shows the results obtained. Here, the crosslinked elastomers were measured for initial hardness after heating at 60° C. for 30 minutes and standing at 23° C. for 3 hours. Further, the crosslinked elastomers were also measured for hardness after standing at various temperatures for 3 days. Table 3 also shows the results of these tests. Furthermore, Samples 3, 4, 9, and 10 were measured for temperature dependence of ball rebound at -20° C. to 60° C. FIG. 1 illustrates the results.
Each crosslinked elastomer was observed for the phenomenon of "cold hardening", i.e., an increase in hardness from the hardness after standing at various temperature for 3 days due to crystallization. Then, the elastomers produced using poly-ε-caprolactone having a molecular weight of 1,500 (average number of caprolactone units of 6) suitable for use in conventional castable elastomers showed an increase in hardness even at temperatures near normal temperature. In those elastomers that were produced using poly-ε-caprolactone units of 3 or less showed no crystallizability but temperature dependence of the physical properties of the elastomer increases unacceptably at around normal temperature so that the resulting elastomer is unsuitable. On the other hand, use of poly-ε-caprolactone gave rise to elastomers which are less dependent on temperature without increasing the hardness.
These facts suggest that an increase in hardness due to crystallization is considered to depend on the number of lactone monomer units and on the contrary, the number of monomer units exceeds a predetermined value, the crystallizability of the polymer increases too high for the polymer to be suitable as an amorphous polymer chain in elastomers. When the average number of monomer units is below a predetermined value (e.g., below 3), the concentration of urethane group in the amorphous polymer chain increases so that the glass transition temperature of the polymer chain increases and gives an adverse influence on the temperature dependence. Therefore, in order for the elastomers to have low glass transition temperatures sufficient for practical purposes (e.g., -20° C. or below) while prevented from crystallizing, it is useful to highly control the molecular weight distribution of ε-caprolactone. Further, based on the knowledge that what is crystallized is the poly-ε-caprolactone unit, it is considered possible to finely control the crystallizability of the poly-ε-lactone unit, which was impossible by the conventional techniques, by selectively arranging molecules that control the crystallization of the linkage unit at both ends thereof.
TABLE 3__________________________________________________________________________Property of Elastomers Hs (after 3 days)Sample Hs Rb Tb Eb Tr -20° C. 0° C. 10° C. 20° C.__________________________________________________________________________A 1 53 48 12.8 560 23.7 95 55 52 50 2 53 60 18.5 520 25.8 54 54 53 53 3 53 66 19.2 520 23.7 52 53 53 53 4 52 72 17.4 510 28.6 65 54 54 53 5 53 69 18.5 510 38.5 85 92 92 52 6 54 71 24.1 520 49.8 94 93 93 85 7 55 73 24.8 520 57.7 94 93 93 87 B 8 54 52 15.3 540 25.1 90 55 54 53 9 49 60 18.8 520 23.6 55 54 49 49 10 48 66 20.2 510 31.5 85 87 52 47 11 53 72 19.3 540 28.3 85 89 88 53 12 54 74 23.1 510 41.7 91 93 93 79 13 92 65 24.2 520 44.2 95 95 94 94 14 93 65 23.8 550 57.7 96 95 94 94__________________________________________________________________________ Hs (after 3 days): Hardness after standing at various temperature for 3 days
Investigation for the Selection of Molecular Weight Distribution
As shown in Table 5, investigation was made of the influence on crystallizability of changes in the molecular weight distribution of caprolactone unit at a fixed number of caprolactone units.
Here, group C consisting of Samples 15 to 19 corresponded to poly-ε-caprolactones having an average number of e-caprolactone unit of 6 and various molecular weight distributions ranging from 1.15 to 2.13 while group D consisting of samples 20 to 24 corresponded to poly-ε-caprolactones having an average number ε-caprolactone of 5 and various molecular weight distributions ranging from 1.18 to 2.21.
Table 4 shows the amount of catalyst and reaction time used in each reaction, the designed and calculated values of the number of ε-caprolactone units, designed and found values of average molecular weight, and molecular weight distribution (Mw/Mn).
TABLE 4__________________________________________________________________________ Ini. ε-CL CAT R.Temp NCl AMW AMW NClSample K. P. P. K. (ppm) ° C. Dd. Dd. Md. Cd. Mw/Mn__________________________________________________________________________C 15 EG 62 1368 TBT 10 170 6 1430 1457 6.1 2.13 16 EG 62 1368 SnCl.sub.2 5 170 6 1430 1414 5.9 1.86 17 EG 62 1368 SnCl.sub.2 5 150 6 1430 1407 5.9 1.45 18 EG 62 1368 MBTO 50 150 6 1430 1478 6.2 1.29 19 EG 62 1368 MBTO 50 120 6 1430 1451 6.1 1.15 D 20 EG 62 1140 TBT 10 170 5 1202 1211 5.0 2.21 21 EG 62 1140 SnCl.sub.2 5 170 5 1202 1238 5.2 1.83 22 EG 62 1140 SnCl.sub.2 5 150 5 1202 1216 5.1 1.41 23 EG 62 1140 MBTO 50 150 5 1202 1254 5.2 1.28 24 EG 62 1140 MBTO 50 120 5 1202 1170 4.9 1.18__________________________________________________________________________ Ini.: Initiator, K.; Kinds, P.: Parts, CL; caprolactone, P.: Parts CAT: Catalyst, K.: Kinds R.Temp: Room Temperature NCl(Dd.):Designed values of the number of caprolactone units, AMW(Dd.):Designed values of average molecular weight AMW(Md.):Measured values of average molecular weight NCl(Cd.):Calculated values of the number of caprolactone units
Next, each of the poly-ε-caprolactone based polyols and equimolar amount of 4,4'-diphenylmethane diisocyanate (MDI) were reacted at 100° C. for 5 hours to obtain various millable polyurethanes.
These millable polyurethanes were evaluated for their stability as an amorphous polymer chain in terms of changes in physical properties upon storage at low temperatures, i.e., by storing them at low temperatures and measuring their glass transition temperature, Tg, and visually observing their crystallizability at temperatures of -25° C. 5° C. and 25° C. Table 5 shows the results obtained.
TABLE 5______________________________________ Properties of GUM Ini. NCl Tg (Prop. after 3 days)Sample K. (Cd.) Mw/Mn ° C. -15° C. 5° C. 25° C.______________________________________C 15 EG 6.1 2.13 -42 Cry Cry Cry 16 EG 5.9 1.86 -42 Cry Cry Cry 17 EG 5.9 1.45 -41 Cry Cry Am 18 EG 6.2 1.29 -41 Cry Cry Am 19 EG 6.1 1.15 -41 Cry Cry Am D 20 EG 5.0 2.21 -38 Cry Cry Am 21 EG 5.2 1.83 -39 Cry Cry Am 22 EG 5.1 1.41 -37 Cry Am Am 23 EG 5.2 1.28 -37 Am Am Am 24 EG 4.9 1.18 -37 Am Am Am______________________________________ Ini.: Initiator, K.: Kinds, P.: Parts, Tg: Glass transition temperature NCl(Dd.): Designed values of the number of caprolactone units, Properties of GUM: Properties of polyurethane Prop. After 3 days: Properties after standing at each temp. for 3 days Am: Amorphous Cry: Crystallization
Further, various crosslinked polyurethanes were obtained using each of the millable polyurethane in the same manner as described above. The crosslinked polyurethanes were tested for their physical properties as described above. Table 6 shows the results.
The change in hardness of the crosslinked polyurethanes indicated the molecular weight distribution of poly-ε-caprolactone based diol, raw material, gave a considerable influence on the increase in hardness due to crystallization at low temperatures (cold hardening) of elastomers and use of polyols having a very narrow molecular weight distribution made it possible to provide millable elastomers having controlled low temperature crystallizability. The present invention attained maximal effects by the use of polyols similar to mono-dispersed polyols as having a molecular weight distribution of 1.5 or less, preferably 1.3 or less, which indicates distribution of caprolactone units. In other words, because the average number of units can be made greater under the conditions where the crystallizability is controlled or limited, it is possible to obtain a glass transition temperature sufficient for practical use as a rubber elastic body so that amorphous elastomers comprising highly crystallizable units that have been contradictory in the prior art can be produced using general purpose production facilities used in rubber industry. The "glass transition sufficient for practical use" may be defined, for example, as about -20° C. This is because at a glass transition temperature of -20° C. or higher, the rubber elasticity exhibited at normal temperature cannot be maintained at those low temperatures which are encountered ordinarily, such as 0° C.
TABLE 6__________________________________________________________________________Property of Elastomers Hs (after 3 days)Sample Hs Rb Tb Eb Tr -20° C. 0° C. 10° C. 20° C.__________________________________________________________________________C 15 54 74 23.1 510 41.7 91 93 93 79 16 55 70 21.5 520 39.8 92 94 94 85 17 53 71 18.5 510 38.5 85 92 92 52 18 53 72 17.6 500 38.5 85 92 88 52 19 52 72 18.5 520 36.1 88 90 89 53 D 20 53 72 19.3 540 28.3 85 89 88 53 21 55 71 16.5 490 25.3 87 90 86 55 22 52 72 17.4 510 28.6 65 54 54 53 23 54 70 18.1 520 30.2 54 53 53 54 24 54 70 17.4 510 28.8 53 54 53 53__________________________________________________________________________ Hs (after 3 days): Hardness after standing at various temperature for 3 days
Investigation for the Selection of the Kind of Polymerization Initiator
In this example, ε-caprolactone was selected as a monomer and the ε-caprolactone and a polymerization initiator were reacted by ring opening polymerization and, hence, the kind of polymerization initiator gave an important influence on the crystallizability of the resulting amorphous polymer chain. Therefore, as shown in Table 7, there were used as a polymerization initiator 1,4-butanediol (1,4-BD), 1,5-pentanediol (1,5-PD), 1,6-hexanediol (1, 6-HD), nonanediol (NP), neopentyl glycol (NPG), 3-methyl-1,5-pentanediol (3MPG), cyclohexanedimethanol (CHDM), p-xylene glycol (PXG), 1,4bis-(hydroxyethoxy)benzene (BHEB), and BPE-20 (SANYO KASEI KOGYO CO., LTD., trade name: an adduct of bisphenol A with 1 mole of ethylene oxide added to each end thereof) and these were reacted with ε-caprolactone under predetermined conditions to produce poly-ε-caprolactone based diols of samples 11 to 53. For each run, the reaction was proceeded under nitrogen flow until the remaining caprolactone monomer was reduced to 1% or less as measured by gas chromatography.
Table 7 shows the amount of catalyst and reaction temperature used in each reaction, the designed and calculated values of the number of ε-caprolactone units, designed and found values of average molecular weight, and molecular weight distribution (Mw/Mn).
TABLE 7__________________________________________________________________________ Ini. ε-CL CAT R.Temp AMW AMW NClSample K. P. P. K. ppm ° C. Dd. Md. Cd. Mw/Mn__________________________________________________________________________25 1,4-BD 87 913 MBTO 50 120 1000 1017 4.1 1.24 26 1,4-BD 90 979 MBTO 50 120 1069 1070 4.3 1.20 27 1,4-BD 90 1140 MBTO 50 120 1230 1206 4.9 1.15 28 1,4-BD 90 1360 MBTO 50 120 1450 1424 5.9 1.18 29 1,4-BD 90 1596 MBTO 50 120 1686 1645 6.8 1.17 30 1,5-PD 104 916 MTBO 50 120 1020 1020 4.0 1.18 31 1,5-PD 104 1026 MTBO 50 120 1130 1107 4.4 1.18 32 1,5-PD 104 1140 MTBO 50 120 1244 1228 4.9 1.15 33 1,5-PD 104 1368 MTBO 50 120 1472 1446 5.9 1.14 34 1,5-PD 104 1596 MTBO 50 120 1700 1667 6.9 1.19 35 1,6-HD 118 798 MTBO 50 120 916 923 3.5 1.20 36 1,6-HD 118 902 MTBO 50 120 1020 1009 3.9 1.18 37 1,6-HD 118 1140 MTBO 50 120 1258 1243 4.9 1.17 38 ND 160 860 MTBO 50 120 1020 1012 3.7 1.16 39 ND 160 1140 MTBO 50 120 1300 1272 4.9 1.15 40 NPG 104 912 MTBO 50 120 1016 1021 4.0 1.27 41 NPG 104 1026 MTBO 50 120 1130 1143 4.6 1.31 42 NPG 104 1140 MTBO 50 120 1244 1240 5.0 1.35 43 NPG 104 1472 MTBO 50 120 1472 1476 6.0 1.23 44 NPG 104 1596 MTBO 50 120 1700 1697 7.0 1.23 45 3-MPD 118 882 MTBO 50 120 1000 1001 3.9 1.24 46 3-MPD 118 1026 MTBO 50 120 1144 1152 4.5 1.15 47 3-MPD 118 1140 MTBO 50 120 1258 1271 5.1 1.33 48 3-MPD 118 1368 MTBO 50 120 1486 1413 5.7 1.18 49 3-MPD 118 1596 MTBO 50 120 1714 1708 7.0 1.26 50 CHDM 144 876 MBTO 50 120 1020 1021 3.8 1.18 51 CHDM 144 1140 MBTO 50 120 1284 1264 4.9 1.15 52 CHDM 144 1368 MBTO 50 120 1512 1476 5.8 1.16 53 CHDM 144 1482 MBTO 50 120 1626 1587 6.3 1.14 54 CHDM 144 1710 MBTO 50 120 1854 1801 7.3 1.15 55 PXG 138 882 MTBO 50 120 1020 1025 3.9 1.26 56 PXG 138 1140 MTBO 50 140 1278 1323 5.2 1.21 57 PXG 138 1368 MTBO 50 140 1506 1556 6.2 1.26 58 PXG 138 1596 MTBO 50 120 1734 1784 7.2 1.14 59 PXG 138 1824 MTBO 50 120 1962 2014 8.2 1.15 60 BHEB 198 1140 MTBO 50 120 1338 1320 4.9 1.15 61 BHEB 198 1368 MTBO 50 120 1566 1554 5.9 1.16 62 BHEB 198 1596 MTBO 50 120 1794 1784 7.0 1.14 63 BHEB 198 1824 MTBO 50 120 2022 2011 8.0 1.14 64 BPE-20 316 1140 MTBO 50 120 1456 1418 4.8 1.19 65 BPE-20 316 1368 MTBO 50 120 1684 1662 5.9 1.19 66 BPE-20 316 1596 MTBO 50 120 1912 1861 6.8 1.18 67 BPE-20 316 1824 MTBO 50 120 2140 2093 7.8 1.18__________________________________________________________________________ Ini.: Initiator, K.: Kinds, P.: Parts, CL: caprolactone, P.: Parts CAT: Catalyst, K.: Kinds R.Temp: Room Temperature NCl(Dd.):Designed values of the number of caprolactone units, AMW(Dd.):Designed values of average molecular weight AMW(Md.):Measured values of average molecular weight NCl(Cd.):Calculated values of the number of caprolactone units MBTO: Monobutyl tin oxide TBT: Tetrabutyl titanate
Each of the poly-ε-caprolactone based polyols and equimolar amount of 4,4'-diphenylmethane diisocyanate (MDI) were reacted at 100° C. for 5 hours to obtain various millable polyurethanes.
These millable polyurethanes were evaluated for their stability as an amorphous polymer chain in terms of changes in physical properties upon storage at low temperatures, i.e., by storing them at low temperatures and measuring their glass transition temperature, Tg, and relative crystallizability at -10° C. to obtain the results shown in Table 8. Here, the relative crystallizability was obtained by measuring heat of fusion of a sample using differential scanning calorimeter (DSC) after holding the sample at -10° C. for 10 hours and comparing the data with those of natural rubber, followed by rating them based on the following classes: weak (W), medium (M) and strong (S).
TABLE 8______________________________________ CAT NCl Tg R. Cry. Sample K. (Cd.) Mw/Mn ° C. -10° C.______________________________________25 1,4-BD 4.1 1.24 -35.8 W 26 1,4-BD 4.3 1.20 -36.5 W 27 1,4-BD 4.9 1.15 -40.5 M 26 1,4-BD 5.9 1.18 -45.3 M-S 29 1,4-BD 6.8 1.17 -48 S 30 1,5-PD 4.0 1.18 -35.2 W 31 1,5-PD 4.4 1.18 -37.2 W 32 1,5-PD 4.9 1.15 -40.1 M 33 1,5-PD 5.9 1.14 -44.2 M-S 34 1,5-PD 6.9 1.19 -46.4 S 35 1,6-HD 3.5 1.20 -31.2 W 36 1,6-HD 3.9 1.19 -33.8 W 37 1,6-HD 4.9 1.17 -40.2 M 38 ND 3.7 1.16 -32.6 W 39 ND 4.9 1.15 -41.3 M 40 NPG 4.0 1.27 -32.8 W 41 NPG 4.6 1.31 -35.3 W 42 NPG 5.0 1.35 -38.9 W 43 NPG 6.0 1.23 -42.6 M-S 44 NPG 7.0 1.23 -45.5 S 45 3-MPD 3.9 1.21 -34.8 W 46 3-MPD 4.5 1.15 -35.2 W 47 3-MPD 5.1 1.33 -38 W 48 3-MPD 5.7 1.18 -39.4 M 49 3-MPD 7.0 1.26 -44 S 50 CHDM 3.8 1.18 -21 W 51 CHDM 4.9 1.15 -34.4 W 52 CHDM 5.8 1.16 -38.8 M 53 CHDM 6.3 1.14 -40.4 M-S 54 CHDM 7.3 1.15 -43.7 M-S 55 PXG 3.9 1.26 -22.2 W 56 PXG 5.2 1.21 -30.3 W 57 PXG 6.2 1.26 -34.9 M 58 PXG 7.2 1.14 -38.4 M-S 59 PXG 8.2 1.15 -41 S 60 BHEB 4.9 1.15 -23.4 W 61 BHEB 5.9 1.16 -28.9 M 62 BHEB 7.0 1.14 -33.2 M-S 63 BHEB 8.0 1.14 -41.2 S 64 BPE-20 4.8 1.19 -22.1 W 65 BPE-20 5.9 1.19 -28.9 W 66 BPE-20 6.8 1.18 -33.8 M 67 BPE-20 7.8 1.18 -41 M-S______________________________________ CAT: Catalyst, K.: Kinds NCl(Dd.):Designed values of the number of caprolactone units, R.Cry.: Relative crystallizability
Various crosslinked polyurethanes were obtained from the millable polyurethanes of samples 24, 27, 32, 37, 39, 42, 47, 51, 56, 60, and 64 in the same manner as described above These crosslinked elastomers were measured for hardness (Hs:JIS A scale) according to JIS K6253, ball rebound (Rb:%) according to JIS K6255 (based on ISO 4662), tensile strength (Tb: MPa) and elongation (Eb:%) according to JIS K6251 (based on ISO 37), tear strength using a notched, an angled test piece (Tr:N/mm) according to JIS K6252 (based on ISO 34). Here, the crosslinked elastomers were measured for initial hardness after heating at 60° C. for 30 minutes and standing at 23° C. for 3 hours. Table 9 shows the results obtained.
TABLE 9______________________________________ Polyol Sample Ini. m.p. Hs Rb Tb Eb Tr______________________________________24 EG 37.1, 42.2 54 70 17.4 510 28.8 27 BD 36.8, 39.2 53 72 21.2 520 32.5 32 PD 32.6, 37.5 53 71 15.1 500 26.6 37 HD 36.6, 40.5 54 73 22.8 520 33.5 39 ND 44.1 55 70 20.6 520 30.0 42 NPG 23.2, 34.2 55 69 6.8 430 20.8 47 3-MPD 24.4, 35.7 54 70 7.6 450 22.5 51 CHDM 23.3, 31.1 55 72 18.7 500 32.3 56 PXG 25.6, 36.0 53 70 20.8 520 30.5 60 BHEB 27.2, 35.3 54 68 19.6 530 29.8 64 BPE-20 15.2, 21.3 54 62 18.1 530 36.7______________________________________
As a result, it revealed that setting simple parameters such as the kind of polymerization initiator and average number of monomer units enables one to finely or precisely control the crystallizability of the amorphous polymer chain in elastomers. While the crystallizability of crosslinked elastomers can be controlled to some extent by crosslinking or by use of additives, elastomers of the rank "strong" of relative crystallizability are difficult to employ at normal temperature (20° C.) since there is the fear that they could cause inconveniences due to crystallizability. Therefore, in the systems using aliphatic diols as a polymerization initiator, the average number of monomer unit should be 6 or less. In other words, when the average number of monomer units is 7 or more, crystallization occurs even at room temperature so that the polyurethane cannot be used as a polymer chain in elastomers. Further, if the polymerization initiator has a methyl group as a side chain, crystallization decreases but strength also decreases considerably. On the other hand, introduction of substituents which are bulky in a plane such as a benzene ring and a cyclohexane ring, instead of a methyl group, relaxes crystallizability to a suitable extent while at the same time imparting ability of exhibiting orientation crystallizability when stretched, thereby giving elastomers having high strength. When cyclic structures are introduced in the molecule as described above, the crystallizability is relaxed and therefore polyurethanes with an average number of lactone units of up to about 8 can be used. However, since the introduction of cyclic structures also increases the glass transition temperature of the polymer chain, it is desirable to use polyurethanes with an average number of lactone units of 4 or more in order to have a Tg of -20° C. or lower.
Further, according to the present invention, the degree of crystallizability of the amorphous polymer chain as described above can be finely or precisely controlled by selecting the number of caprolactone units, molecular weight distribution of each caprolactone unit, the kind of polymerization initiator R 1 , and the like. For example, there can be produced without difficulty those amorphous polymer chains that are amorphous when they are not stretched but are highly oriented so that they behave as crystallized polymer chains when they are stretched to show excellent physical properties.
This feature can be more clearly understood by the following tests.
Comparative Tests on Crystallizability
Crystallizability was compared between Group A including Samples 4 and 5 in which the molecular weight distribution of ε-caprolactone was narrow and Group B including Samples 11 and 12 in which the molecular weight distribution of ε-caprolactone was broad.
1. Measurement of Crystallizability of Amorphous Polymer Chain Before Crosslinking, Measured Using a Differential Scanning Calorimeter (DSC)
Each sample was measured for the crystallizability of amorphous polymer chain before crosslinking using a differential scanning calorimeter (DSC). FIGS. 2 to 5 illustrate the results of DSC measurements on the behavior of fusion of each sample after holding it at -10° C. for a predetermined time. For comparison, FIG. 6 shows results of DSC measurement on natural rubber (NR).
It was observed that Samples 11 and 12 in Group B with a broad molecular weight distribution showed faster crystallization than Samples 4 and 5 in Group A with a narrow molecular weight distribution. It was observed that the samples with an average number of monomer units of 5 were slower in crystallization than the samples with an average number of monomer units of 6. These observations demonstrate that the use of oligomers having a narrow molecular weight distribution enables one to finely control the crystallizability of the amorphous polymer chain by setting a selected average number of monomer units.
2. Comparison of Crystallization of Crosslinked Elastomers by Measuring Wide Angle X-ray Diffraction (WAXD)
Each sample was measured for wide angle X-ray diffraction of the amorphous polymer chain. FIGS. 7 to 10 illustrate the results of WAXD measurements. Specimens used were each in the form of a 1 mm-thick and 3 mm-wide processed sheet and measurement were conducted at varied elongation (%) at 22° C. Samples 11 and 12 in Group B with a broad molecular weight distribution showed a diffraction peak due to crystallization even when the samples were not stretched. The peak of 20=about 21 degree corresponded to the peak position of ε-caprolactone and, hence, it is presumed that crystallization due to stretching of the crosslinked elastomers is attributable to the crystallization of the repeating unit of caprolactone monomers.
On the other hand, Samples 4 and 5 in Group A with a narrow molecular weight distribution were in an amorphous state when they were under the conditions of no or low stretching and from their low glass transition temperature, it is presumed that they can become a rubber elastic body or elastomer. At an increased elongation, crystallization was observed. This indicates that although the samples of the present invention behave as a rubber elastic body under deformation conditions which ordinary elastomers encounter, they are highly oriented and behave similarly to crystallized polymer when they are excessively or drastically deformed as in the case of wear, breakage, or the like. In addition, the degree of crystallization can be finely controlled by adjusting the average number of caprolactone units.
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A method for preparing an amorphous polymer chain in an elastomer which permits use of previously unavailable monomers while permitting control of crystallizability of the amorphous polymer chain. The method of the present invention thus permits an increased range of industrial scale production by broadening the range of raw materials which can be used and by increasing the design options in constructing the chain.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 11/871,288, filed Oct. 12, 2007, which claims the benefit of U.S. provisional application 60/829,451, filed Oct. 13, 2006, both of which are hereby incorporated by reference herein.
BACKGROUND OF THE INVENTION
Several communication tower manufacturers construct triangular self-supporting towers utilizing vertical columns constructed of triangular trusses. These tower columns (often referred to as the tower legs) resemble miniature triangular shop-welded tower sections. When additional loads are added to the tower, these truss legs may no longer be adequate to safely support the calculated tensile or compressive loads. To alleviate this overstress, the structural capacity of the truss columns must be enhanced. Field welding additional steel onto these truss legs is expensive and creates the potential for several problems. The heat of the welding operation destroys the galvanized coating on the existing steel members creating a corrosion problem. The heat of the welding operation may warp the existing steel and the sparks create a fire hazard. This invention was developed to address these problems.
SUMMARY OF THE INVENTION
Provided is a method of reinforcing a triangular truss column comprising: providing two generally vertical pipe reinforcing columns ( 16 ) each having a first pipe reinforcing plate attached at the top of the column ( 17 ) and a second pipe reinforcing plate at the bottom of the column ( 17 ); attaching the first pipe reinforcement plate to a first existing plate ( 13 ) of the triangular truss column; attaching the second pipe reinforcement plate to a second existing plate ( 13 ) of the triangular truss column; and connecting each vertical pipe reinforcing column to the truss column at one or more connection points along the pipe reinforcing column length. Also provided is a reinforced triangular truss column having two generally vertical pipe reinforcing columns attached to the outside of a portion of a triangular truss column.
The pipe reinforcing columns are connected to the truss column in the vertical direction using any suitable means as known in the art without undue experimentation. Some examples are described and shown herein. As one example, a metal strap or band ( 18 ) that spans one side of the triangular truss column is connected to two legs ( 12 ) of the triangular truss column ( 11 ). The strap or band may be connected to the legs of the triangular truss column using any suitable means, including bolts. The band or strap is any suitable width and thickness that provides the desired amount of support. It is not necessary, and is not preferred, that the metal strap be so wide that that it results in wind resistance or excess weight. In another embodiment, the pipe reinforcing columns are connected to the truss column using a band or strap which surrounds the truss column and the pipe reinforcing columns.
In one embodiment, the pipe reinforcing plates are attached to the existing plate of the triangular truss column using bolts ( 15 ). The pipe reinforcing column may be made from any suitable material, and do not need to be made from the same material. Each pipe reinforcing column may be hollow or solid.
As used herein, “generally vertical” or “generally horizontal” indicates the direction does not need to be exactly vertical or exactly horizontal with respect to a fixed point, but includes those situations where there is a small amount of variance, for example, ±10 degrees of variance. Other degrees of variance are included, for example ±5, ±15 and ±20 and all intermediate ranges and values therein.
BRIEF DESCRIPTION OF THE FIGURE
FIG. 1 illustrates a reinforced triangular truss column assembly in elevation view.
FIG. 2 is a horizontal cross section of the reinforced truss column assembly along line 2 - 2 of FIG. 1 .
FIG. 3 is a horizontal cross section of the reinforced truss column assembly along line 3 - 3 of FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
Truss Columns:
A single truss column is constructed of three individual solid round bars shop-welded at the top and bottom to a common plate. These three solid bars are connected to each other with horizontal and diagonal bracing ( 14 ) forming a three-dimensional triangular truss. It requires three truss columns to form a single triangular tower section. These tower sections are then stacked vertically and bolted together at the truss column plates.
Solution:
Presented here is a method to enhance the structural capacity of the existing truss columns that does not require field welding. Two vertical pipes are added to the three solid round rods of the truss column. These pipes have plates welded at the top and bottom. Several of the existing truss column splice bolts are removed. A new pipe column is inserted with new longer splice bolts inserted to connect the top and bottom plates of the new pipe column to the top and bottom plates of the truss column. There are also straps or other devices that connect the new pipe column to the truss column at intermediate intervals to prevent the pipe column from buckling away from the existing truss column. These straps are connected to the truss column with U-bolts ( 19 ) or other suitable connecting means, as known in the art. This invention is useful for any towers with truss-type legs (columns).
The result is that the truss column is no longer comprised of just three solid round rods or legs ( 12 ) but is now is comprised of the original three solid round rods plus two round pipes ( 16 ) which may be hollow.
FIGS. 1-3 show embodiments of the invention. FIG. 1 shows a large-scale view. FIG. 2 shows the use of the invention at the existing tower leg splice plate( 13 ), as described herein. FIG. 3 shows a connection band ( 18 ), as described herein.
All elements of the invention may be made from any suitable material, as known to one of ordinary skill in the art. The materials used may depend on the environment where the tower is used, as known in the art. The diameters of the vertical pipes ( 16 ) may vary, depending on the application. The vertical pipes ( 16 ) may be made from any suitable material, as known to one of ordinary skill in the art. The vertical pipes ( 16 ) may be metal, composite or polymer, for example. The vertical pipes( 16 ) may be hollow or solid. The connecting bands( 18 ) may be constructed from any suitable material, as known to one of ordinary skill in the art.
Although the invention is described with respect to triangular truss towers ( 11 ), it is well known in the art that the invention may be used with four-legged towers, as well, without undue experimentation, using two, three, or four vertical pipe reinforcing columns, using the information provided here and that information known in the art.
It should be understood that although the present description has been disclosed by specific embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention.
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A reinforced triangular truss column having two vertical pipe reinforcing columns added to the three rods of the truss column is provided. Also provided is a method of reinforcing triangular truss columns comprising adding two vertical pipe reinforcing columns to a triangular truss column.
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[0001] This application claims priority under 35 U.S.C. §119(e) from U.S. Provisional Patent Application No. 62/204,483 for a SYSTEM AND METHOD FOR ATHLETIC COMPETITION SIGNALING, filed Aug. 13, 2015 by Nicholas A. Santino, Jr., and from U.S. Provisional Patent Application No. 62/068,892 for a SYSTEM AND METHOD FOR ATHLETIC COMPETITION SIGNALING, filed Oct. 27, 2014 by Nicholas A. Santino, Jr., both US Provisional applications being hereby incorporated by reference in their entirety.
BACKGROUND & SUMMARY
[0002] The disclosed embodiments relate to a signaling device and system for an athletic competition and, more particularly, to an electronic starting device that includes signaling devices with lights to permit accurate starting and timing of races and other competitive events and games that include hearing impaired athletes. Traditionally a centralized combination sound and light system is used to initiate the start of a race, wherein a sound is produced either from a starting whistle, pistol or through an electronic loud-speaker in the proximity to the start line. A flash of light often accompanies the sound so the contestants, as well as the officials, are made fully aware of the signal to begin the competition. The equivalent in outdoor track and field competition is a starter's pistol that emits both a sound and a puff of smoke in response to the starter pulling the trigger of the pistol. Although sound generating devices for starting races have long been used, recently they have met objections in that proper placement of the sound source to permit equitable reception of audible signals by all contestants has been difficult to obtain. Furthermore, while hearing impaired athletes and competitors may be disadvantaged by their inability to easily perceive sound, the disclosed embodiments provide a visual cue and an equitable starting method for all athletes. And, the use of a signaling system employing lights may improve the responsiveness and accuracy for hand-timed events as well.
[0003] Often races are decided by milliseconds; therefore, the seemingly minimal delay between the start and the times the various athletes receive the audible start signal has become increasingly important in sporting events. Therefore, a visual starting cue, in the proximity of the competitor, has become preferable. Additionally, hearing impaired athletes are becoming more involved in competitive sports, most notably in swimming events. Lacking an individual visual cue the hearing impaired swimmer must either use peripheral vision to react to a flash of light near the starter, or in the alternative look up and observe the starter's hand signals, either of which potentially compromises the hearing impaired swimmer's body position at the start. Consequently, in the interest of equality, it is imperative that an electronic starting system include at least a visual cue for the participants.
[0004] In the Swimmers Official's Guidelines Manual (July 2012), hereby incorporated by reference, on page 26 under Modifications for the deaf and hard - of - hearing , the guide states “Deaf and hard of hearing swimmers require a visual starting signal, i.e., a strobe light and/or starter's arm signals. The modification may include the referee reassigning lanes within the swimmer's heat, i.e., exchanging one lane for another, so that the strobe light or starter's arm signal can more clearly be seen by the deaf or hard-of-hearing swimmer.” Given the prerequisite that accommodations for special needs should be as transparent as possible, the interchanging of lanes, visual hand signals and providing a strobe light has been acknowledged as exceedingly intrusive in a hybrid event, and in some cases ineffective. For instance, the preparatory start protocol for any individual competition advises the athlete to first approach the blocks, take their mark and then go, as stated in the Swimmers Official's' Guidelines Manual (p. 8). Furthermore a central strobe light is not necessarily applicable to the referee's announcements of the event as stated in the SOGM on page 9;
“Suggested protocol for forward start whistle preparatory commands when there is only one official (referee/starter):
to bring the swimmers to the starting area, the referee/starter blows a short series of whistles (no fewer than 4) followed by the announcer or referee/starter announcing the event/distance/heat, e.g., “This is the 200-yard freestyle, heat 2,” when all swimmers have approached the blocks, the referee/starter blows a long whistle for the swimmers to step onto the blocks and take their positions, when swimmers are settled into position, give the command, “Take your mark,” when swimmers are stationary, activate the starting signal.
Note: If a swimmer(s) has not responded to the whistle indicating they should step up or step in, the referee/starter should give the verbal commands.”
[0011] It is further noted, in particular, that in conventional swimming events a visual queue must be able to be seen from either a standing position (e.g., on the starting platform), or from an alternate position (e.g., in the water during backstroke events). For example, U.S. Pat. No. 7,193,167 discloses a single start light integrated within a complete starting platform for the purpose of visually alerting an athlete to the start of a race, similar to the aforementioned strobe light as discussed above. The limitation of a solitary start light is that a competitive athlete traditionally relies on a starting sequence including a “step-up” and a “take your mark” indication to psychologically and physiologically prepare for the start of a race.
[0012] In accordance with a feature of the disclosed embodiment, providing a sequence of visual indicators at the start of a competitive race significantly “levels the playing field” so that each athlete has an equal reaction opportunity, regardless of any hearing deficiency. Practically speaking, however, given that existing competitive swimming pools already include a starting platform for each lane, it would be cost prohibitive to replace the existing platforms with new platforms.
[0013] Therefore it is desirable to provide a signaling system that is modularized and/or self-supporting such that it can be used with various styles of starting platforms or in different athletic event venues (e.g., swimming pools, indoor and outdoor tracks, volleyball and basketball courts, soccer fields, etc.). Moreover, the disclosed embodiments provide a plurality of signaling colors in order to improve the capability for the system to indicate different starting commands. For example, providing at least three signaling elements (e.g., flashing red for ready, solid blue for take your mark, solid green for go) to produce a visual output viewable from a plurality of positions about the start platform.
[0014] As further disclosed in alternative embodiments, the signaling system is suitable for use in various configurations, permitting an adaptable configuration that can be used with different starting platforms as well as different venues. For example, each and every starting platform could include a detachable base and illuminating elements electrically connected to a common controller.
[0015] Additionally, it is contemplated that a single controller would independently energize the signaling elements in a defined sequence, where a controller (wired or wireless) selectively operates at least one of the signaling elements simultaneously.
[0016] Furthermore, each one of the three or more light emitting components could include a unique color, or for color blind athletes a flashing pattern or other nomenclature indicative of the light's significance.
[0017] Disclosed in embodiments herein is an athletic competition (e.g., swimming) signaling apparatus, comprising: a translucent housing, said housing including an attachment component coupling the housing to a structure, and at least three independent signaling elements operatively associated with said housing; wherein a first of the at least three signaling elements produces a visual output viewable from a plurality of positions including both a starting position and a staging position, and where the remaining two of the at least three signaling elements are viewable from primarily from the starting position.
[0018] Also disclosed herein is an athletic competition signaling apparatus, comprising: a base resting on a surface adjacent the starting position of an athletic competition, said base including a battery compartment therein for holding a battery, and an attachment component extending from said base; a rod, adjustably attached to said attachment component; a translucent light housing, said light housing including a linear tape with a plurality of light emitting diodes of at least two different and individually activated colors sequentially spaced along the linear tape, said linear tape wrapped about a core and inserted within a translucent hollow tube, said tube also including at least one end cap for receiving the core with wrapped tape therein, and a second attachment component coupling the housing to a support structure such as the rod; and control circuitry, operatively connected to said battery and the signaling elements, said circuitry controlling, in response to a plurality of external signals, the on/off state for the signaling elements; wherein a first of the at least three signaling elements produces a visual output viewable from a plurality of positions including both a starting position and a staging position, and where the remaining two of the at least three signaling elements are viewable from primarily from the starting position.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a view of an exemplary starting platform for a swimming event with an associated signaling device;
[0020] FIG. 2 is a perspective view of an embodiment of the signaling device;
[0021] FIG. 3 is an illustration of a base of the signaling device for use in a self-supporting embodiment;
[0022] FIG. 4 is a representation of the components in a translucent light housing used as part of the signaling device;
[0023] FIGS. 5A-5C are illustrations of the different operating (“on”) modes of the translucent light housing;
[0024] FIG. 6 is a block diagram illustrating circuitry and various components of a 9-12 volt embodiment of the signaling device;
[0025] FIG. 7 is an illustration of the operations carried out by the signaling device system in an exemplary embodiment; and
[0026] FIG. 8 is an illustrative example showing the use of the signaling device in accordance with a track and field venue as an alternative embodiment . . . .
[0027] The various embodiments described herein are not intended to limit the disclosure to those embodiments described. On the contrary, the intent is to cover all alternatives, modifications, and equivalents as may be included within the spirit and scope of the various embodiments and equivalents set forth. For a general understanding, reference is made to the drawings. In the drawings, like references have been used throughout to designate identical or similar elements. It is also noted that the drawings may not have been drawn to scale and that certain regions may have been purposely drawn disproportionately so that the features and aspects could be properly depicted.
DETAILED DESCRIPTION
[0028] For a general understanding, reference is made to the drawings. In the drawings, like references have been used throughout to designate identical or equivalent elements. It is also noted that the drawings may not have been drawn to scale and that certain regions may have been purposely drawn disproportionately so that the features and concepts could be properly illustrated.
[0029] Referring to FIG. 1 illustrated is a conventional swim platform 100 having platform surface 102 for a swimmer to stand upon from step 104 . The platform surface 102 of the competitive starting system is situated on and mounted to the pool deck adjacent to a swimming lane. Foot step 104 is oriented to provide access to surface 102 for the get ready position. A rearward facing bar or handle(s) 106 is positioned either vertically or horizontally beneath the platform so a swimmer is able to grasp bar 106 from within the pool for the ready position of a backstroke event. Platform surface 102 further includes at least one support member 118 , which is inserted into or attached to a corresponding mounting feature within the apron or deck of the pool.
[0030] In one embodiment a deck plate 120 may be located in direct proximity of support member 118 to provide connectivity between one or more signaling devices and a central power source and/or controller via a cable or wiring harness 110 to a central connection unit or alternatively a wireless controller to provide a user control device operable by a race official. Alternatively, in the absence of installed deck plates a cable or wiring harness interface may be used between each signaling device. While various forms of interconnection may be used, conventional color-coded banana-type plugs and jacks are illustrated in several embodiments. Such plugs are available from many sources, including Pomona Electronics (e.g., single solderless stackup banana plugs Model 1325, and double plugs with wire guide Model MDP).
[0031] In one embodiment deck plate 120 may include connectors for both conventional timing system signals, as well as the power and signal connections for the signaling components disclosed herein. Deck plate 120 is a multi-layer plastic that is engraveable (Rowmark® HW-853 series) and provides connection for the signaling light system that may be mounted on or associated with swimmer platform 100 . In one embodiment, for example as depicted in FIG. 2 , the signaling system includes an approximately 16-inch long and generally round translucent tube that forms an outer shell of the light housing. For example, the tube may be an extruded polycarbonate material that is rendered translucent during its manufacture of via a post-manufacturing treatment or coating applied to its interior. While shown in a stand-alone configuration in FIG. 2 , the signaling system is adaptable such that the light housing position may be adjusted or it may be removed or detached from the base so that the light housing is easily connected to and removed from the start blocks. The connections and adjustments are made using attachment components such as block 250 and a rod 252 to fit just under the platform. In a swimming venue, housing 216 , or at least light tube 210 , is attachable adjacent or on platform structure 102 and/or support member 118 by any suitable means, such as a spring clip, adjustable clamp, Velcro®, adhesive or various connection hardware such as nuts and bolts. The ability to retrofit the disclosed signaling light system into existing swim platforms provides several advantages: (i) only placed on platform during competition events; (ii) portable, can be moved between pools or other event venues; (iii) readily adapts a pool or existing venue to accommodate events that include hearing impaired athletes; and (iv) cost effective by avoiding replacement of existing starting platforms.
[0032] In other sporting venues the light housing may simply rest on the ground (e.g., FIG. 8 ), or may be supported in a desired (e.g., vertical or horizontal) position from a weighted base or a multi-leg stand.
[0033] More specifically, as illustrated in the embodiment of FIG. 2 , the signaling apparatus comprises translucent light housing 216 , which is preferably a water tight, corrosion proof enclosure, further including interface cable 226 , a plurality of color illuminating elements of different colors (see e.g., FIG. 4 ), which are viewable from various starting positions including both starting and staging positions. An advantage of the housing 216 is that the activated lights are indeed viewable about the perimeter, from all radial angles (360 degrees) about the housing and thereby eliminates blind spots that may prevent an athlete from seeing the visual cues provided by the lights within the housing. Also referring to FIG. 4 , housing 216 is generally tubular in shape. The housing includes an attachment component such as a rod 252 coupling the housing, via a coupling 264 , to the support base 216 , and a plurality of signaling elements are operatively distributed within the translucent housing. In one embodiment, ⅜″ aluminum rod may be used, and the attachment components such as block 250 and coupling 264 would include connection holes sized to receive the ⅜″ rod, and also a set screw, thumb screw or similar mechanism to hold the rod within the block. The ends of the translucent tube are covered or sealed with a conventional cap or plug 266 to minimize exposure to water, dirt, etc.
[0034] As noted relative to the embodiments disclosed above, and as further described relative to FIG. 6 , the system may also include control circuitry within the support base or housing 216 . The base 216 includes two “levels”. A top level 320 includes the connections and circuitry, while a lower level 322 includes a removable and rechargeable battery 364 . The battery further provides mass in the base to assure stability when a light housing is attached. The control circuitry controls the color selection and on/off state (or flashing pattern) for the signaling elements. As seen in FIG. 3 , an LED illuminated toggle switch 360 is available at one end of the support base 216 , and not only controls the availability of the system and signaling lights, but itself provides a visual indication of the system being “on” and having battery or other source of power. The battery 364 , a Lithium-based 12V battery that may or may not be rechargeable, provides adequate power to not only supply the control circuitry but to also power the signaling LEDs in response to a wired or wireless signal received by the system. The signaling apparatus includes or requires a source of power such as provided by battery 364 , or via a deck plate connection or other source such as 12V connection 368 , and an associated fuse 370 . Base 216 also includes an attachment arm such as an L-shaped rod or handle 380 , whereby the attachment block 250 can be adjustably attached to the unattached (horizontal) end of the rod 380 . In this way the base, via rod 380 , can provide support for rod 252 and associated light housing 210 . In another embodiment, an additional switch 306 may be used to select the mode of operation of the controller—either linked to a timing system or responsive to manual signals (e.g., for training/testing). Lastly, base 216 itself may be formed from two conventional boxes that are modified with the required penetrations and attached to one another, or from a custom-molded unit with upper and lower enclosures to separate the battery from the electrical circuitry and components.
[0035] The control signals may be received via a cable that is either connected to the banana-type jacks 390 on the top of the base, or via one or more of the plurality of pin-type connectors 392 (e.g., a 5-pin connector from wireless receiver) or 394 (e.g., 8-pin connector from adjacent signaling device or deck plate) on the top portion of the support base. It will be appreciated that the wired connection may be facilitated by a deck plate 120 that includes not only timing signal connections, but also connections for power (12V), speakers and the like.
[0036] Referring also to FIG. 4 and FIGS. 5A-5C , the translucent light housing 210 includes a cylindrical translucent tube 216 . A tape or ribbon 452 of multiple-colored light-emitting diodes (LEDs) is spirally wrapped about a cylindrical core 454 and the wrapped core is inserted within the translucent outer tube 216 after electrical connections are made to cable 226 . The tube has caps or plugs 266 applied to the ends thereof to hold the LEDs inside and to prevent the LEDS from environmental exposure (e.g., being splashed, etc.). Depending upon the configuration, one of the plugs may include a hole or aperture to allow cable 226 to pass through, and where the cable is connected to the electronic circuitry in the housing and provides power/signals to the LED tape in order to control the on/off state of the LEDs as well as the color produced.
[0037] In operation, the LEDs are independent controllable by color, and the red, blue or green LEDs may be illuminated independently or concurrently. As illustrated in FIGS. 5A-5C , respectively, the three independent lighting modes are illustrated with the red, blue and green lights, respectively, showing within the translucent housings 210 . Moreover, the lights may be displayed in a continuous-on manner or may be flashed in one or more patterns to signify different steps or commands to the athletes. It is also possible, as will be appreciated, to alter the LED display configuration to not only concurrently display two or more colors of LEDs, but also to intermix the flashing of such LEDs to thereby produce numerous distinct signals in the event that more than three are needed.
[0038] In the illustrated embodiments, the approximately 18-inch long light tube 210 is about 1-inch in diameter and is frosted so as to appear translucent. In the illustrated embodiment the tube 216 can attach via the supporting structure to the base, or alternatively, the tube may be directly connected to a deck plate or other wired system to provide the appropriate power signals to drive the lights. For example, the signaling device 202 may be configured as a single unit under a block for training, or also to an on-deck cable or wired deck plate 120 that handles as many lanes as needed. As will be appreciated, the signaling device illustrated is intended to run the lights in conjunction with providing other timing connections. And in another embodiment or configuration, a plurality of light tubes and/or signaling systems may be run off a separate 12V control unit that can be operated manually, with a wireless fob, or plunger push button(s) (see FIG. 6 ), and in all cases the starting device trips the green light at the same time the timer is started.
[0039] As an alternative to a deck plate or harness, for a wired system, a wireless system can be implemented to control the state of the illuminating elements within the signaling device by the use of either a radio, IR or other frequency, to activate the appropriate lights. Referring to FIG. 6 , for example, using a conventional radio-frequency transmitter (e.g., 315-433 MHz) such as found in a fob available from various sources, the operation of the lights may be controlled by pressing separate buttons (e.g., A, B or C) on the fob. The receiver ( 322 ), connected to or embedded within the controller 610 , receives the signal and makes the connection to provide power from battery 364 and thereby light the corresponding light. A simple schematic for the wireless receiver is illustrated in FIG. 6 . As will be appreciated, the optional relays, which may be operatively included within the microprocessor or as separate components 650 , operate to induce a power connection to the LED light circuits in ribbon 452 in response to the received signals from the fob buttons or from plunger(s) 618 or the timing/starting system 614 . With regard to the wireless inputs, also contemplated is the use of Bluetooth, IEEE 802.15.1 at 2.4 GHz transmitters and receivers, which typically have a range of 30-40 feet.
[0040] In a wireless embodiment, the signaling device associated with each swim platform 100 could be connected to and synchronized to a common controller which would then transmit common signals (e.g., battery power) to each of the housings 216 to signal the athletes of the beginning of a race. It is further anticipated that other display devices, for example an alphanumeric display matrix, could be implemented within each swim platform to encode and display commands for the hearing impaired and or for spectators.
[0041] With regard to the timing starter signals from system 614 , any suitable system providing a low voltage current via suitable switches may be used as an input to circuitry 610 , as an input to a microcontroller or equivalent component 612 , for controlling illumination of the starting sequence lights. One such system is an Infinity Speed Light system. The starting system switches may be activated manually or in the alternative a timer could be used to automatically sequence the lights (see e.g., FIG. 7 ), possibly in a random cadence to mitigate false starts due to the potential for the anticipation of the start light. The controller may also be interfaced with a race timer as well as a sounding device (e.g., horn, buzzer, etc.) to coincide with the start light. In an alternative embodiment, the controller may also include a transceiver for bilateral communications with each of the swim platforms, also having a transceiver therein, for the purpose of transmitting race start and stop events, as well as false starts. As described above, the platform receiver selectively causes power to be supplied to the lights when a trigger signal is received from the transmitter of the controller. Additionally, false starts and standings may be relayed back to the event referee by a wire, or may communicated wirelessly.
[0042] Also contemplated in one embodiment of the signaling system is a configuration where the receiver is either connected to or located in housing 216 (not separately connected) and is operatively connected to the control circuitry of FIG. 6 as illustrated to produce a desired visual signal in response to a user depressing one or more buttons on a wireless transmitter fob 610 .
[0043] The signaling apparatus is well suited for swimming events where, in the past, a sound and arm motion comprised a start signal which has been problematic for athletes in general, but especially inequitable for the hearing impaired. Accordingly a plurality of signaling devices, preferably one attached to each swim platform, are engaged to stage and start a swimming competition by energizing a sequence of at least three lights. In order to discriminate the significance of each signaling operation, a distinct color and/or pattern is assigned to each, as depicted and described relative to the flowchart of FIG. 7 .
[0044] Several of the enclosures or housings described herein may be made from conventional enclosures with modifications to enable the addition of various connections for power, signals and the like. In one embodiment the housings, such as those available from Philmore (e.g., ABS Enclosures No. PB404, PB411 and PB413), are waterproof, meet NEMA 4 specifications and would provide suitable enclosures.
[0045] Having referred to the various components of the system, attention is now turned to the typical operation of the system, and a description is included relative to FIG. 7 . As described herein, an input is received by the microprocessor at 710 and is interrogated. First, the red LEDs are used to tell the swimmer to get up on the block or to get into the water. These lights are controlled MANUALLY in response to a button plunger or wireless fob in a hand of the referee. In the illustrated embodiment, the microprocessor, in response to the “READY” input via a plunger, wireless fob, etc., is detected at step 720 , and then operation 724 is executed by first flashing the red LEDs on and off for approximately 5-seconds and then putting the red LEDs into a continuous on state.
[0046] Next, as detected by step 730 , the Take Your Mark (TYM) input initiates the blue LED lights (step 734 ) used to tell the swimmers take a racing position. These lights are also likely to be controlled MANUALLY by a button plunger or wireless fob in the hand of the starting official who then is “CONTROLLING” the time limit of the lights being on or off.
[0047] Lastly, at steps 740 and 744 , green lights are used to tell the swimmers to “GO”. These lights may be controlled automatically by the starting official when pushing the start button function on the start system and timing system. In one embodiment, in response to the official pressing or triggering the start of the timing system, the same signal is received by the microprocessor and in response to the signal the green or GO light is turned on. It will be further appreciated that for practice sessions, the fob has an adequate number of buttons so as to be employed to produce signals for all three (TYM, SUP and GO) lights as well as possible additional colors and/or patterns. Once the green light has been illuminated, it is kept in an on state for a defined period “N” (e.g., approx. 3 seconds), and after that delay ( 748 ) the system is reset by operation 752 and readied for the next timing sequence and all lights are turned off.
[0048] As noted above, the disclosed signaling system may be employed in other athletic venues. As an illustrative example, reference is made to FIG. 8 , where a track venue is illustrated (indoor or outdoor). In the example, one lane 810 of a track is illustrated. The lane includes a starting block 820 placed near the starting line 824 as in a conventional configuration for a “sprint” start where blocks are used. In the illustrated embodiment, an elongated translucent tube 216 (approx. 32 inches in length), is placed in the lane between the athlete's feet so as not to interfere with the start. In this configuration, the athlete has a clear view of the translucent light tube and can also adjust its placement, forward or backward, at a desired viewing location based upon whether the athlete employs a head down or head up starting stance. In the illustrated embodiment, the tube 216 may be electrically connected to the control system and source of power via a plug configuration that is either available in a modified starting block or is provided via a wiring harness or plug receptacle available in the track surface or rails about the inner edge of the track. And, in a stand-up start, one or more vertical tubes 216 may be placed along an edge of the track to be viewed by the athletes. In another alternative embodiment, the translucent tube(s) or a similar configuration may be placed on top of or embedded within a lane marking line 830 .
[0049] It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims
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In a competitive athletic event the disclosed signaling system provides for visually signaling of participants, for example, a lane specific visible indication to begin a race. A sequence of light colors is used to signal the start of a race, and is believed advantageous over an audible start signal, particularly for athletes who are hearing impaired.
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A portion of the disclosure of this patent document contains material, which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office patent file or records, but otherwise reserves all copyright rights whatsoever. The following notice applies to the software and data as described below and in the drawings hereto: Copyright © 2002, Sun Microsystems, Inc., All Rights Reserved.
FIELD OF INVENTION
The present invention generally relates to the field of managing data tracking. More specifically, an embodiment of the present invention provides a method of reorganizing data in log files for data tracking management.
BACKGROUND OF INVENTION
As integrated circuit (IC) fabrication technology improves, manufacturers are able to integrate additional functionality onto a single silicon substrate. As the number of these functions increases, however, so does the complexity of the designs, and potential defects associated therewith. Often to meet deadlines, many designers work on a same design simultaneously. The partial designs will then need to be put together to make a final product. The timing is of the essence in making sure that the many portions of the design are finished relatively simultaneously and free of defects. In addition, it is imperative that strict deadlines are followed, in part, because a later design stage may depend on information regarding a preceding stage before meaningful design may be commenced.
FIG. 1 illustrates an exemplarily flow diagram of a typical design process 100 for ICs in accordance with the prior art. The process can be generally divided into a front end design phase and a back end development phase. During the front end phase, an engineer designs and develops a logical representation of an IC from a set of specifications in form of a schematic (stage 102 ). At a stage 104 , the schematic is then loaded into a computer from which a circuit netlist is generated. The netlist defines the entire IC design including all components and interconnections.
Moreover, the IC information may be developed using hardware description language (HDL) and synthesis. With the aid of circuit simulation tools available on computers, a designer can then simulate the functionality of a given circuit at a stage 106 . The circuit simulation process may involve several iterations of design modifications and improvements, until the circuit design is finalized at a stage 108 .
The back end development involves several stages during which a final circuit layout (physical description) is developed based on the schematic design of the front end. In a stage 110 , various building blocks (or cells), as defined by the finalized circuit schematic, are placed within a predefined floor plan. For ICs designed based on array or standard cell technology, the various building circuit blocks are typically pre-defined and made available in a cell library. For example, during the stage 110 , a plurality of cells are selected from one or more cell libraries and the cell interconnects are determined. More particularly, groups of cells may be interconnected to function as a flip-flop, shift registers, and the like. The routing of wires to interconnect the cells and achieve the aforementioned goals is preformed during a routing stage 112 , typically referred to as conducting paths, wires or nets. Accordingly, in the stage 112 , interconnects between circuit elements are routed throughout the layout. In a stage 114 , the accuracy of the layout is verified against the schematic and if no errors or design rule violations are found at a stage 116 , the circuit layout information is used for the process of fabrication in a stage 118 .
Accordingly, layout tracking and verification and/or defect tracking of discovered problems are important parts of manufacturing an IC. These tasks may be partially automated by using a software application. In many software applications where the important data is recorded and appended to the end of a file constantly, a meaningful reordering and reorganizing of the data in that file can be a cumbersome task. For example, for a layout tracking tool, layout designers may update a layout chart periodically and a layout manager needs to sort out the layout chart information to keep track of scheduling. Furthermore, in a defect tracking tool example, interested parties need to open the defect log file, read the file from the beginning to the end repeatedly, analyze the records, and sort them so as to understand and follow the defect cycle (who opened, when it was assigned, when it was accepted, when it was fixed, when it was closed, etc.).
In both of these examples, opening the log file(s), analyzing the records, and reordering them can be a time-consuming task prone to many errors. A software application may be utilized to perform such tasks by, for example, opening the current log file for read and a temp file for write, getting the data from log file one portion at a time, organizing the data, writing the organized data to the temp file, closing the log file, and writing the temp file over the log file. However, one or more of the following drawbacks still remain: (1) IO: read from the top to the bottom of the log file repeatedly; (2) Performance: opening and closing files; and/or (3) Human Error: analyzing and recording the appropriate data.
SUMMARY OF INVENTION
The present invention, which may be implemented utilizing a general-purpose digital computer, in various embodiments, includes novel methods and apparatus to reorganize data in a log file. In an embodiment, a method of reorganizing data in an original log file is disclosed. The method includes: obtaining a data record from the original log file; examining the data record; if the data record includes a single-value entry, inserting the data record in a single-value storage linked list; if the data record includes a multiple-values entry, inserting the data record in a multiple-values linked list; and utilizing data from the multiple-values and single-value linked lists to write data to a new log file.
In another embodiment, the new log file includes a reorganized version of the data from the original log file.
In a further embodiment, the method may further include inserting a time stamp into the multiple-values linked list if the data record includes the multiple-values entry.
In yet another embodiment, the method may further include inserting a time stamp into the single-value linked list if the data record includes the single-value entry.
BRIEF DESCRIPTION OF DRAWINGS
The present invention may be better understood and its numerous objects, features, and advantages made apparent to those skilled in the art by reference to the accompanying drawings in which:
FIG. 1 illustrates an exemplarily flow diagram of a typical design process 100 for ICs in accordance with the prior art;
FIG. 2 illustrates an exemplary computer system 200 in which the present invention may be embodied;
FIG. 3 illustrates an exemplarily method 300 in accordance with an embodiment of the present invention; and
FIG. 4 illustrates an exemplarily report 400 in accordance with an embodiment of the present invention.
The use of the same reference symbols in different drawings indicates similar or identical items.
DETAILED DESCRIPTION
In the following description, numerous details are set forth. It will be apparent, however, to one skilled in the art that embodiments of the invention may be practiced without these specific details. In other instances, well-known structures, devices, and techniques have not been shown in detail, in order to avoid obscuring the understanding of the description. The description is thus to be regarded as illustrative instead of limiting.
Reference in the specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least an embodiment of the invention. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment.
In addition, select embodiments of the present invention include various operations, which are described herein. The operations of the embodiments of the present invention may be performed by hardware components or may be embodied in machine-executable instructions, which may be in turn utilized to cause a general-purpose or special-purpose processor, or logic circuits programmed with the instructions to perform the operations. Alternatively, the operations may be performed by a combination of hardware and software.
Moreover, embodiments of the present invention may be provided as computer program products, which may include machine-readable medium having stored thereon instructions used to program a computer (or other electronic devices) to perform a process according to embodiments of the present invention. The machine-readable medium may include, but is not limited to, floppy diskettes, optical disks, compact disc-read only memories (CD-ROMs), and magneto-optical disks, read-only memories (ROMs), random-access memories (RAMs), erasable programmable ROMs (EPROMs), electrically EPROMs (EEPROMs), magnetic or optical cards, flash memory, or other types of media or machine-readable medium suitable for storing electronic instructions and/or data.
Additionally, embodiments of the present invention may be downloaded as a computer program product, wherein the program may be transferred from a remote computer (e.g., a server) to a requesting computer (e.g., a client) by way of data signals embodied in a carrier wave or other propagation medium via a communication link (e.g., a modem or network connection). Accordingly, herein, a carrier wave shall be regarded as comprising a machine-readable medium.
FIG. 2 illustrates an exemplary computer system 200 in which the present invention may be embodied in certain embodiments. The system 200 comprises a central processor 202 , a main memory 204 , an input/output (I/O) controller 206 , a keyboard 208 , a pointing device 210 (e.g., mouse, track ball, pen device, or the like), a display device 212 a mass storage 214 (e.g., a nonvolatile storage such as a hard disk, an optical drive, and the like), and a network interface 218 . Additional input/output devices, such as a printing device 216 , may be included in the system 200 as desired. As illustrated, the various components of the system 200 communicate through a system bus 220 or similar architecture.
In an embodiment, the computer system 200 includes a Sun Microsystems computer utilizing a SPARC microprocessor available from several vendors (including Sun Microsystems of Santa Clara, Calif.). Those with ordinary skill in the art understand, however, that any type of computer system may be utilized to embody the present invention, including those made by Hewlett Packard of Palo Alto, Calif., and IBM-compatible personal computers utilizing Intel microprocessor, which are available from several vendors (including IBM of Armonk, N.Y.). In addition, instead of a single processor, two or more processors (whether on a single chip or on separate chips) can be utilized to provide speedup in operations. It is further envisioned that the processor 202 may be a complex instruction set computer (CISC) microprocessor, a reduced instruction set computing (RISC) microprocessor, a very long instruction word (VLIW) microprocessor, a processor implementing a combination of instruction sets, and the like.
The network interface 218 provides communication capability with other computer systems on a same local network, on a different network connected via modems and the like to the present network, or to other computers across the Internet. In various embodiments, the network interface 218 can be implemented utilizing technologies including, but not limited to, Ethernet, Fast Ethernet, wide-area network (WAN), leased line (such as T 1 , T 3 , optical carrier 3 (OC 3 ), and the like), analog modem, digital subscriber line (DSL and its varieties such as high bit-rate DSL (HDSL), integrated services digital network DSL (IDSL), and the like), cellular, time division multiplexing (TDM), universal serial bus (USB and its varieties such as USB II), asynchronous transfer mode (ATM), satellite, cable modem, and/or FireWire.
Moreover, the computer system 200 may utilize operating systems such as Solaris, Windows (and its varieties such as CE, NT, 2000, XP, ME, and the like), HP-UX, IBM-AIX, PALM, UNIX, Berkeley software distribution (BSD) UNIX, Linux, Apple UNIX (AUX), and the like. Also, it is envisioned that in certain embodiments, the computer system 200 is a general purpose computer capable of running any number of applications such as those available from companies including Oracle, Siebel, Unisys, Microsoft, and the like.
FIG. 3 illustrates an exemplarily method 300 in accordance with an embodiment of the present invention. In a stage 302 , an existing log file is opened for read operations. A stage 304 obtains record data from the existing log file (e.g., which was opened in the stage 302 ). A stage 306 examines the record data (e.g., obtained in the stage 304 ). In a stage 308 , it is determined whether the end of the log file opened in the stage 302 has been reached. If the stage 308 determines that the end of the file has not been reached, a stage 310 determines whether the record data (e.g., examined by the stage 306 ) includes multiple-value data. If the stage 310 determines that the record data includes multiple-value data, a stage 312 inserts the data record in a multi-values linked list.
The method 300 resumes its operations at the stage 308 once it is done with the stage 312 . Alternatively, if the stage 310 determines that the record data does not include multiple value data, a stage 314 inserts the data record in a single-value linked list. The method 300 resumes at the stage 308 after the stage 314 is reached. If the stage 308 determines that the end of the log file has been reached, a stage 316 opens a new log file for write operations. A stage 318 utilizes the single-value and multi-values linked lists to write data to the new log file. In one embodiment, the stage 318 can write data to the new log file in an order including, but not limited to, chronologically, alphabetically, and the like. In further embodiments, the stage 318 may write the data to another linked list in addition to, or instead of, writing to the new log file. It is envisioned that in an embodiment the stages 312 and 314 may additionally insert the date and/or time when the data record is inserted.
Accordingly, in an embodiment where the log file contains data for multiple users, a linked list for the users may be used. In case of data records for a particular instance, for example, a particular defect or a particular user, a linked list may not be required to keep track of all the log files. A structure may be sufficient to achieve such goals. However, in implantations where the log file contains data from multiple users, a linked list implementation may be significantly beneficial.
Additionally, such a data structure may only contain the members which have the multiple values. In an embodiment, each member may have a linked list. For example, in a defect tracking tool, component name, priority, abstract, “assigned to” may have multiple values whereas defect number and “opened by” may have only one value. With respect to a layout log example, date for running some jobs such as PDV, LVS, and alike may have multiple-value data whereas layout designer or cell name may only have single value-data. In a further embodiment, for each multiple-value data, there may be a linked list to link the data together. Accordingly, each time a new data record which contains multiple-value data is detected from, for example, reading a log file, its value may be inserted onto its respective linked list along with the date, for example. Similarly, every time a new data record which contains single-value data is detected, that record may be inserted into the single-value linked list. Having used two linked lists, one can manipulate both the multiple-value data and the single-value data more easily. An example of the structure and link list for a defect tracking tool is provided in C-like language below.
struct single_value {
int
defect;
char
*reportedby;
char
*openedagainst;
char
*ownedby;
};
struct multi_value {
COMP
*comp;
PRI
*pri;
ABS
*abs;
ASSIGNTO
*assignto;
};
struct STATUS {
char
*ts;
char
*st;
struct STATUS
*next;
};
struct COMP {
char
*ts;
char
*name;
structCOMP
*next;
};
struct PRI {
char
*ts;
char
*p;
struct PRI
*next;
};
struct ABS {
char
*ts;
char
*str;
struct ABS
*next;
};
struct ASSIGNTO {
char
*ts;
char
*user;
struct ASSIGNTO
*next;
};
In the above-exemplified data structures, ASSIGNTO, ABS, PRI, STATUS, and COMP are implemented as linked lists. As shown, ASSIGNTO may indicate the person and time of when a defect has been assigned. ABS may indicate the time and text of the abstract of the defect. PRI may indicate the time and priority of the defect. STATUS may indicate the time and status of the defect resolution. And, COMP may indicate the time and name of the component with the defect.
As illustrated in the above structures, for a single-value structure, four fields may be defined. Namely, “defect” indicates the defect number (e.g., as an integer); “reportedby”indicates the name of the person reporting the defect (e.g., as a text or set of characters); “openedagainst” indicates which category encompasses the defect (e.g., as a text or set of characters); and “ownedby” indicates the person responsible for dealing with the defect (e.g., as a text or set of characters). In an embodiment, the category may be the name of a project. Moreover, the multi-value structure includes four fields (i.e., ASSIGNTO, ABS, PRI, and COMP as discussed above).
FIG. 4 illustrates an exemplarily report 400 in accordance with an embodiment of the present invention. The report 400 may be provided as a result of applying the method 300 of FIG. 3 . The report 400 includes an abstract field 402 with, for example, a sample description of the defect being addressed. The report 400 also includes a field 404 which may include a unique number to view the respective problem being solved (e.g., as abstracted by the field 402 ). The report 400 may further include a field for identifying the user who has opened the defect request ( 406 ), associated with the report 400 . A field 408 may include information about what item and/or problem the present report is opened against ( 408 ). The report 400 may also include a field identifying the user who owns the problem ( 410 ). The report 400 may further include one or more sections, for example for identifying the status of the problem or defect tracking ( 412 ), a priority section 414 for identifying the assigned priority to the present problem and a section 416 for indicating who the problem is assigned to. Each of the sections 412 , 414 , and 416 may include time stamp information ( 418 , 420 , and 422 respectively).
In an embodiment, the abstract field 402 may include information such as project, component, defect number, abstract, status, priority and alike. As illustrated in FIG. 4 , the message log field 408 may include log information regarding defects and/or changes made there to. The report 400 may further include fields and/or sections for the component at issue (not shown).
In an embodiment, it is envisioned that advantages of employing a linked list configuration include reduction of limitations on the number of entries, temporary storage of data without having to open and save a file repeatedly, providing a non-fragmented file, and/or utilization of system resources such as an exception handler provided in, for example, Solaris systems by Sun Microsystems, which would save any unrecorded data prior to an involuntary termination of a program.
The foregoing description has been directed to specific embodiments. It will be apparent to those with ordinary skill in the art that modifications may be made to the described embodiments, with the attainment of all or some of the advantages. For example, the techniques of the present invention may be applied to any type of tracking management system (including, but not limited to, defect and/or layout tracking). Additionally, even though certain embodiments of the present invention have been discussed with respect to log files, other types of files may also be utilized without departing from the spirit of the present invention. Therefore, it is the object of the appended claims to cover all such variations and modifications as come within the spirit and scope of the invention.
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Disclosed are novel methods and apparatus for reorganizing data in a log file. In an embodiment, a method of reorganizing data in an original log file is disclosed. The method includes: obtaining a data record from the original log file; examining the data record; if the data record includes a single-value entry, inserting the data record in a single-value storage linked list; if the data record includes a multiple-values entry, inserting the data record in a multiple-values linked list; and utilizing data from the multiple-values and single-value linked lists to write data to a new log file.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an air bag activating system and a strain relief sleeve therefor.
2. Summary of the Prior Art
The present invention concerns, in particular, an air bag activating system in a vehicle having a steering column with a fixed outer shaft containing a cassette which is rotatable with the steering wheel of the vehicle. The cassette contains an electrically actuable air bag activating assembly, a coil of multiconductor flat flexible cable being disposed between the cassette and the outer shaft of the steering column. The coil has a first lead portion connected to crash sensors outside the shaft and a second lead portion extending freely through an opening in the cassette. An electrical connector for mating with the air bag actuating assembly contains electrical terminals each connected to a respective conductor of the second lead portion. The coil of the flat flexible cable is coilable and uncoilable to compensate for the rotation of the steering wheel when the connector is mated with the air bag activating assembly.
According to a prior proposal, the second lead portion is provided with a strain relief sleeve moulded over the second lead portion and being therefore fixed thereto. It may, from time to time, be necessary for the connector to be unmated from the air bag activating assembly in order to allow testing of the crash sensors or, for example, the exchange of a gas generator cylinder of the assembly, for inflating the air bags. Under such circumstances, it may often occur that the connector is pulled in a direction away from the cassette with the risk of the connections between the cable conductors and the terminals of the connector, being impaired, given that the strain relief sleeve is fixed to the second lead portion. These connections will usually be crimped connections according to the teaching of U.S. Pat. No. 4,106,836, for example.
SUMMARY OF THE INVENTION
According to one aspect thereof, the present invention consists of an improvement in an air bag activating system in a vehicle having a steering column with a fixed outer shaft containing a cassette which is rotatable with the steering wheel of the vehicle, and an electrically actuable air bag activating assembly in the cassette, a coil of multi-conductor flat flexible cable between the cassette and the outer shaft having a first lead portion connected to crash sensors outside the shaft and a second lead portion extending freely through an opening in the cassette, an electrical connector for mating with the air bag activating assembly containing electrical terminals each connected to a respective conductor of the second lead portion, the coil of flat flexible cable being coilable and uncoilable to compensate for the rotation of the steering wheel when the connector is mated with said assembly, wherein a strain relief sleeve defining a passage through which a second lead extends is fixed at one end to the cassette and at its other end to the connector where a wave is formed in the second lead within the strain relief sleeve, the strain relief sleeve being stiffly extensible to absorb the load when the connector is pulled away from the cassette and the passage being dimensioned to allow the cable to pass freely therethrough, thereby to relieving the connections between the cable conductors and the terminals of the load when the connector is so pulled.
When the connector is pulled, therefore, cable is drawn to flatten the wave so that no pull is exerted on the connections between the cable conductors and the terminals.
In order to ensure freedom for the strain relief sleeve to stretch without pulling on the cable which would ultimately effect the contact terminations, the passage defined by the strain relief sleeve is preferably has twice the height of the cable thickness which will usually be about 0.25 mm. For economy of the material of the strain relief sleeve, which may, for example, be a soft nylon, the sleeve preferably comprises a pair of spaced, flat lattice structures formed integrally with a pair of spaced, parallel support strips, inner surfaces of the lattice structures and the support strips defining the passage of the strain relief sleeve, and serving to confine the flat flexible cable. Such a strain relief sleeve can readily be produced as a single injection moulded part, by means of a simple two part tool.
According another aspect thereof, the present invention consists in a one piece, folded, elongate, strain relief sleeve made of a stiffly resilient material, comprising a pair of spaced, parallel, longitudinally extending support strips connected together by a pair of spaced, longitudinally extending flat, parallel, lattice structures, each connected to both of said strips, the strips and the lattice structures cooperating to define a longitudinal through passage of elongate cross section for receiving with clearance, a length of flat flexible cable, attachment means being provided at each end of the sleeve, where when the strain relief sleeve is a natural position without stretching forces exerted thereupon the length of the flat flexible cable is greater than the length of the strain relief sleeve, whereby a wave is formed in the cable.
Preferably, each lattice structure comprises a series of V-shaped struts, apiece of the struts of each lattice structure being connected to the inner side of a respective one of the support strips and the legs of the struts of each lattice structure being connected to an edge of a respective other one of the support strips. The expansibility of the strain relief sleeve can be limited by connecting each leg of each V-shaped strut to a corresponding leg of an adjacent V-shaped strut, by means of a base formed integrally with the respective support strip. Since two lattice structures are arranged in rotational symmetry, each support strip is thereby of increased cross section.
BRIEF DESCRIPTION OF THE DRAWINGS
An embodiment of the present invention will now be described by way of example with reference to the accompanying drawings in which:
FIG. 1 is an explanatory diagram of an air bag activating system in an automotive vehicle, showing parts of the system in a first angular position of the steering wheel of the vehicle;
FIG. 2 is a similar view to that of FIG. 1 but showing the parts in a second angular position of the steering wheel;
FIG. 3 is an enlarged fragmentary diagram showing a strain relief sleeve according to an embodiment of the invention, applied to the air bag activating system;
FIG. 4 is a diagrammatic cross sectional view through the strain relief sleeve;
FIG. 5 is an enlarged isometric view of the strain relief sleeve;
FIG. 6 is an enlarged isometric view of the strain relief sleeve in longitudinal section and showing a fragment of flat flexible cable;
FIG. 7 is an enlarged, exploded isometric view of the body of an electrical connector of the air bag actuating system;
FIG. 8 is an isometric view showing the connector body with a cover, the strain relief sleeve and the flat flexible cable assembled thereto, the strain relief sleeve being shown only diagrammatically;
FIG. 9 is a perspective and partially cutaway detail view of an attachment member used to connect the strain relief sleeve to a corresponding component.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown diagrammatically in FIGS. 1 and 2, a steering column 2 of an automotive vehicle comprises a fixed, radially outer shaft 4 clamped, for example, to the dash board of the vehicle, and a radially inner cassette 6 within the shaft 4 and which is rotatable with the steering wheel of the vehicle. Confined between the cassette 6 and the shaft 4 is a coil 8 of multi conductor flat flexible cable FFC 7. There extends from the radially outer end of the coil 8, through an opening 9 in the fixed shaft 4, a first lead portion 10 which is connected to crash sensors 12 in the forward part of the vehicle. There extends from the radially inner end 11 of the coil 7, through an opening 14 in the cassette 6, a second lead portion 16 which is connected at its radially inner end to terminals 28 (FIG. 3) of a first electrical connector 18 which is mated with a second electrical connector 20 (FIG. 3) of an electrically actuated, air bag activating assembly 19. The connector 20 is for supplying activating voltage from the sensors 12 to an electrically actuable device (not shown) for causing a gas generator cylinder 22 in the shaft 4 to supply inflating gas to air bags (not shown) for protecting the driver and the front seat passenger of the vehicle in the event of an accident thereto. As the cassette 6 is rotated with the steering wheel, the coil 8 of flat flexible cable FFC 7 simply coils or uncoils to compensate for the movement of the cassette, depending upon the direction of rotation of the steering wheel. FIGS. 1 and 2 illustrate the case where the cassette and thus the opening 14 are rotated through 90° in the direction of the arrow A in FIG. 2. As mentioned above, the outer shaft 4 is stationary and so does not rotate with the cassette 6.
It may, from time to time, be necessary for the connector 18 to be unmated from the connector 20 on the cylinder 22, in order, for example, to allow testing of the sensors 12 or the cylinder 22 to be exchanged. When such work is being carried out there is the danger of the connector 18 being pulled, tightening up the coil 8 so that the connections 27 between the conductors of the cable and the terminals 28 of the connector 18 are impaired. These connections will usually be crimped connections according to the teaching of U.S. Pat. No. 4,106,836, for example, which are described below. As shown in FIG. 3, this disadvantage is avoided according to the present embodiment, by providing a strain relief sleeve 24 anchored at one end to the connector 18 and at its opposite end to the cassette 6. The strain relief sleeve 24 defines a through passage 26 which is substantially oversized relative to the flat flexible cable FFC of the lead portion 16, the height H of the passage 26 being preferably about twice the thickness of the cable FFC, that is to say about 0.50 mm, the thickness of the cable being 0.25 mm. In any event, relative axial movement between the cable and the sleeve 24 must be free. When the connector 18 is pulled in any direction, away from the cassette 6, the strain relief sleeve 24 elongates longitudinally, but only slightly, to absorb the load, and the flat flexible cable is free to move therein, as will be described with reference to FIG. 9, to compensate for its elongation. Thus the connections 27 between the terminals 28 of the connector 18 and the conductors of the lead portion 16 are relieved of load despite the connector 18 being pulled away from the cassette 6.
The strain relieve sleeve 24 will now be described in detail with reference to FIGS. 5 and 6. The sleeve 24 is an elongate, one piece, injection moulding of a stiffly resilient plastics material, for example, a soft nylon and can be produced by means of a simple two part tool. The strain relief sleeve 24 comprises a pair of longitudinally extending, rectangular cross section support strips 30 and 31, respectively, which are parallel to one another. The strips 30 and 31 are spanned throughout their length by a pair of opposed, parallel, spaced lattice structures 32 and 34, respectively, arranged in rotational symmetry. The passage 26, which is of elongate rectangular cross section is defined by the spacing between the support strips 30 and 31 and the lattice structures 32 and 34. Each lattice structure 32 and 34 comprises a series of V-shaped struts 36. The apiece 38 of the struts 36 of the lattice structure 32 are connected to the strip 30, being formed integrally with the inner side 40 of the strip 30. The apiece (not shown) of the struts 36 of the lattice structure 34 are similarly integrally formed with the inner side of the strip 31. The end, remote from the apex, of each leg 33 of each V-shaped strut is connected to a corresponding leg of the next adjacent V-shaped strut by a common base 42. The bases 42 of the struts 36 of the lattice structure 32 are formed integrally with the proximate upper edge 44 of the strip 31, the bases 42 of the struts of the lattice structure 34 similarly being formed integrally with proximate bottom edge of the strip 30. Since the lattice structures 32 and 34 are arranged in rotational symmetry, each of the strips 30 and 31 is in effect reinforced by the bases 34 which limits the extensibility of the strain relief sleeve 24.
At the left hand end (as seen in FIGS. 5 and 6), that is to say the connector end, of the strain relief sleeve 24, is an attachment member 46 comprising parallel cheeks 48 each formed integrally with a respective one of the support strips 30 and 31 and being spanned by a cross piece 50. Beneath the cross piece 50 the attachment member 46 defines a latching groove 52 extending transversely of the length of the sleeve 24. At its right hand end (as seen in FIGS. 5 and 6), the sleeve 24 is formed with an attachment member 54 comprising a pair of parallel cheeks 56 having at their free ends rounded dowels extending at right angles to the planes of the flat lattice structures.
With further reference to FIG. 9, the attachment end 54 is now described in greater detail. The attachment member 54 includes a support span 156 that interconnects the parallel cheeks 56. The support span 156 includes an upper surface 158 upon which the flat flexible cable portion 16 rides. An anchor post 160 extends outward from one of the parallel cheeks 56 and the upper surface 158 of the support span 156. The anchor post 160 includes a post portion 162 and an overlying cap portion 164 that extends thereover in an L-shaped manner whereby a notch 166 formed in the FFC 16 enables the FFC 16 to be anchored to the strain relief sleeve 24 at the attachment member 54. Provided that the FFC lead portion 16 is longer than the strain relief sleeve 24 therealong a wave 168 can be formed in the FFC lead portion 16 between the two parallel cheeks 56. This wave 168 represents excess cable length that may be taken up in response to the stretching of the sleeve 24 without the exertion of a force on the contact crimps described blow. In addition, it may be advantageous to have the upper surface 148 located offset from the passage 26 such that the FFC 16 is easily insertable along the passage 26 so that the FFC 16 passes over the anchor post 160 without having to be deflected and is then buckled slightly both to form the wave 168 and so that the notch 166 fits under the cap portion 164 and about the post portion 162.
As shown in FIGS. 7 and 8, the connector 18 comprises an insulating housing body 60 and a cover 62 therefor. The terminals 28 of the connector 18 comprise receptacles 64 for mating with pins 65 (FIG. 3) of the connector 20. One of the receptacles 64 has a slotted plate contact 66 for receiving one end of the coil of a smoothing choke 68, the other of the receptacles 64 having a crimping contact 70 for crimping about a conductor of the lead portion 16 of the flat flexible cable. A further terminal 72 comprises a similar crimping contact 74 and a slotted plate contact 76 for receiving the other end of the choke coil. The contacts 70 and 74 have pointed lances 75 for insertion through the insulation of the cable and for crimping down to engage the cable conductors, according to the teaching for example, U.S. Pat. No. 4,106,836.
The housing body 60 has cavities for receiving the respective terminals, a flat platform 78 for supporting the contacts 70 and 74, a pair of clips 80 for latching to the cover 62 and a pair of forward cheeks 82 spanned by a bar 84 for latching engagement in the groove 52 of the attachment member 46 of the sleeve 24. The cover 62 has a cable engaging lip 86. The flat platform 78 enabling the connector 18 to be terminated to the cable when the contacts are set in the housing 60, thereby allowing the connectors 19 to be delivered in partially assembled form and not requiring special tooling to terminate the cable.
The choke coil 68 is first assembled to the housing body 60, after which the terminals 28 and 72 are assembled to the housing body 60. The leading end of the lead portion 16 is passed through the passage 26 from the cassette end of the strain relief sleeve 24 as indicated by the arrow B in FIG. 6, until the free leading end portion of the lead portion 16, after passing under the cross piece 50 projects from the connector end of the strain relief sleeve 24. The connector end of the sleeve 24 is then lowered into the forward end of the housing body 60 so that the bar 18 thereof is received in the groove 52 of the attachment member 46, with the projecting end part of the lead portion 16 lying on the lances 75 of the contacts 70 and 74. The lances 75 are then crimped down to complete the connections between the conductors of the lead portion 16 and their respective terminals. The cover 62 is then latched to the housing body 60 with the lip 86 disposed between the cheeks 82 and pressing the end part of the lead portion 16 down against the bar 84 with the cheeks 48 between the cheeks 82 as shown in FIG. 8. The connector end of the strain relief sleeve 24 and the lead portion 16 are thereby fixedly secured to the connector 18. The cassette end of the strain relief sleeve 24 is then fixed to the cassette 6 by engagement of the dowels 58 in recesses 88 communicating with the opening 14 (FIG. 3) whereby the assembly of the strain relief sleeve to the connector 18 and the cassette 6 is completed.
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A stiffly extensible strain relief sleeve (24), in order to protect the crimped connections (27) between the conductors and the terminals (28) when the connector has been unmated from the activating assembly (19) and is accidentally pulled, fixed to a clock spring cassette (6) and a connector (18). The sleeve (24) has a passage (26) which is oversized with respect to the lead portion (16) and through which the lead portion (16) extends freely. When the connector (18) is pulled, the sleeve (24) elongates slightly and cable is drawn from a wave 168 formed therein to compensate for the elongation of the sleeve (24).
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This is a continuation-in-part of Ser. No. 08/064,598, filed May 21, 1993, now abandoned.
This invention relates to a ducted axial fan. These fans are known to generate tonal noise at harmonics of the rotation rate times the number of blades in the fan as well as some random noise from air turbulence. It is also well documented that most of the noise is generated at the tips of the blades and that the tonal components increase rapidly in intensity when the fan must work against back pressure.
Prior efforts to solve this problem through active cancellation have been limited to cases where the diameter of the duct is small and its length long with respect to a wavelength of the tonal noise. This allows for effective coupling of the anti-noise from a small number of speakers in the duct with the non-rotating noise field downstream in the duct.
The instant invention solves the problems inherent in the situation where the diameter of the fan is large when compared to a wavelength of the tonal noise from the blade tips. This occurs whenever the fan is large, rotating at high speed and/or has a high number of blades.
OBJECTS OF THE INVENTION
Accordingly, it is an object of this invention to improve upon the prior art in active axial fan noise cancellation to handle cases where the diameter of the fan is large compared to a wavelength of the tonal noise from the blade tips.
This and other objects will become apparent when reference is had to the accompanying drawings in which:
FIG. 1 is a perspective view of a general configuration of a typical ducted axial fan, and
FIG. 2 is a perspective view of the ducted axial fan comprising the instant invention.
FIG. 3 shows a bi-directional controller.
DESCRIPTION OF THE INVENTION
This invention recognizes that the predominant perceived tonal noise from a ducted axial fan is the secondary acoustical wave generated when the rotating pressure wave produced by the fan hits physical supporting members near the fan. Most of the work to date in active control of fan noise cancels this secondary acoustical wave. It has proven difficult to accomplish this cancellation when the dimensions of the fan and/or duct are large (more than 1/4λ) compared to the wavelength (λ,) of the noise due to the complexity of dealing with the multiple propagation modes that the acoustical wave can use to travel down the duct.
The primary pressure wave is different on each side (inlet/outlet) of the axial fan. On both sides it is a maximum at the blade tips (mostly due to the higher speed of the blades at the tips) and is almost zero at the axis of the fan. One solution would then be to position a set of speakers around the duct at or near the plane of the fan and operate a multiple interacting algorithm (MISACT) to cancel the noise. The required number of speakers is determined by the complexity of the pressure waveform around the circumference of the duct but will be a minimum of two per fan blade for smaller fans and more for fans with larger diameters.
FIG. 1 shows an axial four-bladed fan 10 adapted to rotate within duct 11. The tips 12 of blades 13 of fan 10 generate tonal noise at harmonics of the rotation rate times the number of blades in the fan as well as random noise from air turbulence.
In general, the propagating pressure wave is different on either side of the fan. This will require twice as many speakers and that they be in pairs, on either side of the fan and double the number of cancellation channels. FIG. 2 shows a diagram of the physical actuator system.
In FIG. 2, the fan 20 having blade tips 25 is adapted to rotate within duct 21, microphones 22, 23 are located downstream and upstream, respectively and a series of actuators, e.g., speakers 24, are located around the periphery of duct 21. In cases where the pressure waves are different on opposite sides of the fan, a second set of actuators 26 are located around the duct periphery of duct 10. It should be noted that all the speakers are equally spaced around the duct.
Since the noise sources (fan tips) 25 are close to the anti-noise speakers, the frequency limits are not as severe as the limits in matching acoustical modes. Since some noise is also generated along the length of the blades, this approach may not achieve perfect cancellation at higher frequencies, but it should generally do a good job.
To control the speakers, one can employ a system as shown and described in U.S. Pat. No. 5,091,953, hereby incorporated by reference herein. This system is known as a MISACT (Multiple Interacting Sensors and Actuators) system.
One problem with a direct application of MISACT to this problem is the complexity and speed of the calculations required to implement that solution to this problem. Recognizing that the rotating pressure wave has a slowly changing (almost unchanging) shape, an alternate solution is feasible. Therefore an anti-noise generating element is used which has one channel of active control (two channel MISACT for bi-directional cancellation) to determine the shape of the required anti-pressure wave and then output a replicated (by the number (N) of fan blades) version of this shape rotating around the set of speakers in sync with the fan rotation. A bi-directional system requires only a two channel MISACT controller with an added function to do the synchronous time to spacial transformation. The MISACT controller will need to have a number of D/A output channels (and amplifiers) equal to the number of speakers per fan blade. It will only require two A/D input channels (assuming no serious propagation mode problems at the microphones).
The generation of the rotating sound field is a straight forward addition to a MISACT controller. The present MISACT system generates an image of the required antinoise output wave form and stores it in memory. It then reads this memory in a rotating cycle, synchronous with the noise cycle. All that is needed here is to read the output wave form with N different pointers (N being the number of speaker pairs per fan blade) that are equally spaced around the anti-noise cycle. The resulting 2*N output signals are then each amplified and distributed to a number of speakers equal to the number of fan blades.
Since the anti-noise output waveform is slowly varying, the update algorithm can be slowed down to maintain stability in the presence of the non-linear relationship between the generated anti-noise waveform and the residual noise sensed by the microphone on each side of the form.
Having described the invention, attention is directed to the appended claims.
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A ducted axial fan for large diameter ducts (11) which includes equidistantly spaced sensors (22,23) upstream and downstream of an axial fan and spaced actuators (24, 26) located around the periphery of said duct to cancel tonal noise caused by the air turbulence generated by the rotation of the fan.
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BACKGROUND
[0001] Machine tools and particularly those having the possibility of performing multiple operations are ubiquitous in industry. Such tools as turret lathes have become an important tool for any machine shop to have and operate. While the tools certainly help production throughput, they often require tool changes and non-tool-change related operator intervention throughout a machining operation. Some operational changes can be effected through control systems located externally of the machine and some require an operator to access the interior of the machine. Accessing the interior of the machine can be messy due to coolants used and can potentially be dangerous if the operator fails to employ proper protocols.
[0002] In view of the foregoing, configurations that reduce operator intervention requirements are always welcomed by the art.
SUMMARY
[0003] A hands-free quick-change air tool configuration for a machining apparatus includes a tool holder configured to receive a normally hand-held air operated tool; an air manifold operably receptive of the tool holder; and a plunger-type seal configuration operably interconnected to an air supply and in operable communication with the air manifold.
[0004] A method for deburring a part in a machining apparatus includes installing the configuration as claims in claims 1 in a machining apparatus; inputting instructions to a control unit to cause the air tool to be aligned with the part; and inputting instructions to activate a solenoid associated with supplying air from an air source to the air manifold.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] Referring now to the drawings wherein like elements are numbered alike in the several Figures:
[0006] FIG. 1 is a representation of one embodiment wherein a standard hand-held air tool is mounted in a tool holder to a machining apparatus that is plumbed to provide air as a power fluid to the air tool;
[0007] FIG. 2 is a view of the turret depicted in FIG. 1 from a reverse vantage point illustrating the air/coolant plumbing configuration;
[0008] FIG. 3 is a view of the tool holder and air tool depicted in FIG. 1 ; and
[0009] FIG. 4 is a view of an air connector configured for reception in the air tool and an air manifold.
DETAILED DESCRIPTION
[0010] The invention described herein succeeds at both of reducing the need for operator intervention in machining operations by providing remotely actuatable air driven tool capability within the machine and reducing costs of adding tools having alternate capabilities than standard tools for such a machine by advantageously facilitating the use of normally hand-held air driven tools in the machine.
[0011] Referring to FIG. 1 , the reader's attention is directed to air tool 10 , which is depicted in this embodiment as an air grinder. The air tool may be recognized by some as a standard type of air tool normally used in a hand-held paradigm. Tools like the depicted air tool 10 are ubiquitously available and inexpensive to purchase. They are powered by compressed air often referred to as “shop air”, which is readily available in most machine shops for various purposes. In ordinary use, an operator will use a quick connect coupling (available everywhere in connection with air tools) to connect to and supply air to an air powered tool and then use that tool by hand to effect a result as desired.
[0012] In connection with this disclosure however, the air tool 10 is mounted in a tool holder 12 configured to be connected to an air manifold 14 . The air manifold 14 is connected in a conventional way to a mounting location in a machining apparatus such as to a turret 16 of a turret lathe 18 , as shown. The air tool 10 is secured in the tool holder 12 in an “on” position. As one familiar with the use of air tools will recognize, each tool has a configuration allowing an operator to operate the tool. In the case of an air grinder like that illustrated, the “switch” is commonly a paddle-type switch. In one embodiment of the invention, the tool holder 12 is configured to hold the paddle-type switch in the depressed position. In this position, a supply of pressurized air to the air tool in the tool holder will automatically cause the air tool to operate. In one embodiment, the tool holder 12 is configured as two pieces. A body 20 cooperates with a cap 22 to mount and hold the air tool 10 therein. As illustrated the body and cap are secured to one another using a number of fasteners.
[0013] Air tools and other air driven accessories will also have an air inlet. The air inlet is very well known and hence does not require illustration. Suffice to say that it is in many cases at a base of the air tool and is so with the air tool depicted in FIGS. 1 and 3 hereof. In order to provide quick and easy air connection, an NPT (national pipe tapered) connection (see FIG. 4 ) is provided for threaded connection to the air tool 10 and mounted connection to the air manifold 14 .
[0014] Referring to FIG. 2 a part of the air manifold 14 is visible, the view being from behind the turret 16 shown in FIG. 1 . This portion of the air manifold is referred to herein for convenience as plumbing 30 . Plumbing 30 includes an air inlet 32 and a liquid inlet 34 that both feed a switchable fluid port 36 . Switchable fluid port 36 is connected to a fluid conduit 38 that feeds the air tool 10 . The port 36 is switchable to feed air or coolant depending upon what tool is connected to the turret 16 . If a conventional tool is connected to the turret 16 in the relevant position, a coolant supply would be desirable whereas if an air powered tool is connected in that position as illustrated in FIG. 1 , air would be provided to the tool 10 .
[0015] In order to feed pressurized air to the plumbing 30 , a plunger-type fluid sealing arrangement 40 is employed (see FIG. 2 ). This is similar to those commercially available to convey cooling fluid to a turret 16 but in connection with the disclosure hereof is used for air conveyance, a fluid not normally conveyed to a turret 16 . When the turret moves to a locked position after rotation, the plunger type fluid sealing arrangement 40 will be in compressed engagement with a seal port 42 , commonly both made of polytetrafluoroethylene or other relatively hard, long wearing yet deformable material. When the components 40 and 42 are pressed together by the turret moving to the locked position, the connection between 40 and 42 is capable of conveying pressurized fluid, in this case air or other compressed gas that is capable of powering an air type tool.
[0016] The configuration allows for pressurized air to be available within the machine via solenoid actuation and for an air powered tool to be mounted and operated within the machine without an operator even opening the door to the machine. Thereby, the operator is protected from his or her own failure to follow safety protocols and overall safety is thus enhanced through the employment of the configuration as disclosed.
[0017] In a particular embodiment of the invention disclosed herein a deburring function is enabled by the configuration disclosed. Conventionally deburring of a machined part would be effected by an operator opening a machine door and reaching in with a deburring tool to debur the part while the machine rotated the part being machined. Made possible by the configuration disclosed herein however, the air tool is tipped with a bit 48 capable of deburring the part being machined. To accomplish the deburring operation, the operator merely programs the machine to rotate the turret 16 to align the tool 10 with the part and activate the pressurized air flow. The air tool will then debur the part without the door of the machine being opened by the operator and the operator need not reach into the machine at all.
[0018] It is to be appreciated that not only does the invention increase operator safety and improve efficiency in machining; it also enables the use of inexpensive air tools in place of very expensive alternatives. The industry is thus benefited in efficiency, cost and safety.
[0019] While one or more embodiments have been shown and described, 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 illustrations and not limitation.
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A hands-free quick-change air tool configuration for a machining apparatus includes a tool holder configured to receive a normally hand-held air operated tool. The air manifold is operably receptive of the tool holder. A plunger-type seal configuration is operably interconnected to an air supply and is in operable communication with the air manifold. A method for deburring a part in a machining apparatus is included.
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FIELD OF THE INVENTION
The invention relates to an installation for the wet or dry treatment, e.g. washing, dyeing, bleaching, steaming, drying, finishing and/or sizing of web, yarn, strand or filiform textile goods, with at least one treatment unit and with a carrier for the support of the textile goods.
THE RELATED ART
Textile goods such as webs, yarn, strands or filiform materials are subjected to many wet treatments, but also to dry treatments, such as thermosetting and thermal brine treatment and thermal developing. For their production, expensive machinery and installations with sizable dimensions have to be made available. However, before production starts, tests on a smaller scale have to be performed, in order to establish whether the desired results can be achieved with the planned process and materials. Such tests can not be run on the scale of the industrial installation primarily due to their high cost, and for this reason laboratories are used, which basically recreate on a considerably reduced scale the construction of the industrial installation. Installations of the mentioned kind usually have a length of up to 120 m. However, when these installations are recreated as a model on a smaller scale, certain conditions result which do not correspond to the realities of production. As a result of their considerably reduced dimensions, these laboratory facilities furnish results as to treatment times, temperatures, physical forces (shearing forces during washing) which most times differ from the results of the industrial installations.
Also, there is an increasing demand on the market for cuts of materials with full width for the production of entire garments. Presently, these cuts (2-4 m) are produced mostly in large-scale installations or compact installations ( reduced large-scale installations). Generally, in order to be able to dye such cuts on one of the above continuous installations, "minimal-length" pieces (200-600 m) have to be available. This way, undesired lengths of material are produced and installations built for industrial-scale production are unproductively used during the so-called "sampling" process.
Large-scale continuous installations are usually single key-in machines which cost between about 300,000 and 3,000,000 dollars. To start them several times a year (at least two times, often even four times) for the sampling results in considerable economic strain and at the same time disturbs the normal production process.
In the last years, the trend towards more frequent and short-term fashion changes has increased. The so-called "designer fashion", i.e. of garments provided with a visible "trademark" (label) is also spreading. The need of one or more collections for presentation (for instance for the stores) requires the availability of cuts of material in various colors.
It is therefore the object of the invention to create an installation of the kind mentioned in the introduction, which can recreate the conditions of large-scale installations also for the production of short lengths of material, e.g. cuts or lab samples, so that the performed dyeing of lab samples or cuts corresponds to the results to be expected in the industrial process.
According to the invention, this problem is solved due to the steps which are the subject of the characterization part of patent claim 1. Advantageous developments result from the dependent claims.
As a result of the teaching of the invention, it is possible to achieve dimensions, treatment times, technological and technical process parameters, as well as process developments similar to the ones of the large-scale installations, which in spite of that can be accommodated in a very limited space. On continuous large-scale installations, various processes can be carried out, through successively arranged units, e.g. foulard impregnating, steam developer, washing machine, dryer, etc., which "refine" the textile product. In the installation of the invention, such individual units are also used, with the advantage that the process sequence can be changed at will, or the same process can be carried out successively several times The programmable support for the material carries the material to the treatment units , whereby the succession and the number of treatment can also be preprogrammed, which is not possible in the fixed large-scale installations. The material support, on which the textile goods revolve in the manner of an endless belt is preprogrammed to move from treatment stage to treatment stage. At the same time the material support has also the function of a squeezing mechanism, which takes care to squeeze out the excess liquor after each treatment stage. Due to the above arrangement, continuous processes are carried out "digitally-continuously".
For a batter understanding of the invention, the following treatments are mentioned, which among others can be carried out on an installation according to the invention:
1. Preliminary treatment of a cotton fabric
______________________________________prewashing in a washing tank (2x)enzyme impregnation in the impregnation tank (1x)desizing in the steamer (1x)washing in the washing tank (3x)peroxide impregnation in the impregnation tank (1x)bleaching in the steamer (1x)drying in the blast-dryer (1x)______________________________________
2. Dyeing of a prebleached polyester-cotton blend:
______________________________________impregnation with dispersion dye in the impregnation (1x)tankpredrying in the infrared dryer (1x)drying in the hot-flue (1x)thermal brine treatment in the hot-flue (1x)intermediate cleaning in the wash tank (2x)drying in the hot-air blower (1x)impregnation with sulfur dyes in the impregnation (1x)tankfixing in the steamer (1x)rinsing in the washing tank (2x)oxidizing in the wash tank (1x)brightening with soap in the wash tank (1x)washing in the wash tank (3x)drying in the blast dryer (1x)______________________________________
3. Indigo-dyeing of a cotton warp in three "slivers"
______________________________________prewashing in the washing tank (2x)immersion in the indigo-dye bath (1x)oxidizing in the air passage (1x)immersion in the indigo-dye bath (1x)oxidizing in the air passage (1x)washing in the washing tank (3x)drying in the blast dryer (1x)______________________________________
4. Finishing of a pregassed denim fabric
______________________________________prewashing in the washing bath (3x)finishing with softeners in the impregnation bath (1x)drying in the blast dryer (1x)______________________________________
In all four of these treatment types the turning speed of the good, the treatment times of the individual process stages, the condition of the liquor, concentrations, squeezing pressure, residual wetness and so on are compared with the large-scale installation, in order to obtain a comparable result.
The reproducibility for similar treatments is insured due to the electronic, freely-programmable control and the automatic control of the process parameters.
The practitioner (textile chemist) can establish the programs without special previous knowledge; no limits are set to his tendency to research and find new developments, which means that the invention is also especially applicable to "Research and Development". The technology as well as the sequence of stages and the treatment times can be modified at will, so that large-scale continuous installations can be imitated, independently of the composition of their individual units. The practitioner faced with new investments can establish the sequence of the units and their dimensions correspondingly to the demand of the market.
Last, but not least, the reduction of the effects on the environment have also to be mentioned, since the invention limits itself to the use of minimal amounts.
BRIEF DESCRIPTION OF THE DRAWING
Further aims, features, details and advantages of the invention result from the following description of embodiments with the aid of the attached drawing. It shows:
FIG. 1 a schematic longitudinal section of an embodiment of an installation for the process cycle of the invention with stepping unit.
FIG. 2 a schematic representation of the essential part of an installation according to the invention in a certain stage of the process, e.g. dyeing stage or the wetting stage, or the rinsing stage, or the application of chemicals, etc.
FIG. 3 a schematic representation of the installation of the invention in another phase of the process, such as for instance the opening of the squeezing mechanism with subsequent raising of the material support.
FIG. 4 a schematic representation of the installation of the invention in a further phase of the process, such as for instance the steaming sequence.
FIG. 5 a schematic cross section of an embodiment with raised material support, for instance the air passage.
FIG. 6 a top view of the installation according to FIG. 2.
FIG. 7 a schematic longitudinal section of an embodiment of the installation according to the invention with fixed material support, but with raisable and lowerable treatment vats and winding-on devices for the material, for a fully automated process.
FIG. 8 a schematic representation in cross section of an embodiment of the installation of the invention with a material support capable of carrying a larger amount of material to be dyed in a treatment vat.
FIG. 9 a schematic representation in longitudinal section of an embodiment of the installation of the invention with fixed material support, but with raisable and lowerable treatment vats for a fully automatized process.
DETAILED DESCRIPTION
In a machine frame 1, on a horizontal bearing surface 2 several treatment vats 3 are arranged at equal distance from each other. These treatment vats are received in holders 4, which can also be provided with a heating device 5, in order to heat the liquid contained in vat 3, if necessary. Below the bearing surface 2, a pair of horizontal tracks 6 is arranged and a horizontal frame 7, drivable by a program-controlled stepping motor 9 via a chain pull 8, can be moved on these tracks.
On this frame 7, swivel arms 10 and 11 are arranged in pairs and at a distance from each other. In the representations of FIGS. 1, 2 and 3, the swivel axes 12 and 13 of the swivel arms 10 and 11 are perpendicular to the plane of the drawing. Between these two swivel arms 10 and 11, a piston-cylinder unit is provided, which in FIG. 1 is indicated only by a broken line, and by means of which the swivel arms can be swung within the drawing plane (FIG. 1 and FIG. 3). The swivel arm 10 carries at its upper end three support rollers 15; the other swivel arm 11 carries a squeezing roller 16, which can be driven by means of a motor 17 affixed to the frame 7, via guide rollers 18, 19, 20 as well as via chain 21. The squeezing roller 16 can also be designed as a "floating roller", as it is usually done in many squeezing mechanisms.
On the frame 7 a vertical guide 22 is arranged, which in FIG. 1 would be located behind the drawing plane and which is not shown in this figure, for the sake of the overview. This guide 22 is illustrated in FIGS. 5 and 6. Due to this vertical guide 22, a support 23 is slidably supported , suitably over a program-controlled stepping motor which is not shown here, and this support 23 carries a vertical frame 25 via a bracket 24. The vertical frame sides of frame 25 are telescopic and each has an external part 26 and an internal part 27. Now the rollers 28 and 29 are rotatably supported on these parts of the frame sides. These rollers can also be supported in a fixed manner and a control tension roller can be mounted instead of the displacement body. The drive takes place via a friction wheel 30 or via a chain.
In the upper part of the machine frame 1 (FIG. 1) two box-like chambers 33 and 34 which can be raised and lowered are provided, respectively aligned with one of the treatment vats 3. In the one chamber 33 a steaming device 36 is located, and in the other chamber 34 a warm-air blower 37 with infrared rods for drying is located.
In the following, a segment of the operation in the installation is described in detail, without specific reference to a certain treatment stage or a certain treatment process.
The textile goods to be treated are placed on the rollers 28 and 29, as an endless band. The rollers 28 and 29 form the support for the textile material, i.e. the material carrier. Then, the material carrier is raised by means of the support 23 along the vertical guides 22 (FIG. 5), whereby the swivel arms 10 and 11 diverge. Now, the horizontal frame 7 runs to the left according to the programmed step sequence, until the material carrier reaches a position above the vat 3. At this point, the support 23 is lowered, the material carrier is dipped in the vat 3 (FIG. 3), the swivel arms 10 and 11 are brought together by the piston-cylinder unit 14 and the motor 17 actuates the pressure roller 16 and thereby also the roller 29, via roller 31 and the friction wheel 30, so that now the textile material is endlessly turned in the treatment vat 3.
When the dwelling time established for the textile material has passed, the swivel arms 10 and 11 are brought back to their open position (FIG. 3) by reactuation of the piston-cylinder unit 14, after which the material carrier with the rollers 28, 29 and the roller 31 can be raised over the support 23. Thereby, the support 23 is raised until the lower roller 28 of the material carrier is at the same height level with the pressure roller 16, whereafter the swivel arms 10 and 11 are again brought to their closed position (FIG. 4). In this position of the installation components, (FIG. 4), the residual liquid can be squeezed out from the textile material by the pressure roller 16 and the carrier roller 28, which here takes over the function of a back-pressure roller. The squeezed liquid runs back into the vat 3. After the squeezing process, the above-mentioned treatment can either be repeated, or the carriage continues to travel according to the preprogrammed step sequence to the next treatment vat, in order to continue there the dipping and squeezing process.
If the program includes also steaming, the chamber 33 is preheated with steam. For the steaming stage, the chamber 33 descends over the material support containing the revolving textile goods. If the goods have to be dried, the chamber 34 with the infrared rods descends over the material support. Here also, the goods are in motion and, according to the preestablished time or to the residual humidity, it is completely dried by a hot-air blower. When the drying is concluded, the chamber 34 is raised again, the blower and the heater are turned off and the material carrier with the textile goods travels to the next treatment unit.
FIG. 6 shows a top view of the installation according to FIG. 2.
In FIG. 7, within the framework of the invention, the treatment vats 3 are designed to be lowered and raised with respect to the material carrier. Here also, instead of the displacement body, a tension control roller 45 is mounted. When longer lengths of material, e.g. more than 8 m need to be dyed, it is advisable to eliminate the endless textile band. Instead the textile goods are wound on fabric rollers 46, which means that the lower fabric roller 6 unwinds and the upper roller winds up, as shown in FIG. 7. The textile goods are marked by dash-dot line 43.
FIG. 8 shows a cross section with several freely rotating rollers, which serve to take up endlessly even more textile material (for instance a 8 m piece).
It is self-understood that the above-described technique is limited to a certain roller width or a certain material width. This way, the invention allows the dyeing of goods with the smallest width (test batches) to normal width (150-160 cm) and wide width (320 cm and more) such as used for table and bed linen. Also, it is self-understood that the roller widths and the other technological parameters can be adjusted to a large-scale operation, in order to insure the congruency of the process.
If several treatment baths are required, as usually happens in such processes, the frame 7 travels with raised carrier and lifted chambers 33 and 34 into the next position, and the previously described work scenario starts again. These motion sequences are suitably program-controlled, so that after a starting impulse is triggered, they follow their course automatically.
As previously mentioned, the installation is relatively small, the vats 3 contain only a small amount of treatment liquid but the machine parts acting upon the textile goods still have a size which corresponds to the production installation, so that even in these small test units it is possible to develop the forces which act upon the textile goods during travel through the production installation.
Machine frame 1 according to the embodiment example is additionally movable, so that it can be attached to various test units. Basically, it would be possible to design the bearing surface 2 with the vats 3 movable with respect to the swivel arms 10 and 11. However, this would require a considerably longer construction of the installation, so that this type of support for the parts and of relative movement of the parts is not considered suitable If in the shown embodiment example a drive motor is located on the horizontally slidable frame 7 for the actuation of the pressure roller 16, which acts upon this pressure roller 16 via guide rollers and drive members, it would also be possible to place a drive motor in the roller 16 itself. If in the shown embodiment example the swivel arms 10 and 11 are supported swingably about the low-lying axes 12 and 13, it can also be considered within the framework of the invention to arrange the pressure roller 16 and the thrust rollers 15 on a horizontally movable carriage From FIG. 6 can be seen that the thrust rollers 15 respectively arranged in pairs rest respectively only against the outer edge of the roller 31. If the frame 7 in the shown embodiment example is moved by stationary motor via a cable or chain pull 8, naturally it would also be possible to move the frame 7 by means of a motor mounted on the frame 7 and a fixed tooth rack. The vats 3 are set in the holder 4 and can be lifted out of the holders. Since this vat contains only a small quantity of the respectively required treatment liquid, the weight of these filled vats is relatively small, so that the vats can me manipulated without special auxiliary equipment.
With the installation according to the invention, it is possible to subject small amounts of textile samples such as threads, yarns, strands, woven fabrics or knits to the desired process sequences, namely in conditions corresponding to the ones existing in the industrial production. On the carrier with the rollers 28, 29 and 31, the textile goods are to be moved endlessly in the respective bath; the textile goods can through this way undergo all the treatment stages, much like in a production installation, with the result of these treatments being comparable to results obtained in production installations.
The dimensions of the rollers, the roller diameters, the revolving speed of the material to be treated, the bath ratio, the treatment times and the width of the material, etc. are precisely adjustable to the large-scale installations, and therefore the results of various treatments correspond precisely to practice, and the treatment parameters can be directly transferred (without factors).
An embodiment not shown in the drawing is also conceivable, wherein the carrier has several freely rotatable rollers 40 with basically vertically superpositioned axes, between the upper roller 29 and the lower roller 28, whereby here the goods to be treated run around the roller 29, the roller 28, and then around several rollers 40 and then again around roller 29. With the same rotational speed of rollers 28 and 29 and the same diameter as in the first above-discussed embodiment example, the dwelling time of the material to be treated in the treatment liquid is extended and at the same time the penetration of the dye is intensified. These interposed rollers 40 in this carrier also serve as displacement bodies. Similar considerations apply also to an embodiment of the carrier as shown in FIG. 8. With a correspondingly high level in vat 3, the goods to be treated are dyed without the access of oxygen. For various known dyeing processes this is important. Here, over the lower roller 28 several rollers with a smaller diameter ar arranged in two different horizontal planes, whereby the driving force acts upon at least one of the upper rollers, while the underlying rollers 42 of the lower roller group serve as guide rollers.
FIG. 9, just like FIG. 7, shows an embodiment with fixed material carrier 28, 29, but with raisable and lowerable treatment vats 3 for a fully automated process, whereby in comparison to FIG. 7, in FIG. 9 the possibility to raise and lower the treatment vats 3 is additionally illustrated in the drawing.
In accordance with the invention, the rollers of the wet treatment installation can be just as large (in length and diameter) as the rollers used in the industrial installations; but still all the parts of the installation are located in a very limited space, particularly a space which can be used also in test conditions, and thereby the forces and tensions arising in the industrial production are reproduced in the installation of the invention.
In order to demonstrate the size proportions of an installation according to the invention it can be mentioned that the machine frame 1 has a length L (FIG. 1) of 2 m and a width of 1 m. For piece material, suitably for a length L of 2 m corresponding to the width of the material at a width of for instance 4 m, a width of 4.20 m will be selected. Thereby, in the case of piece material, the length of the rollers is adjusted to the width of the material, while their diameter lies for instance between 50 and 170 mm, which means particularly the diameter of the rollers 28, 29, 31 and 16 corresponds to the diameter of the rollers used in industrial installations. However, in the case of test units, rollers with a smaller diameter can also be used.
A special advantage of the installation according to the invention--as can be seen from the above description of the embodiment examples--is that the textile goods can be guided as an endless band on the material carrier in each treatment phase (with the rollers 28, 29 and in certain cases 31) and that the textile goods and the material carrier can travel from treatment unit to treatment unit and pass through them. This allows fully automated and preprogrammed treatments in all considered kinds of treatment. According to program, the textile goods and the material carrier can also travel independently from the sequence of the treatment units, to be moved back and forth--according to program--between, respectively under or over these nits, so that the same installation according to the invention can be flexible used for instance for at least more than one of the four treatment kinds described in the introduction of the specification.
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The invention relates to an installation for the wet and/or dry treatment, such as washing, dyeing, bleaching, steaming, drying, finishing and/or sizing of a web, yarn, strand or filiform textile goods with a carrier supporting the textile goods, consisting of several rollers, on which the textile goods are guided as an endlessly running band and with at least one or several treatment unit(s), wherein the carrier with the textile goods can travel in any desired succession. The dimensions of the rollers basically correspond to the ones of rollers in industrial installations, but can be reduced when the installation has to operate under lab-test conditions. Compared to industrial installations, this installation has an extremely compact construction.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The subject invention relates to monitoring systems and, more specifically, to methods and apparatus for monitoring air delivery systems, including air conditioning and heating systems, and relates also to systems for assuring the quality of inside air in buildings and other structures.
2. Information Disclosure Statement
The following comments are offered by way of background.
Dirty air systems cause or are associated with many problems such as:
High employee absenteeism and loss of productivity due to colds, flue, itchy eyes, skin rashes, respiratory problems, and the like, all the way to serious illnesses such as legionella, pathogenic virus, and more.
Fungus growing in ductwork can corrode microcomponents and metal surfaces on delicate instruments, crash computer heads, cause failures in electronic phone equipment, contaminate laboratory work, and more,
Become a serious fire hazard. Particularly when fire dampers and other mechanisms within the system malfunction,
Create unsightly grilles and diffusers, ceiling tiles, generally dirty appearance, requiring costly maintenance,
Cause rapid deterioration of soft furnishings such as drapes, carpet and upholstery,
Increase energy costs due to lower performance levels, and/or
Create air flow problems such as lack of air, hot or cold spots and make it impossible to balance a system properly or achieve proper temperature, and decrease equipment life and increase related maintenance problems.
The need for a clean system has become obvious to most building owners and managers in recent years. What has NOT become obvious is how to do it!
Some contractors have made a good living from the fact that most people cannot visually inspect their ductwork. Major cleaning contracts have been awarded solely on the fact of dirty grilles and diffusers. Unanswered questions such as the following can be costly and dangerous:
How much of the visible dirt is due to a venturi effect, and not dirty ducting?
Could some areas be dirty while others are clean, yet you paid for cleaning the entire system?
Has cause and effect been established so the customer can be guaranteed that cleaning of the system will accomplish the desired goals?
Are the ducts truly clean or is the bacteria level still unacceptable for the building's environment?
Have pre/post conditions and findings been documented so the customer has proof and a permanent management tool?
In an effort to counter these problems chunks of contaminants have been removed from duct work and have been subjected to analyses for asbestos, fiberglass, rust, particulate content, etc. In practice, however, such a procedure was complicated and difficult to perform and to implement on a regular basis.
In a different vein, methods and means for microorganism analysis have been known for a long time, as may, for instance, be seen from U.S. Pat. No. 2,879,207, by Edward J. Poitras, for Filtration and Incubation Unit, issued Mar. 24, 1959 to Millipore Filter Corporation.
SUMMARY OF THE INVENTION
It is general object of this invention to overcome the disadvantages and to meet the needs mentioned in the above Information Disclosure Statement and in other parts hereof.
It is a germane object of the invention to provide a perfect air delivery monitoring system.
It is a related object of this invention to provide methods and apparatus for regularly monitoring an air delivery system including an air duct for contaminants.
It is also an object of this invention to improve ultimately the living environment inside buildings and other structures.
Other objects will become apparent in the further course of this disclosure.
From a first aspect thereof, the subject invention resides in a method of monitoring an air delivery system including an air duct for contaminants, comprising in combination the steps of providing an aperture in a wall of the air duct, covering that aperture with an insert having a bore, providing that insert with a filter element accessible from outside of the air duct, permitting air with contaminants to escape from the air duct through said bore, and trapping such contaminants with the filter element for subsequent laboratory analysis.
From a related aspect thereof, the invention resides also in apparatus for monitoring an air delivery system including an air duct for contaminants, such air duct having an aperture in a wall thereof, and, more specifically, resides in the improvement comprising, in combination, an air duct insert having a bore and covering said aperture, and a filter element in communication with that bore in a portion of the air duct insert accessible from outside of that air duct.
The invention also resides in apparatus comprising, in combination, an apertured filter element housing, a cylindrical air duct insert for said circular aperture in the air duct, a receptacle for that apertured filter element housing integral with the insert, an air conduit through that insert to that receptacle, and a mounting flange around the insert.
BRIEF DESCRIPTION OF THE DRAWINGS
The subject invention and its various aspects and objects will become readily apparent from the following detailed description of preferred embodiments thereof, illustrated by way of example in the accompanying drawings, in which like reference numerals designate like or equivalent parts, and in which:
FIG. 1 is a section through a monitoring apparatus according to a preferred embodiment of the subject invention, as installed at an air duct of which a fraction has been shown; and
FIG. 2 is a flowsheet showing a removed filter element housing and a removed filter element on a reduced scale, as well as the transportation and processing thereof, and the inspection and analyses of filter element contaminants.
DESCRIPTION OF PREFERRED EMBODIMENTS
The subject invention alleviates the above mentioned problems and avoids underlying disadvantages by constantly monitoring an air delivery system 10 including an air duct 12 for contaminants 13. To this end, an aperture 14 is provided in a wall 15 of the air duct. That aperture is covered with an insert 16 having a bore 17, which may be a longitudinal or axial bore communicating with the inside of the duct 12.
The insert 16 is provided with a filter element 18 accessible from an outside 19 of the air duct.
Air with contaminants 13 is permitted to escape from the air duct 12 through the bore 17 and such contaminants are trapped with the filter element 18 for subsequent laboratory analysis.
According to the illustrated embodiment of the invention, the filter element 18 is encapsulated in an apertured filter element housing 20, and such apertured filter element housing is mounted in the insert 16 in communication with the bore 17. Such filter element housing is opened or openable for a removal of the filter element 18 for laboratory analysis.
In practice, the apertured filter element housing 20 containing the filter element 18 is removed from the insert 16. A contaminated or used filter element may thus be carried, transported or sent to the lab, such as indicated by an arrow 53 in FIG. 2, where the housing 20 is opened for a removal of that filter element 18 for laboratory analysis, such as symbolically indicated by the block 54.
According to a preferred embodiment of the invention, the filter element 18 is encapsulated in an apertured filter element housing having mating housing parts or halves 21 and 22, and such apertured filter element housing is mounted in the insert 16 in communication with the bore 17, such as through a first filter element housing bore or inlet 28 in the first housing half 26.
A second filter element housing bore or inlet 29 enables flow of air from the duct 12 through the filter element 18 via bores 17, 28 and 29 for an entrainment of contaminants 13 in the filter element.
The housing parts or halves 26 and 27 may be interconnected by a manually releasable press fit 31, by mating threads (now shown), or in another suitable manner. After the apertured filter element housing 20 containing the filter element 18 has been removed from the insert 16, such as indicated by the arrow 56 in FIG. 2, the housing halves 26 and 27 are removed from each other for a removal of the contaminated filter element 18, such as indicated by the arrow 57 in FIG. 2, for laboratory analysis, such as symbolically indicated by the block 54.
According to the illustrated embodiment of the invention, an apertured cover 32 is provided for the insert 16, and the filter element housing is releasably retained with that cover in that insert.
The cover 32 may be threaded to the insert 16, such as at 34 and may have a bore or aperture 35 in communication with the filter element housing outlet 29. In practice, the bores or apertures 17, 28, 29, and 35 may be multiplied or staggered as desired or as necessary to assume optimum use of the filter element 18. However, air under pressure leaving the inlet 28 expands in the chamber 30 of the filter element housing, whereby the filter element 18 is covered by air for optimum entrainment of contaminants 13.
A circumvention of the filter element 18 by the contaminated air flowing from the duct 12 into the insert 16 is reliably avoided. For instance, the filter element housing 20, housing half 26, or inlet 28 is provided with a nipple 36 matching with the bore 17 for tightness and stability. The housing half 27 and the cover 32 have interacting or matching nipples 37 and 38 at air outlets 29 and 35.
The illustrated filter element housing halves 26 and 27 have shoulder portions 41 and 42 abutting respectively the insert 16 and the cover 32 at insides thereof for mounting stability of the filter element housing in the closed insert 16.
Shoulder portion 41 and also shoulder portion 42 may be circular or circularly in engagement with the insert inside and with the cover inside, respectively, for further air tightness around the filter element housing 20.
A flange 44 may be provided for the insert, and such insert 16 may be attached with such flange to the air duct wall 15 around the aperture 14. Sheet metal screws 45 or other suitable fasteners may be used for this purpose. The insert 16 may be threaded into the flange 44, such as shown at 46. In this manner, the bore of the flange may provide an inspection hole 48 or access for a duct cleaning tool.
In structural terms, the invention resides in apparatus 50 for monitoring an air delivery system 10 including an air duct 12 for contaminants 13, comprising the combination of an air duct insert 16 having a bore such as at 17 and covering an aperture 14 in an air duct wall 15, and a filter element 18 in communication with that bore in a portion 51 of the air duct insert 16 accessible from an outside 19 of the air duct.
A preferred embodiment of the invention includes an apertured cover 32 for the insert 16, with the filter element 18 releasably retained between that cover and the insert 16.
If the filter element 18 is encapsulated in an apertured filter element housing 20 according to an embodiment of the invention, then that filter element housing is releasably retained between the cover 32 and the insert 16, such as in a chamber 51 in the insert 16 or formed jointly by that insert and its cover 32.
The illustrated embodiment includes a mounting flange 44 around the insert 16, as already mentioned above.
The illustrated preferred embodiment of the invention presents an apparatus 50 for monitoring an air delivery system 10 including an air duct 12 for contaminants 13, comprising, in combination, an apertured filter element housing 20, a cylindrical air duct insert 16 for a circular aperture 14 in an air duct wall 15, a receptacle 51 for the apertured filter element housing integral with the insert 16, an air conduit 17 through that insert to that receptacle, and a mounting flange 44 around the insert 16. Within the scope of the invention, that flange may be integral with the insert. However, it is presently preferred that insert and flange be detachable from each other whereby the insert 16 can be conveniently removed from the flange 44 for inspection of the inside of the duct 12 and/or for a cleaning thereof.
An apertured cover 32 for the receptacle 51 may, for example, be threaded on the insert 16, and the filter element housing 20 may again comprise two apertured housing halves 41 and 42.
The parts of the apparatus 50 may be molded or manufactured of any suitable material. By way of example, plastics are suitable for this purpose. Reference in this may in this respect be had to the above mentioned U.S. Pat. No. 2,879,207.
In this respect, and in general, a bacteria or microorganism analysis may be effected at 54 to determine the microbiological content of the removed filter element. That filter element may also be subjected to a microscopic inspection and to an inspection or analysis for asbestos, fiberglass, rust and other particulate content. The technology to do all that exists, but the subject invention has put it together for air delivery system monitoring.
In this or any other manner within the scope of the subject invention, professionals concerned with an enhancement and maintenance of indoor quality of life not only are provided with an excellent and continuous management tool, but maintenance contractors and building owners alike are provided with honest assessments and appraisals for and of their works and of their systems as well.
The subject extensive disclosure will render apparent or suggest to those skilled in the art various modifications and variations within the spirit and scope of the subject invention and equivalents thereof.
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An air delievery monitoring system covers an aperture of an air duct with an insert having a bore. A filter element in communication with the inside of that air duct through that bore is made accessible from outside of that duct. Air escapes from the duct through the bore in the insert to the filter element which traps contaminants in such air for subsequent laboratory analysis. The filter element is preferably encapsulated in an apertured filter element housing which is mounted in the insert in communication with its bore. After removal of that housing from the insert, the contaminated filter element can be transported or sent to the laboratory for the performance of several analyses thereon.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation in part of PCT/US00/06701 and claims the benefit of United States Provisional Application 60/132,570.
TECHNICAL FIELD
[0002] This invention relates to the art of telephones. In particular, the invention relates to a programmable telephone having memory and display features and also to a data distribution system for use with such a telephone to connect a database directly to a large number of telephones simultaneously.
BACKGROUND ART
[0003] The ordinary telephone in general use, commonly termed a POT (plain old telephone) comprises a hand set and a keypad and may contain a display for visually displaying phone numbers, date and time, caller ID, etc. Such telephones are connected to other telephones through a network including hard wires and wireless links whereby users talk to other users directly or leave messages.
[0004] Computers that can be connected to the telephone system are also in widespread use, the communications link often being a modem and associated programming that connect the computer to other computers via the Internet through the services of an Internet Service Provider (ISP).
[0005] Both of these systems require connections to be made by an interfacing unit in the local telephone exchange. Thus, all present telephone calls and computer connections to the Internet pass through a local telephone exchange, which means that each connection must at some point include a telephone number and be individually dialed before the connection can be made. This requirement places a severe restriction on the ability to communicate with a large number of telephones and easy access to the Internet.
SUMMARY OF THE INVENTION
[0006] In accordance with one aspect of the invention, a new, more versatile telephone includes a microprocessor that provides the telephone with many of the features of a computer and allows a wide variety of communication services to be supplied directly to the telephone through existing telephone lines. Thus, the telephone of the invention includes a handset and keypad, as are known in the art, and further includes a visual display and processor unit that is programmed to allow a wide range of services to be provided directly through the telephone and for information to be visually displayed. Further, the telephone of the invention can be a stand-alone or it can be operatively connected with a computer to cooperate therewith.
[0007] One feature that can be included with the new telephone is a memory element that contains a long-distance access code for accessing a particular long-distance provider and is capable of recalling the code when a user places a long-distance call. The memory is capable of being programmed to allow one or more new access codes to be stored in the memory in place of initial codes. Thus, the user can modify the long-distance code whenever he desires to change the long-distance service.
[0008] The new telephone is also capable of accepting the access code memory-reprogramming data from a variety of external sources. For example, while it is possible to reprogram the access codes through the telephone's keypad, it is preferable that the telephone be provided with a reprogramming connection through a telephone or other line connected directly to a remote site, such as the Internet, or to a computer connected to the remote site.
[0009] In accordance with a preferred embodiment of the invention, a telephone console is provided with a programmable electronic memory for providing long-distance access codes when a user places a long-distance call. Thus, the telephone provides the tone signals necessary to transmit the access codes to the local telephone company's switches to connect the user's telephone to the specified carrier. The memory device that records the long-distance codes may be a microprocessor that is known in the art.
[0010] In another embodiment, the user's telephone is electronically connected to a computer to allow communication or data signals received by the computer to be supplied to the telephone. This can be done in a variety of ways, for example, by connecting telephone inputs to the serial or parallel outputs of the computer. As well, a separate data output may be provided for the computer. In one embodiment, the computer may be connected to the Internet by modem or otherwise, and the connection between the computer and the telephone will allow data received by the computer, as by downloading from the Internet, to be transmitted to the telephone.
[0011] One method for operating the telephone system of the invention to change long-distance access codes is for a website provider to contract with the various long-distance providers for a set of services and to advertise those services by way of an Internet website. For example, the website would contain a listing of long distance services for various service parameters, and the telephone subscriber would review those available services. Such a listing of services may, for example, contain the names of long-distance providers that would provide the lowest cost service for a given set of parameters, e.g., average length of call or geographic zones. Preferably, these services have been negotiated by the website provider such that they are economically attractive to the users.
[0012] The website has embedded in it the access codes for the various long-distance services. In operation, the user selects a particular long distance provider according to the user's characteristics and then directs his computer to download the access codes, which have been provided by the long-distance carriers. Thus, the user may be asked to “double-click” on the icon for a particular long-distance provider to cause the website computer to download the particular access codes to the user's telephone or computer. These access codes could then be printed out for manual entry into the telephone, loaded directly into the telephone of the invention, or the user's computer may output the codes through the line connected to the telephone to automatically program access codes to the new long-distance provider.
[0013] Other codes can be provided as well, such as alternative codes to use when the primary circuits are full.
[0014] The user can connect with the long-distance provider by activating the access code, as by pressing a selected button on the telephone that causes the microprocessor to generate the necessary codes. When the connection with the long-distance provider is made, the user enters the desired telephone number in the usual fashion.
[0015] The telephone includes other features. For example, many telephones have visual displays (e.g., liquid crystal displays), and the telephone of the invention utilizes the LCD to display other information, including advertising, news, etc. Data representing these messages will be included with the data supplied from a database, downloaded from a website, or from other sources and transmitted when the user is using the telephone or when the telephone is not active as will be described. The messages can be updated automatically or by connecting with the website and downloading new messages.
[0016] The telephone of the invention can be portable or a portable computer can be connected to the telephone line. This allows the user to take the telephone or computer having the downloaded information for use at remote sites. For example, if the downloaded information is the newspaper, or section thereof, the user can take the telephone or computer and read the information at the office or on the bus or subway. In a contemplated use, the user subscribes to the sports sections of several newspapers. These sections are stored in the database and downloaded into the user's smart telephone when telephone traffic is light, such as at midnight, whereby the information is available for use in the morning.
[0017] Another contemplated use is for advertisers to supply webpages to the database for downloading into a subscriber's smart telephone or computer. The webpage could have coupons or other information that the advertiser could change daily by electronically transmitting a new webpage to the database.
[0018] In accordance with a further aspect of the invention, the digital switch of a public telephone exchange is provided with a line data distributor that allows selective connection directly between customer telephone lines and an input from a data distributor. The data distributor may include inputs from a database, the Internet, or the like for transmission of data as described above. This direct connection allows the information to be transmitted to the customer lines without passing through the normal switching process, obviating the necessity of dialing the telephone number for each of the subscribers.
[0019] The line data distributor of the invention preferably comprises a plurality of software controlled electronic switches and splitters, each switch being capable of receiving a respective customer output line from the telephone exchange as an input and connecting that line to the respective customer's telephone line. The switch controls the connection between the telephone exchange and the customer line such that each respective customer's telephone line is connected to a respective output of the local exchange or is connected to a data input line, which allows data to be directly supplied to the plurality of customer's lines without passing through the public exchange. The line data distributor also includes an input from a data distributor processor for supplying data from the data distributor processor, including information such as advertising, electronic newspapers, and the like.
[0020] The line data distributor can accept/retrieve information from a database and periodically send such data to selected customers lines. This information can be sent without “ringing” the telephone whereby it is displayed directly on the telephone display or stored in the processor memory of the telephone for later display. The information may include such items as the newspaper, newsletters, electronic junk mail, special coupons, weather reports and alerts, etc.
[0021] Thus, the line data distributor provides a means to connect lines directly to a common data bus without dialing or switching to a particular line. The line data distributor is an electronic switch that is controlled by software stored in an external database. The software allows or denies data delivery to selected customers'telephones via a common access. Several line data distributors can be strategically placed in the electronic switches of the telephone exchanges downstream of concentrator points to allow data to be delivered from a single source quickly and efficiently without having to dial each line separately and without using valuable switch time slots or packets.
[0022] The line data distributor may be external to the telephone exchange switch or internal. Preferably the switch is part of a user's AIU, line card, or remote concentrator line card. It will be appreciated that the line data distributor is preferably located beyond the concentration units so that each switch is associated a respective individual customer line. This arrangement allows simultaneous access to all of the customers.
[0023] Thus, the invention provides flash delivery of data to a large number of customers without dialing each number. The line data distributor may employ software similar to that used to specify “recent change profiles” in a telephone exchange by specifying which customer is to be provided with which one of several services that are provided, e.g., advertisements, weather alerts, newspapers, etc.
[0024] A recent change database preferably controls the switches in accordance with information regarding whether a telephone customer has subscribed to any of the data services. For example, in one embodiment the recent change order has inputs regarding whether a subscriber has elected to receive a newspaper, advertisements, or the like. Also, the recent change database can be programmed with profile data. In accordance with this feature, demographic, economic, and other characteristics of the telephone user would be provided to the recent change database in the form of a code that operates to control the switches. This information could also be arranged to correlate with a header on the data itself to open or close an individual switch for particular data delivery.
[0025] While the line data distributor may generally pass normal calls directly through for normal processing, it can also route calls electronically directly to a multiplexer/converter. The output ATM packets are addressed and routed to the correct ISP for high speed Internet access.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] [0026]FIG. 1 is an overall schematic illustrating a system in accordance with the invention.
[0027] [0027]FIG. 2 is a schematic of a line data distributor in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] With reference to FIG. 1, a system in accordance with the invention includes a telephone set 2 having an LCD display 4 and a handset 6 . The telephone also includes a microprocessor (not shown) for controlling the operation of the telephone to provide such features as an answering machine; cordless/standard phone operation; and a color, liquid-crystal view panel. The telephone allows data communication and downloading of data from the telephone line as well as directly from the Internet, including long-distance carrier access digits, weather data, advertisements, etc. Further features include:
[0029] Event reminders can be programmed in the main software to flash on display reminding the user of special occasions and appointments, etc.
[0030] A Rolodex-type capability to store names and telephone numbers in a database for dialing, printing mailing list from main CPU.
[0031] A display of the precise time can be obtained by connecting the display to a service providing such information.
[0032] Use as a two-way radio, base to phone, or phone-to-phone with a second cordless phone.
[0033] Detailed personal information is stored in the telephone and delivered automatically when a 911 call is made. Such information is then automatically available and can be relayed to the emergency vehicle to provide valuable information and save time in an emergency.
[0034] Two telephone line inputs, one for direct to telephone company facilities and a second to a computer 8 to allow integration with the computer.
[0035] While only one customer's telephone 2 is shown in FIG. 1, it will be appreciated that the telephone system of the invention includes a large number of such telephones. In accordance with the invention, a line data distributor 12 connects these telephones to a public telephone exchange 10 .
[0036] [0036]FIG. 2 illustrates the line data distributor 12 . The output lines 20 from the public exchange are connected as inputs to the line data distributor. Each of the lines 20 corresponds to a customer's line, and the outputs 22 of the line data distributor are connected to the customer's (subscriber's) lines. The line data distributor provides a series of electronic switches 23 , which are preferably integrated circuits, and splitters that are software controlled by the data from the recent change database 14 and control connection of the customer lines 22 to the exchange lines 20 or the data from the data distributor processor.
[0037] The line data distributor 12 receives control information from a recent change database 14 . This database includes information that controls the services to be provided to each of the customers, such as delivery of advertisements, newspapers etc.
[0038] The line data distributor also provides an output 26 that may include a multiplexer/demultiplexer 28 for allowing a number of separate calls to be converted to ATM and addressed for transmission to the correct ISP or PVC pipe.
[0039] The line data distributor 12 receives data inputs from a data distributor processor 16 . This processor receives data for distribution from a source of data 18 , which may include a database, a connection to or data from the Internet, a connection to or data from a satellite receiver 24 , and the like.
[0040] The database may, for example, include data similar to web pages that are provided by advertisers. Thus, these pages are stored in the database 18 for delivery to the telephones 2 via the line data distributor 12 . The pages can be loaded into the database in any convenient manner, including transmission from other databases over other telephone lines, a connection to the Internet, diskettes, etc. Thus, the advertiser can develop a “web page” or other advertisement, including coupons and the like for delivery to the customers' telephones 2 , which have the processor and displays as described above and can update the page as necessary via any of several existing data links.
[0041] Thus, the telephone system integrates the telephone network and the Internet whereby customers can access Internet web pages through the telephone system via the data distributor processor 16 and the line data distributor. This allows customers to receive data with the press of a touch-tone pad.
[0042] As well, customers can communicate through the system by way of the output line 26 and the multiplex 28 through ATM or special routing.
[0043] In operation, the RCOS database is programmed to control the switches 23 based on previous selections by customers. If a customer has elected to receive information to be provided by the operator of the database, the appropriate switch 23 will be controlled to transmit data from the database processor 16 to that customer's line at the appropriate time. The control 14 will be coordinated with the data distributor processor 16 so that the customer need not elect to receive all or none of the data. The election may include only part of the data by coordinating the control of the switch with the transmission of the data.
[0044] In those instances where a customer's line is busy when the data is to be distributed, the recent change database controller 14 and the data distributor processor will cause a second attempt to be made to all lines that were busy on the first attempt. After a predetermined number of tries, the customer will be informed of the need to dial the database directly to receive the information.
[0045] The line data distributor of the invention may be part of a retrofit of existing telephone systems or may be incorporated into new switches, e.g., packet switches.
[0046] Modifications within the scope of the appended claims will be apparent to those of skill in the art.
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A telephone system includes a data distributor between the outputs of a public exchange switch and customer lines. The data distributor provides a controllable, simultaneous and direct connection between a source of data and a plurality of the customers' telephones to facilitate direct delivery of data to a large number of customers. Telephones for use with the system provide processors for receiving and displaying data and for transmitting responses by the customers.
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This application is a continuation, of application Ser. No. 065,162, filed June 19, 1987, which is a cont. of Ser. No. 741,667, filed May 24, 1985, now abandoned.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to an incontinence device particularly adapted for the use of female patients.
(2) Technical Considerations and Prior Art
The problem of incontinence in women has long been difficult to solve. In hospitals the use of a self-retaining catheter inserted into the urethra is normal practice, and while this successfully controls involuntary flow, it brings with it the problem of infection. In addition, professional help is normally required in replacing the catheter, which makes it inconvenient for use when the patient is not in the hospital. The use of known incontinence clothing has little more than an external cosmetic effect, and since urine flow is not prevented, the patient remains continually wet and uncomfortable.
Incontinence in females may be a transient condition or a long-term condition or an involuntary condition.
SUMMARY OF THE INVENTION
The present invention in its various aspects consists essentially of a simple molded device which can be worn in the vagina, and which is easy to use in that it can easily be inserted and removed by the patient herself and worn, when required, at home. It may conveniently be molded in a one-piece form which is cheap to manufacture and easy to clean or cheap enough to be disposable.
The condition referred to above as transient may be when the incontinence has been caused by trauma, such as an operation, and the patient can be expected gradually to regain control of bladder function. Here a drainage version of the device in accordance with the invention may be most appropriate, since it will accommodate inadvertent bladder leakage but enable the user to observe her increasing degree of control and gain confidence therefrom.
This form of device is also useful where the patient has long-term incontinence and, for example, is bedridden.
The condition referred to as long-term may, on the other hand, require more complete control as indeed may the transient condition when the patient has left the hospital. Here a restrictive version of the invention is used in which the internal portion of the device occludes the urethra so that the device is removed to discharge the bladder.
The condition referred to above as involuntary is a further condition of female incontinence which is known as stress incontinence. This is a condition in which involuntary discharge of urine occurs only in certain circumstances, such as when the person coughs or jumps. This is caused by the bladder dropping. Known techniques which have been applied to try to control this condition comprise the so-called watch spring pessary and a surgical procedure in which a ligature is placed around the urethra. Both techniques aim to relocate the urethra in the normal position. The former technique is not very effective, the device tending to slip from the correct position, and the latter technique involves a surgical procedure.
An incontinence device in accordance with the present invention may consist of two limbs which together form a generally U- or V-shaped configuration, a first or upper limb affording the internal portion of the device and a second or lower limb affording the external portion of the device and to which is attached the tensioning means.
The first limb may be shorter than the second limb, or they may be of essentially equal length, but this is not essential. The upper limb may be significantly shorter provided the necessary seal can be maintained. On the other hand, an arrangement in which the lower or outer limb is shorter is not excluded.
In those forms of the incontinence device which are provided with occlusion means, these may be provided on the upper limb by a forwardly facing protuberance, the pressure of which on the vaginal wall causes or assists the urethral occlusion.
The device is held in position by a rearwardly-extending portion which is pressed against the dorsal vaginal wall.
This rearwardly-extending portion may be either a rigid loop attached to the upper limb, or a molded extension to the base of the U, or preferably may be generally shaped so as to conform to the lower vaginal wall proximate to the vaginal opening.
In another form of the invention, a rearwardly-extending portion extends from the region of the upper end of the interior portion and across the vagina laterally and extends into the region of the cervix or past it but stops short of the dorsal wall of the vagina. This assists in maintaining the device in the laterally correct position and is particularly useful in the stress incontinence version of the invention.
The device is made of a rigid or semi-rigid substance and is preferably provided with soft pads or coverings for comfort.
The tensioning means may conveniently comprise a strap or cord attached at one end to a belt, the tension being due to the elasticity of the cord or that of the belt, or both, the belt also constituting the securing means.
It may be desirable, for comfort, for the strap to be of a soft or padded material or for it to be sheathed.
In another form of the invention, the device is generally rigid but is provided with a flexible portion between the limbs allowing hinging motion therebetween.
In order to produce or assist in producing a fluidtight seal between the anterior vaginal wall and the inner face of the first limb, a suitable substance of putty-like consistency may be used.
The invention may be put into practice in various ways, and a number of specific embodiments will be described by way of example with reference to the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a perspective view of a first embodiment of the invention showing a drainage version of the invention;
FIG. 1B is a front elevation of the device shown in FIG. 1A;
FIG. 2 is a medial cross section of the embodiment of FIGS. 1A and 1B illustrating the drainage channel and tube outlet;
FIG. 3A is a medial cross section of the lower part of the female body, showing the embodiment of FIG. 1 in position, in which position it is held either by an external strap (chained line) or by the external strap and an internal loop (dashed line);
FIG. 3B is a view similar to FIG. 3A showing a first modification of the first embodiment, provided with sheathing of the strap and a modified internal positioning arrangement;
FIG. 4 illustrates one method of securing the embodiments of the invention in position, in which an extensible strap and belt are used;
FIG. 5 is a perspective view of the second embodiment of the invention showing a restrictive version of the invention;
FIG. 6 is a medial cross section of the lower part of the female body showing the embodiment of FIG. 7 in position, in which position it is held either by an external strap (see FIG. 4) (chained line) or, in a first modification of this second embodiment, by the external strap and by an internal loop (dashed line);
The differences between FIGS. 3A, 3B and 8 reflect the wide range of different shapes and sizes of the vaginal cavity, which in fact really only exists as a cavity when a member is inserted into it. The most constant feature is the location of the anterior dorsal vaginal wall and its relationship to the pubic bone (25 in FIG. 3B). However, even the shape of the pubic bone can vary widely.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In the first embodiment, the invention takes the form shown in FIG. 1 and consists of two integrally-connected limbs 1 and 2, the inner or upper limb 1 broadening out into a tongue or, in elevation (see FIG. 1B), light-bulb-shaped plan, and the outer of limb 2 being narrower and not broadening out at its end. The limbs 1 and 2 together provide a generally U- or V-shaped configuration, the inner face 3 of the lower limb of the U being generally flat or concave. The inner face 4 of the upper limb 1 affords a centrally disposed, medially extending duct, channel or groove 5 defined by the edges of the limb 1, which edges are slightly rounded at its far end 6.
The limbs 1 and 2 form internal and external legs respectively with the external leg (limb 2) being connected to the internal leg (limb 1) by a U-shaped portion (generally at inner face 4) so that the external leg forms with the internal leg a generally J-shaped structure. As can be seen from FIGS. 3A and 3B, the external leg (limb 2) is dimensioned to conform to the mons veneris of the female using the device.
The edges 4 of the channel 5 may also be rounded along its length. The channel issues out of the end 6 of the limb 1 and extends around the base of the U some distance (e.g., about 20 to 30%, e.g., 25% of the length) along the lower limb 2, where it terminates on the surface of the limb 2 in a rounded end 7. The channel 5 communicates with an internal duct 8, at or near its end 7, which duct extends more or less diagonally through the limb 2 to emerge through its outer face at 9, at or near the end of the limb 2. This angle enables the bladder to be emptied even when the woman is sitting down. The duct 8 is thereconnected to, or continues as a tube 10. In use, the limb 1 of the device is inserted into the entrance of the vagina and is positioned so as to be located in the vagina as shown in FIG. 3A, with the limb 1 being placed against the anterior vaginal wall 11, the channel 5 being positioned so as to follow the course of the urethra 12. It is not essential for the limb 1 to extend as far into the vagina as shown in FIG. 3A. It may be shorter, provided an adequate seal can be maintained between the vaginal wall 11 and the edges 4 of the channel 5. The lower limb 2 points forwardly and is positioned against the outer surface of the body, within the vulva 13. The urethral opening 14 is thus positioned within the channel 5. Any urine escaping from the urethral opening 14 will pass along the channel 5, through the duct 8, and pass into the tube 10 where it may be collected by any suitable means, such as a receptacle attached to the patient's leg.
The device is held in position by means of external tensioning means, one form of which is a strap 15 which is attached to or is a continuation of the second limb 2 from its forward end 16. The strap 15 (which may be padded or sheathed for comfort) may conveniently be attached to a belt 17 as shown in FIG. 4 and is maintained in tension by its own elasticity or that of the belt 17, or both. When the strap 15 is sheathed, this is conveniently achieved by a plastics tube 16A which may extend (as shown in FIG. 3B) from the end of limb 2 (to which it may be connected) out beyond the vulva 13, e.g., as far as 16B (see FIG. 3B). This prevents the tensioning means from rubbing the user. The means 15 may only be elastic within such a tube and thereafter be connected to the belt by an inelastic connection. The belt may be elastic or inelastic. This tension causes the limb 1 to be pressed against the anterior vaginal wall 11. The necessary seal between the vaginal wall 11 and the edges 4 of the channel 5 may be enhanced by lining the edges 4 with any suitable material, such as a soft pad, or a cohesive gum of suitable consistency may be used. Suitable gums include a mixture of Karaya gum, glycerine and gelatine mixed to a putty-like consistency, or, alternatively, liquid polymers, such as cellulose-polybutene combination, may be used.
FIG. 3B shows a further modification in which a dorsal extension 1A of generally duck-billed shape extends rearwardly from the top back face of the limb 1 towards or past the cervix, but stops short of the dorsal wall of the vagina and extends across this region of the vagina. A dorsal extension of this sort is also shown and described in FIG. 11 (see reference 207). This extension helps maintain accurate lateral location of the device in use.
In a first modification of the device, the necessary support may be increased internally, particularly against lateral movement. This may take the form of a generally rigid but resilient loop 18, which is attached to the back or outer face of the limb 1, as shown in FIG. 1 and 3A by dashed lines. In this modification, the belt and strap again hold the device in place and cause the limb 1 to be pressed against the anterior vaginal wall 11 in the position previously described. The loop 18 being pressed against the upper dorsal vaginal wall 19 behind the cervix 20 with the natural elasticity of the vaginal wall 19 helps to hold the device in place, particularly against lateral movement.
In a third modification, the end of the channel 5 is left open, rather than communicating with the duct 8 and tube 10 (which are then no longer needed and can be omitted).
The device may be made of any suitably flexible material, such as rubber, or it may be made of a more rigid material, such as polypropylene, and provided with pads of compressible material for comfort in the necessary regions. The structure should be sufficiently rigid to ensure secure location in the vagina and to enable the force exerted by the strap 15 to pull the limb 1 against the vaginal wall 11. If the device is made of a generally rigid material, the base of the U, between the limbs 1 and 2, may be made of a more flexible material to allow some hinging movement between the limbs, thus accommodating personal differences in vaginal shape. When the loop 18 is present, the hinging embodiment can be used or the device can be made of more flexible material throughout. The use of a non-reactive material may be useful to patients with allergies to rubber of silicone products.
This first version, the drainage version, of the invention deals with incontinence by collecting the urine.
The second version, the restrictive version, of the invention mechanically causes retention of the urine.
In the second embodiment, this restrictive version of the invention takes the form shown in FIG. 5 and consists of two integrally connected limbs 101,102. The limbs 101 and 102 together provide a generally U- or V-shaped configuration, the inner face 103 of the lower limb 102 being generally flat or concave. The inner face 104 of the upper limb is generally flat or convex and terminates in an inwardly-facing protuberance 105, of which the edges are rounded as shown in FIG. 7. In use, the limb 101 of the device is inserted into the entrance to the vagina and is positioned so as to be located in the vagina, as shown in FIG. 8, with the limb 101 positioning the inwardly facing protuberance 105 so as to be being placed against the anterior vaginal wall 11, following the line of the urethra 12.
The lower limb 102 points forwardly and is positioned against the outer surface of the body within the vulva 13. The device is held in position by means of tensioning means, one form of which is a strap 115 which is attached to or is a continuation of the lower limb 102 at its forward end 116. The strap 115 (which may be padded for comfort or sheathed, as described above in connection with FIG. 3B) may conveniently be attached to a belt 17 (as shown in FIG. 4 above) and is maintained in tension by its own elasticity or that of the belt 17, or both. This tension causes the limb 101 to be pressed against the anterior vaginal wall 11 directly over the course of the urethra 12. The pressure of the limb 101, and particularly that due to the protuberance 105, causes the urethra 12 to collapse (as shown in FIG. 8), so preventing urine flow.
In a first modification of this second embodiment of the device, the necessary support may be increased internally particularly against lateral movement. This may take the form of a rigid loop 118 which is attached to the back or outer face of the limb 101, as shown in FIGS. 5 and 6 by dashed lines. In this modification, the belt and strap again hold the device in place, the limb 101 being pressed against the anterior vaginal wall 11 in the position previously described. The loop 118 being pressed against the upper dorsal vaginal wall 19 behind the cervix 20 with the natural elasticity of the vaginal wall 19 helps hold the device in place particularly against lateral movement.
It is not essential for the limb 101 to extend as far into the vagina as shown in FIG. 6. It may be shorter, provided that it extends far enough above the urethral opening 14 to allow the occlusion of the urethra 12 without significant leakage. The protuberance 105 at the end of the limb 101 is likewise not essential to the invention; the pressure of the limb 101 alone on the urethra 12 can be sufficient to cause it to collapse, but the protuberance aids certainty of operation.
The device may be made of any suitably flexible material, such as rubber, or it may be made of a more rigid material, such as polypropylene, and provided with pads of compressible material, for comfort, in the necessary regions. The structure should be sufficiently rigid to ensure secure location in the vagina and to enable the force exerted by the strap 15 to pull the limb 101 and the protuberance 105 against the interior vaginal wall 11 sufficiently hard to occlude the urethra 12. If the device is made of a generally rigid material, the base of the U, between the limbs 101 and 102, may be made of a more flexible material to allow some hinging movement between the limbs, thus accommodating personal differences in vaginal shape. When the loop 118 is present, the hinging embodiment may be used, or the device may be made of a more flexible material throughout.
Referring now to FIG. 11, this shows the third embodiment of the invention, the stress incontinence version.
Here the inner limb 201 is generally of spoon shape, while the outer limb 202 is narrower. Again, the tensioning means extend away from the end of the limb 202 as in the other embodiments and as illustrated diagrammatically at 15. A slot-like duct 205 extends around the bend which joins the limbs 201 and 202, enabling urine to be discharged from the urethral opening 14 without the device needing to be removed from the vagina. The top edge 206 of the inner limb 201 holds the user's urethra in or near the normal position and reduces or alleviates stress incontinence.
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An incontinence device for use by females wherein the device includes a forwardly facing internal leg, the internal leg having a curved surface dimensioned so as to conform to the anterior vaginal wall. The device further includes an external leg connected to the internal leg by a U-shaped bite portion to define therewith a generally J-shaped structure. The external leg is dimensioned so as to conform to the mons veneris of the female using the device. The device includes a further internal leg extending rearwardly therefrom toward the cervix.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a shoe for a crawler belt or chain, hereinafter referred to as "crawler shoe" used in an endless track vehicle, such as a construction or agricultural machine or the like.
2. Description of the Related Art
As shown in FIG. 2, in the prior art, such an endless track vehicle has crawler belts or chains, each of which has a plurality of crawler shoes 10 mounted thereon. Each crawler shoe 10 comprises a metal shoe 11 made of iron or the like having a plurality of integral projections 11a, 11b that project towards the ground contact side of the shoe and an elastic shoe 12 made of a rubber or the like, integrally molded and fixed to the metal shoe 11 around the projections on its ground contact side, so as to prevent a paved road from being damaged by the crawler shoe 10. The elastic shoe 12 and the metal shoe 11 of the crawler shoe 10 have bolt inserting screw holes (not shown) that penetrate through them for mounting one on the other. The crawler shoes 10 are connected to each other, in turn, by means of links 30 and pins 20 with bolts and nuts to constitute an endless crawler belt or chain.
In such a conventionally known crawler shoe 10, elastic shoe 12 has rounded or convex portions 13 on the surface of the respective ends of the shoe in the traveling direction (i.e., at the corners or intersections between the side surfaces 14 that extend in a direction transverse to the traveling direction and the ground contact surface 15). As shown, there is a difference between the rubber thickness of the elastic shoe 12 above the projections 11a and 11b and the rubber thickness of the elastic shoe 12 in the areas between the projections. Thus, when the elastic shoe 12 comes into contact with a road surface 50, the stresses exerted on the rubber will be concentrated in the areas above the projections.
In addition, when a crawler shoe 10, extended around a driving or idler sprocket 40, comes into contact with a road surface 50 at a "final link plunge angle θ", the leading rounded end portion 13 of the elastic shoe 12 in the traveling direction will strike the road first and be compressed between the road surface 50 and a first projection 11a on the metal shoe 11. This subjects the rubber around this portion 13 to an expansion strain or deformation due to the shearing forces encountered.
The "final link plunge angle θ" is the angle of a link 30 when the immediately preceding link 30a is in a position parallel to the road surface 50 and its shoe 12a is in contact with the surface and is represented as follows: θ=360°/n, where n=number of links that would fit around sprocket 40.
Therefore, during traveling on a gravel road, if pebbles or the like on the road are encountered by the leading side faces 14 of the elastic shoes 12, the rubber there will be deformed and sometimes a part of the rubber may be broken off.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a crawler shoe in which the concentration of forces exerted on the elastic shoe in the areas adjacent the projections can be moderated and the shearing rigidity of the end portions of the shoe in the traveling direction can be increased.
Another object of the present invention is to provide a crawler shoe in which the drawbacks as mentioned above with reference to the prior art can be overcome.
According to the present invention, there is provided a crawler shoe for use with a plurality of other crawler shoes pivotally linked together to form a chain of shoes for use with an endless track vehicle, said crawler shoe having a ground contact side facing toward a ground surface and comprising a metal shoe having integrally formed thereon at least two spaced projections projecting toward said ground contact side and an elastic shoe integrally molded and fixed to said metal shoe over said projections on its ground contact side, said elastic shoe having a ground contact surface and a hard reinforced member embedded in said elastic shoe between two adjacent projections.
In the crawler shoe according to the present invention, the difference in the thickness of the resilient or rubber shoe in the areas or portions above the projections and in the areas or portions between the projections is reduced. Therefore, when the shoe comes into contact with a road surface, stress concentrations will be moderated.
In addition, at the final link plunge angle, the shearing rigidity of the elastic shoe in the portion contacting the road surface is increased.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a crawler belt having a plurality of crawler shoes constructed according to the present invention, illustrating one shoe in contact with the road surface and the immediately following one at a plunge position; and
FIG. 2 is a cross-sectional view of a conventionally known crawler belt, illustrating one shoe in contact with the road surface and another at a plunge position.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will now be described in detail with reference to the embodiment shown in FIG. 1.
In the crawler shoe 10 shown in FIG. 1, the parts or elements corresponding to those shown in FIG. 2 are indicated by the same reference numerals.
Crawler shoe 10 has a metal shoe 11 which is provided, at the respective end portions thereof in the traveling direction and in a central portion, with three integral projections 11a and 11b that project outwardly from the metal shoe 11 toward the ground contact side of the shoe and the ground surface and extend in a longitudinal direction transverse to the traveling direction of the shoe. In accordance with the invention, two hard reinforced members 18a and 18b are buried or embedded and sealed in during vulcanization the resilient shoe 12 in the areas between adjacent projections 11a and 11b. These reinforced members 18a and 18b are buried in such a manner that they are spaced from each other in the longitudinal direction of the elastic shoe 12, except for the areas around the mounting bolt screw holes (not shown).
The relationship between the rubber thicknesses t 1 and t 2 of the elastic shoe 12 at the location where the reinforced members 18a and 18b are buried in the elastic member 12 between the projections 11a at the end portions of the shoe in the traveling direction and the projection 11b in a central portion and the rubber thickness t 3 of the resilient shoe 12 at the area adjacent or above projection 11b, which thicknesses are fixed by the thicknesses of the reinforced members 18a and 18b, is defined as follows:
0.5 t.sub.3 (t.sub.1 +t.sub.2) 2.0 t.sub.3, preferably
0.8 t.sub.3 (t.sub.1 +t.sub.2) 1.3 t.sub.3
If (t 1 +t 2 )<0.5t 3 , the rubber thickness is so small that the resilient effect of the rubber shoe cannot be realized. On the other hand, if (t 1 +t 2 )>2.0 t 3 , the thickness of the reinforced member is so small that stresses will be unfavorably concentrated in the rubber at the areas above the projections 11a and 11b.
The depth of the reinforced members 18a and 18b (i.e., their position in the resilient shoe 12 relative to the thickness thereof) is such that, if the projections 11a and 11b and the reinforced members 18a and 18b have their upper ends or surfaces extending in the circumferential direction of the crawler belt 10, at least a part of the reinforced members 18a and 18b will extend beyond and be nearer to the ground contact surface 15 of the shoe than the upper surface of the projections 11a and 11b.
Contrary to this, if the depth of the reinforced members 18a and 18b is less or more than this relative to the projections 11a and 11b, the shearing rigidity of the elastic shoe 12 is unfavorably reduced compared with that obtained from the structure mentioned above.
The material of the above-mentioned reinforced members 18a and 18b can be selected from a metal, such as iron, a fiber reinforced plastic (FRP), a plastic or the like.
The outer surface of elastic shoe 12 of crawler belt 10 has tapered surfaces 16 at the intersections between the vertical side faces 14 at the ends of the shoe in the traveling direction and its ground contact surface 15, which on contact is horizontal with respect to the traveling direction. In other words, on the outer surfaces of the shoes in its end portions that are above or vertically opposite from projections 11a.
The intersection point A of the ground contact surface 15 of elastic shoe 12 with tapered surface 16 is located nearer to the central portion of the resilient shoe 12 in the traveling direction than the corresponding projection 11a. In addition, tapered surface 16 has a predetermined inclination such that the end point A of the ground contact surface 15 is nearer to the road surface 50 than the surfaces of elastic shoe 12 in the vicinity of the projection 11a when the crawler shoe is at a position of a final link plunge angle.
In the embodiment shown, although the entire bodies of the reinforced members 18a and 18b are embedded in the elastic shoe 12, the upper surfaces thereof may be exposed on the ground contact surface 15. Also, although the ground contact surface 15 of the elastic shoe 12 has a flat surface as shown in the drawing, it may be formed as a convex surface.
The other portions of the crawler shoe are the same as those shown in FIG. 2, and therefore will not be explained in further detail.
According to the present invention, the rubber thickness of the resilient shoe 12 in the areas between two adjacent projections 11a and 11b is reduced compared with that in the prior art and, therefore, the differences in the thickness of the shoe in these areas compared to the thickness of the resilient shoe in the portions above the projections will be minimized. As described, this is a result of the reinforced members 18a and 18b being disposed between the projection 11a of the metal shoe 11 at the end portions thereof in the traveling direction and the projection 11b in a central portion thereof.
Therefore, the difference in the coefficient of elasticity of the rubber of the elastic shoe 12 in the areas above or adjacent projections 11a and 11b and the areas between the projections can considerably be reduced. Thus, when an elastic shoe 12 comes into contact with the road 50, the stress concentrations exerted on the rubber in the portions adjacent the projections 11a and 11b will be dispersed and moderated.
Also, in the crawler belt 10 constituted as mentioned above, the portion of the elastic shoe 12 in the areas between projection 11a and the ground contact surface constituted by the tapered surface 16 does not contact the road surface 50, at the time of final plunge angle θ. Rather, the end point A of the ground contact surface 15 located nearer to the center of the shoe first comes into contact with the road surface 50. Therefore, the shearing forces around these portions are reduced and these portions will be subjected mainly to compression forces. In particular, the shearing rigidity of the resilient shoe 12 in the areas between the projections 11a and 11b will be higher due to the reinforced members 18a and 18b and almost no strain due to shearing forces will be generated in the elastic shoe 12 in the areas adjacent the projections 11a.
Therefore, during traveling on a gravel road, even if pebbles or the like on the road are encountered by the side faces 14 of the resilient shoes 12, the rubber there will not be damaged.
In the above-mentioned embodiment, although the tapered surfaces 16 are formed on the resilient shoe 12 in the regions above the projections 11a of the metal shoe 11 at its ends in the traveling direction, the cross-sectional shape of the elastic in this areas can optionally be different from that mentioned above.
It should be understood by those skilled in the art that the foregoing description relates to only a preferred embodiment of the disclosed invention, and that various changes and modifications may be made to the invention without departing from the spirit and scope thereof.
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A crawler shoe used in an endless track vehicle having metal shoes made of iron or the like. The metal shoe has two integral projections projecting toward the ground contact side of the shoe. A resilient shoe made of rubber or the like is integrally molded and fixed to the metal shoe around the projections. A reinforced member is embedded in the elastic shoe between two adjacent projections.
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BACKGROUND OF THE INVENTION
The present invention relates to an arrangement, for drawing samples or specimens from melts, in which the drawn samples solidify in the absence of air, and in which the gases emitted during cooling and solidification are quantitatively collected.
In the determination of gas content, as well as certain elements of melts that are subject to change due to the influence of air, the drawing of samples or specimens plays a very large role, for two reasons. First, the melt loses certain gaseous constituents during solidification, particularly H 2 , CO and in some cases N 2 , H 2 O, CH 4 as well.
Secondly, in pouring the melt into an open form, the melt reacts with the oxygen and water vapor in air or on the surface of the form. Since the melts, at their extremely high temperatures, have a high affinity and a rapidity of reaction with the gaseous reagents from the air, uncontrollable errors result.
Swiss Pat. No. 409,469 discloses a procedure for drawing samples that permits the determination of the true gas content of melts, whereby the melt flows into a mold after melting through a replaceable meltable cap, which is sealed by rubber rings to the sample form, and flows through a replaceable metal orifice connected to the sample mold by rubber sealing rings. As soon as the mold is filled and the flow of melt ceases, the melt solidifies in the region of the orifice, producing a hermetic seal against the outside atmosphere. Here the mold has to have such thick walls or has to be constructed of a massive amount of copper to conduct away the heat of the incoming melt, to reach a temperature under 70°C. This is required to prevent the elastic seals between orifice and valve from emitting gas or leaking. Any gases that may have been liberated from the sample during solidification, appear between the sample and the wall, as the solidifying melt contracts. These separated gases can be removed through a valve with an elastic seal, and can be fed to an apparatus for analysis.
The gas remaining in the solidified sample can be exactly determined. After removal of the precision-cast, a highly-polished sample from the mold, a portion of the probe can be subjected to heat extraction. The total gas content of the melt is then the sum of the gas emitted during solidification in the mold and the gas found during heat extraction. The amount of hydrogen emitted in this way during solidification is, on the average, 5 - 30% of the total hydrogen content of the melt.
In scientific investigations of thousands of samples with the above procedure, many exact measurements, demonstrating the laws of movement of hydrogen as well as other gases, could be made. However, it became evident that it would be desirable to improve the above procedure fundamentally in several respects for routine application. With the above procedure, all parts must be cleaned very carefully before each application with particularly pure solvents, particularly CCl 4 , because, e.g., the smallest fractions of a mg. of fat, if it came into contact with the liquid melt, could strongly influence the test results. The parts of the mold have to be combined and highly evacuated before each application, with the sealing being accomplished by elastic seals. This presupposes a certain special know-how, since with improper treatment traces of impurities can strongly influence the precision of the results, as described above.
Accordingly, it is an object of the present invention to provide an arrangement for drawing samples, which retains the advantages of the above procedure, namely: drawing of samples and their solidification under seal against air, and the collection of the gases emitted during and after the solidification. But disadvantages from poor cleaning or from overheating of the sample drawing element or its rubber seals are eliminated.
Another object of the present invention is to provide an arrangement of the foregoing character which is simple in design and may be economically fabricated.
A still further object of the present invention is to provide an arrangement, as described, which is reliable in operation and may be readily maintained.
SUMMARY OF THE INVENTION
The objects of the present invention are achieved by providing an arrangement in which a metallic, thin-walled, hollow element, narrows at its lower end into an orifice. There the element with all its inserts is degassed under protective gas or vacuum at a high temperature (300 - 1200°C.), for particularly removing hydrogen and organic impurities that decompose at high temperatures. It is then evacuated and metalically sealed. Sample from elements that can be constructed from inexpensive, stamped parts, are evacuated at the beginning and sealed metallically, and are capable, in this evacuated state, of practically unlimited storage. They are always ready for use, they do not need to be cleaned before use by the person applying them, but are brought to a standard of cleanliness not possible with known procedures. This is accomplished by glow and degassing under vacuum, producing, in particular, freedom from hydrogen.
While the known procedure was so constituted that the mold could be used over and over with cleaning and replacement of a new cap and a new orifice, the new element for drawing samples is intended for a single application. Therefore it becomes far lass expensive and more favorable with respect to weight than the relatively expensive and heavy copper molds in the old procedure.
The advantage of these new elements for drawing samples lies above all in their readiness for rapid use and their analytical reliability. With few operations they can be inserted into a submersion facility. The drawing of samples by submersion in the melt requires very little time, since the actual submersion time, as well as the filling of the sample form element with melt, requires only 0.2 - 1 sec. After the cooling time, the element for drawing samples is drilled under seal against air, so that the emitted gases, particularly hydrogen, can be lead off to conventional analytical apparatus. The remaining elements to be determined in the solidified sample, are obtained through cutting open the element for drawing samples with, e.g., a cutting disc, removing the solidified sample, and subjecting it to further analytical procedures.
A further advantage of the procedure according to the invention is that the element for drawing samples, even when it is subjected to high temperatures, never leaks. Nor does it render the analytic results useless through the development of secondary gases, as is unavoidably the case with the use of elastic seals in the known procedures. Thus it is also possible to extract the hydrogen in its entirety from certain materials. This is possible because means are provided for maintaining the sample in the element for drawing samples at a high temperature, thus extracting the hydrogen shortly after drawing from the solidified sample in the element for drawing samples.
Thus, according to the invention there is obtained a procedure which permits a precise and rapid determination of the hydrogen content of melts, since shortly after drawing, the largest portion of the hydrogen has diffused from the drawn sample and is present in the collection spaces of the element for drawing samples, from which it can be removed after drilling and analytically determined.
A further advantage of the procedure, according to the invention, consists of the feature that with melts which emit water vapor during the drawing process, (which is of particular importance for the analysis of pure copper melts, for example) the water vapor reacts with reagents brought into the collection space to form hydrogen, acetylene, and other gaseous substances that are analytically and easily determinable.
The novel features which are considered as characteristic for the invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is an elevational view and shows a simply-constructed embodiment of an element for drawing samples, in accordance with the present invention;
FIG. 2 shows a second embodiment of an element for drawing samples;
FIG. 3 shows an element for drawing samples with inserted parts that cause the sample to solidify while separated from the walls of the element;
FIG. 4 shows an element for drawing samples containing inserted parts causing an increase in the solidifying surface of the melt, and causing faster gas emission from the melt;
FIG. 5 shows an element for drawing samples, in which an additional volume of melt is drawn separately and simultaneously with the sample, causing the sample to remain at a higher temperature for a longer time;
FIG. 6 shows an element for drawing samples constructed as a heat storage element, so that the heat contained in the melt is retained for a longer time;
FIG. 7 shows schematically a submersion facility with an inserted element for drawing samples according to the invention; and
FIG. 8 shows a facility for drilling into the element for drawing samples in a hermetically-sealed manner by means of which emitted gases can be led off for analytical determinations.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawing, FIG. 1 shows an element for drawing samples consisting of a housing 1 ending in a narrow aperture 12. After degassing through glow in a protective gas or in vacuum, the meltable cap 2 is metallically attached and sealed to housing 1 at point 11. The meltable cap can have, at point 69, a smaller thickness of wall (0.1 - 1 mm). Later, when the element is submerged in the melt, this wall melts easily, which also minimizes the amount of material from the meltable cap entering the sample that is to be drawn into the space 8. The entire element for drawing samples can be covered on a part of its surface, especially where an attack by the melt on submersion into the melt is to be avoided, by a protective coating 19, e.g., a finish. This protective coating 19 is applied after closing the element for drawing samples 1, 2.
The meltable cap 2 must in each case be constructed of such a metal that, on drawing the sample from the melt, no disturbing additives can enter the drawn sample. The aperture 12, on the other hand, must consist of such a metal that it forms a good metallic seal with the inflowing melt.
With steel melts it has been found advantageous to use meltable cap 2 as well as orifices 12 made of steel, since this material has the same melting point as the melt, and closes well at 12 with partial heat-sealing. With copper melts, copper is advantageous as the material for the meltable cap 2 and the orifice 12. With aluminum or aluminum alloy melts it is favorable to construct the meltable cap 2 from aluminum. The orifice, however, should be of steel, copper, or aluminum. If steel or copper are used for the orifice 12, it is necessary, particularly with those metals that do not weld with a good seal with other metals, to apply to the orifice 12, tin, copper, silver, silver solder, or similar materials that form a well-sealing metallic connection with the drawn melt sample after solidification. Since these connecting materials are entirely degassed, according to the invention, before the final closure of the element for drawing samples, there is no uncontrolled gas absorption by the drawn melt sample.
With highly-agitated melts of e.g., steel, an aluminum wire 80 can be inserted into the space 7 and 8, which is well degassed during the degassing procedure prior to closure of the element for drawing samples, and is continually sealed from air until the sample is drawn. After the sample is drawn, the insert 80 at least partially binds the oxygen content of the drawn sample, without drawing any hydrogen into the sample.
It has been found in practice that a sample entering the element for drawing samples usually does not form a heat seal with the walls of the housing 1, except at orifice 12. If such a heat seal is to be avoided with increased certainty, it is possible to provide the inner wall of housing 1 with a thin isolating coating, as for example by coating with a finish (not shown in the drawing). Here care must be taken to insure that the orifice 12 is absolutely free of such a coating finish. It is understood that the glow degassing process is of considerably greater duration with a housing 1 that has been provided with an isolating coating on its inside. The drawing of the sample occurs through submersion of the meltable cap 2 in the melt. This occurs preferably with the aid of a submersion facility as described below. After the meltable cap 2 has melted through, particularly in the area 69, the melt spurts through space 7 and orifice 12 into the space 8 of the element for drawing samples, and fills the element in substantially a fraction of a second. As soon as the melt stops flowing, the solidification process begins, and this seals the orifice 12 hermetically against the outside atmosphere.
In those cases, in which, e.g., solder has been applied at 81, a well-sealing connection is established even between metals where a good weld is often obtained only with difficulty, e.g., when orifice 12 consists of copper or steel but has a tin or silver coating, and the drawn sample consists of an aluminum alloy. As soon as the melt has solidified, it contracts, and there is a liberation of gases between the housing 1 and the melt sample solidified in space 8.
For analytical determination, according to the procedure described below, the gases separated during the solidification are removed. This is done by drilling into the element for drawing samples under seal against air, and connecting the element to apparatus for analyzing the gases. Finally, the sample solidified in space 8 is removed from the space, by cutting open the housing 1, for example, in the area above the orifice 12 with a cutting disc. The extracted sample is cut up and analyzed further by such processes as heat extraction, spectral analysis, C-determination, etc.
FIG. 2 shows an element for drawing samples in which a closing element 5, divides the inner space of the element into part 8 and part 6. The closing element 5 can be held in position by a flange 13 or by other means. The closing element 5 accomplishes prevention of the entry of melt sample from space 8 into space 6, but must allow liberated gases to pass from space 8 into space 6. If the closing element 5 is constructed of metal or of ceramic material allowing no gas to penetrate, it has been found advantageous to provide element 5 with one or more holes 79 of such small diameter (0.1 to 1 mm) that the melt solidifies when it enters them. It has also been found advantageous to construct such closing elements 5 from porous, heat-resistant, ceramic material (e.g., SiO 2 , Al 2 O 3 ) or graphite, the pores of which allow easy passage of gas while holding back the melt.
The insertion of a guiding member 18 for the melt, for example, of SiO 2 , Al 2 O 3 , or glass, causes the melt to flow centrally into the orifice 12, favoring a faster solidification of the melt in the outer area of orifice 12. FIG. 2 also shows the final closure 77 of the element for drawing samples, accomplished simultaneously with the evacuation of the element. This must be metallic, sealing connection, which must be accomplished under vacuum, and can consist, e.g., of butt welding, electric welding, soldering, etc. It is also possible to accomplish closure at this point by a metallic deformation carried out under vacuum. It is also possible to degas and evacuate the element for drawing samples at a high temperature after it has had the metallic sealing meltable cap 2 attached. This is done by drilling a hole 70, which must be finally closed by soldering or welding 71 under vacuum.
FIG. 3 shows an element for drawing samples, in which the melt enters an inserted pipe 4, which is held and centered by the closing element 5, that allows the passage of gas. The inserted pipe 4 can be made of ceramic material, e.g., SiO 2 , Al 2 O 3 or metal; or of porous material: graphite, ceramic sintered materials, etc. If porous, gas-passing material is used for the inserted pipe 4, this part can be made in one piece with closing element 5. In FIG. 3, closure of the element for drawing samples is accomplished, after glow and degassing, by a cap 3, which is closed, for example, at point 10 by soldering under vacuum.
FIG. 4 shows an element for drawing samples, which contains a second insertion pipe 17 within inserted pipe 4, providing a much enlarged surface to the inflowing metal, causing it to solidify as a thin layer. This accomplishes that the gases emitted from the melt, particularly hydrogen, can leave the solidifying melt more rapidly. As a rule, heatresistant materials, e.g., SiO 3 , Al 2 O 3 , and similar materials are used for the inserted pipe 17. In FIG. 4, the centering closing element is designated by 15 and the closing element for inserted pipe 17 is designated by 16. Element 14 is a spring for keeping closing element 16 in position and for support of inserted pipes 4 and 17.
FIG. 5 shows an element for drawing samples, in which the lower meltable cap 62 is widened and lengthened, and metallically connected to housing 1 at point 71. Thus, there arises a space 64, which has approximately the length of the inserted pipe 4. As soon as the element for drawing samples is submerged in the melt, the melt enters at point 69 into space 7, and from there it fills space 64 and space 8 simultaneously. The solidification produces a sealing closure at 12. By means of cooling insertions 66, the solidification in the vicinity of orifice 12 can be accelerated. A coating finish 75 protects the housing 1 from direct attack of the melt. A heat-isolating insertion 76 protects the walls of meltable closing cap 62. Moreover, in the embodiment of FIG. 5, coating 19 prevents an attack by the melt on the meltable cap from the outside.
It is possible to introduce reagents, e.g., Li, Ca, Mg, Al, CaC 2 , and others into the element for drawing samples at points 72 or 78, which react with water vapor to produce hydrogen or acetylene. This is of importance when melts giving off water vapor on solidification are drawn. The purpose of the construction shown in FIG. 5 is that the solidifying sample in space 8 is kept for a longer time at an elevated temperature (400° - 950°C.), by the additional melt solidifying in space 64. This accomplishes that the sample in space 8 emits a particularly large portion of diffusable, gaseous products, which are collected in spaces 9 and 6. With this procedure, it is often advantageous to construct the inserted pipe 4 as well as the closing element 5 from porous material, e.g., pure graphite.
FIG. 6 shows another embodiment for the prolonged heat retention of the sample contained in space 8. In this case, the inserted pipe 4 is surrounded by a heat-storing radiation shield 68. Insert 82 is of heat-insulating material. Near 63 it is shown how the solidifying melt closes the orifice 12 after the drawing is completed. The sample mass glowing and solidifying in space 8 yields its heat by conduction and/or radiation to the inserted pipe 4 and the heat-storing radiation shield 68.
It has been found advantageous to choose the relationship of the weight of heat storage element 68 to the weight of the drawn sample in 8 in such a way that the inflowing metal and the heat storage element 68 reach a temperature of 600° - 900°C. With steel, having a melting point of 1600°C., theoretically the heat storage capacity of the parts 4 and 68 should be one third of the capacity of the steel melt solidifying in space 8, resulting in a temperature of about 1060°C. In practice, however, measurements have shown a resulting temperature of 850° - 900°C. According to the law of heat radiation, it is easily understandable that the cooling time of the melt solidifying in space 8 is stretched to several minutes by correct dimensioning of the insert 68. This is sufficient to allow the largest portion of the hydrogen from the solidified sample in space 8 to escape, especially if the space 6 is sufficiently large. For most analytical purposes it is sufficient to make the space 6 from 5 to 50 cubic centimeters. The smaller the weight of the sample in space 8, which can be, e.g., 1 to 20 g., the smaller can be the space 6. The optimum results depend on melting point and heat storage capacity of a melt, including the heat of fusion, from which the most favorable relationship of the weight of drawn melt to the weight of insert 68 can be easily calculated.
FIG. 7 shows a submersion facility with inserted element for drawing samples, where the element is held in place by inserts 22 and 23 within the submersion pipe 20. A spring 21 holds, for example, insert 22. Insert 23 is protected by insulation 24 from attack of the melt. The submersion pipe 20 is, furthermore, protected by protective heat-insulating housings 25, 26, and 27 against melt, slag, etc., to the depth of submersion. During submersion it is possible to feed protective gas, e.g., argon, into the submersion facility, namely from the protective gas reserve vessel 34 through open valves 33 and 29, preventing thereby entry of the space 44. By means of cap 27, having at its bottom, or perhaps on the side, an opening 37, the ability to submerge through layers of slag 41 can be improved. Here the entry of slag into the space 44 is prevented by continued blowing of protective gas from the reserve vessel 34.
The protective cap 27, too, can be protected against too rapid an attack of melt and slag by a protective coating, e.g., a finish which is not shown. As soon as the submersion facility enters the melt 40, the cap 27 melts off in a direction from the bottom upwards. During this entire time, protective gas is allowed to flow from the reserve vessel 34 through the submersion facility 20, so that a pressure is maintained in space 44, with bubbles 42 escaping.
The use of protective gas is of particular importance because the parts of the melting cap 27 are removed by the bubbles from the actual sample. The optimum gas flow can be adjusted, e.g., by a needle valve or a throttle. The actual drawing of the sample occurs, after the prescribed depth has been reached, in that simultaneously valve 29 is closed while valve 30 is opened, as indicated by connection 31. With valve 36 open, the melt would rise in space 44 due to the hydrostatic pressure in space 44 after the disappearance of the excess pressure in the submersion facility. Meanwhile, the gases present in space 44 can leave through the path 38, 39, 28, 30, 36.
In many cases, in which an accelerated rise of the melt in space is desired, a source of vacuum 35 can speed up the departure of the gases from space 44 with valve 36 closed and valve 30 open. After resetting the valves 29 and 30 the melt spurts into space 44, hits protective insulator 24, and is held up at insert 23 having thin passages at 38. These passages have such small diameters that the melt solidifies immediately on entering them. The solidification is particularly rapid when the insert 23 is made of a good heat-conducting material, preferably a material with a lower melting point than that of the melt. The melt rising in space 44 melts through cap 2, spurts into the space 8, and closes the orifice 12 through solidification and heat sealing. The entire submersion procedure can be rapidly carried out. The melting of cap 2 and the filling of space 8 generally takes only fractions of a second. The person operating the submersion facility merely has to operate valves 29, 30, everything else proceeds independently of subjective influences.
The submersion facility must now be removed from the melt. The element for drawing samples 1, now filled with the sample, is removed from the submersion facility. The sample is now solidified in space 8, and is hermetically sealed against the influence of the atmosphere by the welded orifice 12. The gases emitted by the sample can only enter the spaces 6 and 9, and remain there until the analytic determination.
FIG. 8 shows a gas removal hood 50, which permits total removal of the gases emitted by the melt during solidification in the element for drawing samples. The function of the hood 50 is as follows: With the aid of the rubber seal 51 the hood is set in an airtight manner on the element for drawing samples, e.g., on the cap 3. Now the inside of the hood 50 is evacuated, then a hole 56 is made by a drill or puncturing device 54 into the wall of the element for drawing samples. In FIG. 8 this is illustrated by a hammered device, in which the stylus 54 is driven through the rubber seal 52 so that its point 55 penetrates the cap 3. Instead of the puncturing device 54, a spiral drill could also be used. Point 53 is the connection for feeding the gases pumped from opening 56 to conventional apparatus for the analysis of gases.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.
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An arrangement in which samples drawn from a melt are sealed against air, and are allowed to solidify, while the gases given off are collected for analysis. A hollow, thin-walled, metallic element is used, which narrows at its lower end into an orifice. The element is degassed at high temperature before being sealed for use, to remove hydrogen and organic impurities.
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FIELD OF THE INVENTION
[0001] The invention relates to the monitoring and measurement of fluid flow in a conduit and particularly to magnetic flow meters for use in the semiconductor industry.
BACKGROUND OF THE INVENTION
[0002] The theory of operation of a magnetic flow meter (‘magflow meter’) is based on Faraday's law of induced voltage, wherein an electromotive force (EMF) is produced that is proportional to the velocity of a conducting medium that flows through a magnetic field. Typically, in the case of a magflow meter, the flowing medium is a conductive medium passed through a section of conduit that is subjected to a transverse magnetic flux. As the conductive fluid passes through the conduit, the resulting EMF is detected by electrodes that are mounted to the conduit walls and in physical contact with the medium. To prevent shorting of the EMF, the conduit walls are constructed of a non-conductive material.
[0003] Magflow meters have found application in the process control industries (chemical, food-and-beverage, pulp and paper, water treatment) because they have low measurement error (0.2% of reading attainable) over a broad range (typically 30:1) and they require no moving parts (unlike turbine meters or paddlewheel technology) or flow restriction (unlike differential pressure meters) to operate. Magflow meters can also be configured to resist the deleterious effects of the harsh chemicals of the flow stream medium through proper selection of the materials for the electrodes and conduit walls.
[0004] Previous designs have utilized a conduit fabricated from a non-conducting material to provide the desired electrical isolation. The electrodes are mounted so that the tips are flush with the interior wall. Other designs have implemented a conduit constructed of a non-conducting liner within a metallic outer housing, with the tips of the electrodes protruding into the flow stream.
[0005] Various prior art designs possess certain disadvantages that prevent the realization of the full benefits of the magflow meter. Most magflow meters utilize a dielectric sleeve within a metal housing. Outfitting a metal housing with a dielectric liner is a costly process. Current magflow meters are complicated assemblies requiring hardware to be welded or otherwise attached to the metal housing for the mounting of the electrode and electromagnetic assemblies. Furthermore, these approaches typically teach the use of metallic electrodes, which are incompatible with applications and processes in other industries.
SUMMARY OF THE INVENTION
[0006] Despite the technological advantages of magnetic flow meters, they have not typically been used or applied in the semiconductor industry. This is thought to be due to the ultra pure and highly corrosive nature of the liquids (acids and bases such as HCl and NH 4 OH) and gases commonly used in the industry. Purity must be maintained to sub-parts per billion (“PPB”) levels. To maintain this level of purity, materials in contact with the corrosive fluid must neither corrode nor produce any ionic contamination. Therefore, flow meters completely constructed of non-metallic and non-corroding wetted materials such as PTFE or PFA (or other polymers in the same family) are strongly preferred. This requirement has eliminated magnetic flowmeters from use because the electrode in contact with the liquid must be able to conduct the EMF signal and therefore are usually constructed of metals such as 316 stainless steel, hastelloy or platinum.
[0007] In addition, magflow meters are typically large, bulky devices not conducive to the small size and flow rate requirements of the semiconductor industry. A primary driver of the size is the requirement in the process industry to fiction properly over a wide range of pressures and temperatures, necessitating the formation of the conduit from either an expensive material such as ceramic or a PTFE or PFA lined metallic pipe.
[0008] The invention in the following example embodiments is a magnetic flow meter wherein the flow conduit is constructed entirely from an insulative, non-conducting material without a metallic outer housing. The non-conducting conduit has a flow cross-section that defines a wetted perimeter containing a fluid that flows along an axis normal to the flow cross-section. The conduit is fitted with a pair of magnetic poles that spans the flow cross-section in a diametrically opposed configuration. The magnetic poles define a first lateral axis that substantially intersects the flow axis. A pair of electrodes is also disposed on the sides of the conduit, defining a second lateral axis that intersects both the flow axis and the first lateral axis formed by the magnetic poles. The electrodes are made of a conductive polymer material that is resistant to the corrosive media of the flow stream. The electrodes penetrate the wetted perimeter of the conduit to make contact with the fluid flowing within.
[0009] An advantage of the various embodiments of the invention is that the conduit is fabricated from a dielectric material, without incorporating a metallic outer housing, thus reducing the cost and complexity of lining the conduit. Furthermore, the conduit is fabricated to easily and directly accept the electrode and electromagnetic assemblies, further reducing cost and assembly complexity.
[0010] Another advantage of the various embodiments of the invention is that the conductive polymer (or plastic) electrodes are resistant to chemical attack. As disclosed in U.S. Pat. No. 5,449,017, the conductive polymer (or plastic) electrodes may be constructed from a polymer material suitable for the particular medium under measurement, including but not limited to blends of PTFE or PFA. These electrodes also feature shields that are molded into the electrode assembly to reduce background electrical noise.
[0011] An aspect of the invention addresses a problem of signal attenuation in electromagnetic flow meters. When an electrode contacts an electrolytic fluid (e.g. water or an acid or a base), the electrical connection between the fluid and the electrode is not a simple resistance. Rather, the fluid/electrode interface creates a complex impedance (an impedence having a reactive component) that is also a function of several physical properties or factors, such as the electrical conductivity of the fluid with which it is in contact, as well as the size and material of the electrode. With a standard metal electrode, this complex impedance forms a voltage divider with the capacitance of the electrical connection means that connects the electrode to the electronics. Therefore, an attenuated voltage is presented to the amplifier, the attenuation being a function of the capacitance of the connection means relative to the complex impedance of the fluid/electrode interface. The dominance of the voltage divider effect is especially prevalent in small magnetic flow meters, because the electrodes are compact and have a high complex impedance at the fluid/electrode interface.
[0012] Another advantage of one of the various embodiments of the invention utilizes an electrode construction that electrically drives an electrode shield circuit (electrodes and cabling), thereby reducing the effective cable impedance relative to the complex impedance of the fluid/electrode interface to provide a more accurate measurement of the electromotive force.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The invention may be more completely understood in consideration of the following detailed description of various embodiments of the invention in connection with the accompanying drawings, in which:
[0014] FIG. 1 is a cut away view of a prior art magnetic flow meter;
[0015] FIG. 2 is a cross-sectional view normal to the flow channel, with schematic of appurtenances, of the invention;
[0016] FIG. 3A is a cross-sectional view of the invention, normal to the flow channel;
[0017] FIG. 3B is an isometric projection of the invention;
[0018] FIG. 3C is a cross-sectional view of the invention, normal to the flow channel;
[0019] FIG. 3D is a cross-sectional view of the invention, normal to the flow channel;
[0020] FIG. 4A is a cross-sectional view of the invention, through the plane of the flow channel;
[0021] FIG. 4B is a cross-sectional view of the invention, through the plane of the flow channel;
[0022] FIG. 5 is a schematic of a prior art electrode assembly;
[0023] FIG. 5A is a schematic of a prior art electrode assembly;
[0024] FIG. 5B is a schematic of a prior art electrode assembly; and
[0025] FIG. 6 is a schematic of an electrode assembly according to the present invention.
[0026] While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The invention is generally directed to an apparatus and a system for measuring the flow velocity of corrosive chemical fluids in a semiconductor fabrication facility. While the invention is not necessarily limited to such an application, the invention will be better appreciated using a discussion of example embodiments in such a specific context.
[0028] Magnetic flowmeters are used to measure the volumetric flow rate of electrically conductive liquids. They operate on Faraday's principle of induced voltage, expressed by
emf∝B·L·U
where emf is a electromotive force (volts), B is a magnetic flux density (gauss), L is a spanwise length or thickness through the conductive liquid across which emf is generated (e.g., cm), and U is the local velocity of the conductive liquid being metered (e.g., cm/sec).
[0029] Referring to FIG. 1 , there is illustrated a prior art magnetic flow meter 1 that includes a housing 2 defining a conduit 3 having a central flow axis 4 , a wetted perimeter 5 , and containing a fluid flow 6 that flows substantially parallel to flow axis 4 . A pair of magnetic poles 7 is situated on the perimeter of housing 2 generating a magnetic field B there between. A pair of electrodes 8 is disposed on either side of housing 2 and penetrate wetted perimeter 5 so as to be in contact with fluid flow 6 . Electrodes 8 are connected to a read out device 9 for detection of an electromotive flux emf.
[0030] Referring now to FIG. 2 , an example embodiment of a magnetic flow meter 10 according to the invention is shown in cross-section. Meter 10 includes a unibody housing 20 , which is represented as a hollow cylinder that defines a conduit 30 and a wetted perimeter 37 , configured for containing a fluid flow 40 . Magnetic poles 50 are mounted on the top and bottom of housing 20 . Because housing 20 is constructed of a dielectric material, each magnetic pole 50 is mounted in a bottomed port 52 that is formed within the wall of housing 20 . Bottomed ports 52 are so-defined because they do not penetrate wetted perimeter 37 , but instead terminate within housing 20 , thus defining a bottom portion 57 . Bottomed ports 52 are aligned along a first lateral axis 95 that passes through flow axis 35 .
[0031] The embodiment of FIG. 2 also illustrates a pair of electrodes 70 as being located on the same plane as and about 90-degrees with respect to magnetic poles 50 . Each electrode 70 is mounted in a through-port 72 that penetrates housing 20 and wetted perimeter 37 , thus creating a fluid communication between each through-port 72 and conduit 30 . Electrodes 70 are aligned along a second lateral axis 105 that intersects both flow axis 35 and first lateral axis 95 . The 90-degree orientation, though preferred, is not necessary for the magnetic flow meter to be operative. The cross section of FIG. 2 shows the relationship between a magnetic field 60 and an electromotive flux (“EMF”) field 90 that is sensed between electrodes 70 .
[0032] Electrodes 70 are also connected to a read out device 80 that senses a voltage potential caused by EMF 90 . Read out device 80 may be configured to convert the voltage to engineering units (e.g., cm/sec.) before displaying.
[0033] Referring to FIG. 3A , another embodiment of the invention is shown in cross-section wherein magnetic flow meter 10 is formed from an insulative, non-contaminating, chemically inert material mass or body 110 . As used herein, the term “insulative” refers to a property of the material of mass or body 110 that is both electrically non-conducting and chemically resistant and inert to a corrosive chemical fluid flow 40 , thereby “isolating” fluid flow 40 . Conduit 30 is formed to flow through insulative mass 110 . A pair of electromagnetic coils 130 is housed within mass (or body) 110 . In this configuration, magnetic poles 50 are driven by electromagnetic coils 130 , which are connected by a magnetic return path 100 . FIG. 3A also shows electrodes 70 as being terminated with an electrode connector 120 . Electrode connectors 120 are each connected to instrumentation cable 125 that is subsequently routed to a read out device 80 (not shown).
[0034] FIG. 3B shows an isometric projection of another embodiment of the invention that is shrouded and protected from the environment. A flow passage 30 is formed through insulative mass (or body) 110 with the various components (magnetic poles 50 , electromagnetic coils 130 , shielded electrodes 70 and magnetic return path 100 ) contained within insulative mass 110 . By housing the components within insulative mass 110 , the components are protected from typical operations in the manufacturing environment, such as dust and dirt, maintenance wash downs and chemical spills. The cost and complexity of manufacturing is also significantly reduced.
[0035] Referring to FIG. 3C , another embodiment of the invention is shown that includes an inner portion 140 of a housing 20 C. Inner portion 140 is capped off with outer portion 150 A and 150 B. This arrangement allows the electromagnetic coils 130 to be mounted in housing 20 C and then capped off so as to be protected from the environment.
[0036] A similar embodiment of the invention is shown in FIG. 3D . This embodiment shows outer portions 150 A and 150 B configured in a clamshell arrangement. In this embodiment, the outer portions 150 A and 150 B combine to circumscribe inner portion 140 . Electrode connectors 120 are then connected to electrode 70 to form a hermetic seal that protects the interior components from the environment.
[0037] Referring to FIG. 4A , a depiction of a side view of the FIG. 3C embodiment is shown in cross-section. This figure shows flow conduit 30 passing through inner portion 140 along flow axis 35 . An end 75 of electrode 70 can also be seen on the wetted perimeter 37 of flow conduit 30 . Note that end 75 is in fluid contact with fluid flow 40 .
[0038] Another related embodiment of the invention is illustrated in FIG. 4B , which includes flow conduit 30 is formed into a convergent/divergent flow passage 160 . This geometry of conduit 30 acts to constrict fluid flow 40 as the fluid flow passes through magnetic field 60 , thereby increasing flow velocity U. Because the electromotive flux generated is proportional to U, convergent/divergent flow passage 160 acts to generate a greater electromotive flux 90 , thereby improving the signal-to-noise ratio detected by read out device 80 .
[0039] Referring now to FIGS. 5A and 5B , a prior art electrode assembly 165 is pictorially and schematically represented. Assembly 165 includes a central conducting member 190 connected to the non-inverting input 253 of an amplifier 250 via an electrical connecting means 215 . The inverting input 257 of amplifier 250 is connected to an electrical ground 230 . Central conducting member 190 passes through housing 2 and a dielectric liner 193 and is electrically isolated from housing 2 by means of an insulative sleeve 191 . Central conductor 190 contacts an electrolytic fluid 195 (e.g. water or an acid or a base) at a fluid/conductor interface 198 . A complex impedance 200 having an active component 201 and a reactive component 202 develops between fluid 195 and central conductor 190 . Complex impedance 200 forms a voltage divider with the impedance of electrical connection means 215 . Therefore, an incorrect or attenuated voltage is presented to amplifier 250 . This “voltage divider effect” is a function of a parasitic capacitance 260 of the connection means 215 (represented in FIG. 6 by a capacitor in phantom) and the complex impedance 200 . The dominance of the voltage divider effect is especially prevalent in compact magnetic flow meters with metallic probes, because the electrodes are small and therefore complex impedance 200 at interface 198 is high. Also, impedance 200 is a function of several physical properties, including the electrical conductivity of fluid 195 , the size of central conductor 190 , and the material of central conductor 190 . Because the conductivity of fluid is susceptible to change unrelated to the flow rate, the attenuation can be dynamic.
[0040] An embodiment of an electrode assembly 167 according to the invention is shown in FIG. 6 . Assembly 165 includes an electrically shielded electrode 170 . Electrode 170 has a longitudinal axis 180 along which central conducting member 190 is located. Central conductor 190 is in a concentric arrangement with an annular conducting member 225 . Both the central conducting member and the annular conducting member are connected to a signal amplifier 220 via electrical connecting means 215 ( 215 A, 215 B). Annular conducting member 225 and central conducting member 190 are electrically isolated from each other by way of a first insulative member 210 . A shield member 240 surrounds and is concentric with annular conducting member 225 . Shield member 240 is connected to electrical ground 230 . The schematic of a signal amplifier 220 shows amplifier 250 with non-inverting input 257 connected to central conductor 190 and inverting input 253 connected to annular conducting member 225 . A jumper connection 270 connects the inverting input 253 to the op amp output 280 . The FIG. 6 embodiment operates to drive inherent capacitance 260 to a low impedance, thereby reducing the dynamic error caused by the interaction between the complex impedance 200 .
[0041] Conducting members 190 and 225 may be fabricated from a conductive plastic, as disclosed in U.S. Pat. Nos. 5,316,035 and 5,449,017, both of which are hereby incorporated by reference. Herein, the term “plastic” refers generally to polymers, fluoropolymers or other dielectric materials particularly suited to resist the deteriorating effects of a corrosive atmosphere environment both within and outside the magnetic flow meter. Examples of a “plastic” include, but are not limited to, polyvinylidine fluoride (PVDF), polyetheretherketone (PEEK), perfluoroalkoxy (PFA), polytetrafluoroethylene (PTFE) or other materials known to persons of skill in the art to be of suitable chemical resistance. Wherein this application reference is made to a “conductive plastic,” the plastic is filled with particles or fibers of a conductive material that are added integrally and distributed throughout the plastic. The conductive material thus impregnated may include, but is not limited to, carbon or iron or both. Such plastics may be used in the central and annular conductive plastic sensing elements 190 and 225 , and shield member 240 .
[0042] While the particular magnetic flow meter embodiments presented and discussed in detail above are fully capable of obtaining the objects and providing the advantages stated, it is to be understood that they are merely illustrative of the present invention. Various other modifications and changes with which the invention can be practiced and which are within the scope of the description provided herein will be readily apparent to those of ordinary skill in the art.
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A magnetic flow metering device and method is disclosed for the measurement of corrosive flow streams. The device utilizes a unibody construction wherein the flow conduit is constructed entirely from an insulative, non-conducting material without resorting to a metallic outer housing. The portions of the electrodes in contact with the flow stream are made of a suitable conductive polymer material, resistant to the corrosive media. The electrodes also feature shields that are molded into the electrode assembly to reduce background electrical noise. The invention also utilizes an electrical configuration that actively drives the electrode shield circuit (electrodes as well as cabling) to provide a more accurate measurement of the electromotive force.
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BACKGROUND OF THE INVENTION
The present invention relates to an arc-heating type extra-furnace refining apparatus arranged such that electrodes are immersed in slag on molten steel in a ladle to thereby form an arc between the electrodes and the molten steel to heat the molten steel. More particularly, the invention is concerned with an arc-heating type extrafurnace refining apparatus in which the sealability between the covering of the ladle and the electrodes is improved.
In the arc process (hereinafter, referred to simply as "AP") of making an extra-furnace refinement of molten steel tapped from a converter, as shown in FIG. 1, electrodes 8 are immersed in a slag 6 on molten steel 4 charged into ladle 2 and an arc is formed between the molten steel and the electrodes to heat the molten steel. Simultaneously, lance 10 is immersed into the molten steel to thereby introduce a gas into the molten steel to stir the same. In this case, since lid or covering 12 is set on ladle 2, electrodes 8 and lance 10 are inserted into the ladle via insertion holes 14 provided in covering 12. At the top of ladle 2, dust collecting duct 15 is mounted, which is intended to collect exhaust gas containing the dust which is produced at the time of heating the molten steel or stirring the molten steel by bubbling or conducting powder injection.
Meanwhile, since electrodes 8 are kept at a high temperature and supplied with a high voltage, a small gap is allowed to exist between each electrode 8 and covering 12. For this reason, the flame which has been generated in the vicinity of the electrode portions within the ladle comes outside via the gaps. This flame causes an upward flow of the gas in the ladle as indicated in FIG. 1 by arrows which causes atmospheric air to be sucked into the ladle through, for example, seal 16 between covering 12 and ladle 2. As a result, reoxidation of the molten steel takes place in the ladle and, at the same time, the content of nitrogen [N] in the molten steel increases with the result that what is called "pickup" occurs.
In order to prevent the occurrence of the [N] pickup phenomenon, as shown in FIG. 2, refractory board 18 made of ceramic fiber is disposed between electrodes 8 and the covering 12 to thereby seal the gap therebetween. This sealing means, however, has a drawback in that refractory board 18 fails to function as a sealing means in the final half of AP because it is damaged by the flame which has been generated in the beginning stage of arc-heating. For this reason, where the gap between the electrode and the covering is sealed with the use of the refractory board, a [N] pickup of 0.25 to 0.75 ppm/min. still occurs.
On the other hand, a method of blowing Ar gas onto the portions of electrodes 8 in the vicinity of insertion holes 14 to thereby seal the gap between the electrodes and the covering can also be contemplated as a countermeasure. This gas seal, however, fails to have a sufficient sealing function because the Ar gas is pushed upwards by the upward flow of gas coming out of insertion holes 14. For this reason, the conventional sealing means fails to sufficiently prevent the reoxidation of the molten steel as well as not preventing the pickup of [N] and, in addition, requires the use of a large amount of seal gas (Ar gas). In this old sealing means, it is necessary to use Ar gas of, for example, approximately 300 Nm 3 /hour or more and this becomes a factor of increasing the refining cost.
SUMMARY OF THE INVENTION
The object of the invention is to provide an arc-heating extra-furnace refining apparatus which has improved sealability between the electrodes and the covering of a ladle involved, thereby enabling the prevention of [N] pickup as well as eliminating the reoxidation of molten steel, and thereby enabling a reduction in the amount of sealing gas used.
An arc-heating extra-furnace type refining apparatus in accordance with the present invention comprises a ladle capable of having molten steel received therein, rod-like electrodes which are immersed into the slag on the molten steel within the ladle so as to form an arc between the electrodes and the molten steel, a ladle covering having insertion holes permitting the insertion of the electrodes, and sealing means which is disposed on the insertion holes, and which has a first sealing member slidably fitted onto the electrode in the longitudinal direction thereof and a second sealing member disposed in such a manner as to hermetically seal both the first sealing member and the ladle covering and to provide a gap between the second sealing member and the electrode.
According to the present invention, it is possible to permit the ladle interior to be maintained in a highly sealed condition and arc-heat the molten steel in this condition. And yet, this type of sealing does not deteriorate with the lapse of treating time. Further, even when the electrode is moved about, the condition of sealing can be maintained. As a result, the degree to which the [N] pickup in the molten steel occurs during the arc process (AP) can be descreased down to 0.05 ppm/min. or less.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view showing a prior art arc-heating type extra-furnace refining apparatus;
FIG. 2 is an enlarged view showing the electrode and its neighbouring zone of the refining apparatus shown in FIG. 1;
FIG. 3 is an enlarged view showing the electrode and its neighbouring zone of an arc-heating type extra-furnace refining apparatus in accordance with a first embodiment of the invention;
FIG. 4 is a plan view of FIG. 3;
FIG. 5 is a graph showing the effect which is obtained with the use of the refining apparatus shown in FIG. 3;
FIG. 6 is a plan view showing the electrode and its neighbouring zone of an arc-heating type extra-furnace refining apparatus in accordance with a second embodiment of the invention;
FIG. 7 is a vertical sectional view of FIG. 6;
FIGS. 8 and 9 are graphs which show the effects obtainable with the use of the refining apparatus shown in FIG. 6;
FIG. 10 is an enlarged sectional view showing the electrode and its neighbouring zone of an arc-heating type extra-furnace refining apparatus in accordance with a third embodiment of the invention;
FIG. 11 is a plan view of the refining apparatus shown in FIG. 10;
FIG. 12 is a graph which shows the effect obtained with the use of the refining apparatus shown in FIG. 10;
FIG. 13 is a sectional view of an arc-heating type extra-furnace refining apparatus in accordance with a fourth embodiment of the invention; and,
FIG. 14 is a plan view of the refining apparatus shown in FIG. 13.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the first embodiment of the invention shown in FIGS. 3 and 4, rod-like electrode 20 is inserted into the ladle via insertion hole 24 which is formed in covering 22 of the ladle and which is circular in cross section. On covering 22 in vicinity of the insertion hole 24, annular base seal 26 is installed, which constitutes a second sealing member. On this base seal 26, annular cap seal 28 constituting the first sealing member is installed in a manner that it is slidable with respect to base seal 26. Base seal 26 has an inner diameter greater than the outer diameter of electrode 20 and an outer diameter greater than the diameter of insertion hole 24. Base seal 26 is installed on covering 22 in a manner such that it is inserted over electrode 20 so that small gap 32 may be formed between its inner peripheral surface 30 and the outer surface of electrode 20. Annular embossed portion 34 is formed on the outer peripheral edge portion of base seal 26 over the entire circumference thereof. Cap seal 28 has an inner diameter substantially equal to the diameter of the electrode 20. Accordingly, cap seal 28 has its inner peripheral surface 36 in to slidable contact with electrode 20 and thus is made movable in the longitudinal direction thereof. On the other hand, the outer diameter of cap seal 28 is greater than the inner diameter of base seal 26. For this reason, cap seal 28 can be engaged with base seal 26. Further, since outer peripheral surface 36 of cap seal 28 is smaller in diameter than the inner wall surface of embossed portion 34, cap seal 28 can slide on the base seal 26 in the area surrounded by annular embossed portion 34.
Base seal 26 and cap seal 28 can be formed using, for example, a refractory having a composition of, alumina (Al 2 O 3 ) 90%-silica (SiO 2 ) 10%.
Base seal 26 is formed in inner peripheral surface 30 with horizontal injection nozzles 38 permitting gas to be horizontally injected toward electrode 20, and is also formed on its underside with vertical injection nozzles 40 permitting gas to be downwardly injected. These injected nozzles 38 and 40 are connected with an external gas supply source for supplying an inert gas such as, Ar gas. That is, Ar gas is discharged by way of injection nozzles 38 to form a purge in the horizontal direction to thereby provide a horizontal gas seal. Additionally, Ar gas is discharged by way of injection nozzles 40 to form a purge in the vertical direction to thereby provide a vertical gas seal as well.
In the arc-heating type extra-furnace refining apparatus having the above-mentioned construction, when the molten steel is arc-heated using the arc formed between the molten steel and electrodes 20, the flame within the ladle is prevented from coming outside the same and any upward flow of gas passing through the insertion hole is also prevented from occurring since the electrode 20 is hermetically connected with covering 22 by means of cap seal 28 and base seal 26. Accordingly, suction of any atmospheric air into the ladle is prevented and thus it is possible to minimize [N] pickup as well as the reoxidation of the molten steel.
Further, cap seal 28 is kept in contact with electrode 20 and is light in weight and small in size. Therefore, even when electrode 20 is moved horizontally, cap seal 28 can slide on base seal 26 in a manner to follow electrode 20. Even in such a case, therefore, a state of sealing can be maintained between electrode 20 and covering 22. On the other hand, when electrode 20 is vertically moved, cap seal 28 can slide along electrode 20 in the longitudinal direction thereof. In this case as well, therefore, the state of sealing can be maintained.
Further, according to this first embodiment, since the Ar gas is discharged through injection nozzles 38 to form a horizontal gas seal, the flame which rises upwards from the interior of the ladle is cut off by such horizontal gas seal. Further, since the Ar gas is discharged through injection nozzles 40 to form a vertical gas seal, even when the molten steel is splashed upwards over the zone located in the vicinity of insertion hole 24, the splashed steel is prevented from clinging to electrode 20 or covering 22.
In this way, according to the present invention, it is possible to avoid the occurrence of any operational trouble as well as to prevent not only the occurrence of [N] pickup but also the reoxidation of the molten steel. Table 1 below shows examples in which molten steel is arc heated using the arc-heating type extra-furnace refining apparatus in accordance with the first embodiment of the invention, while Table 2 below shows comparative examples in which molten steel is arc heated using a prior art refining apparatus.
TABLE 1______________________________________ Treating Content Rate Flowrate Time In of [N] of [N]-- of Ar SecondaryNo. AP Pick-up Pick-up Gas Voltage______________________________________1 45 2 0.04 250 3602 52 1 0.02 200 3103 50 0 0 200 3104 48 2 0.04 230 3605 42 1 0.02 240 3606 39 0 0 230 4107 55 1 0.02 180 3108 48 2 0.04 190 3609 49 0 0 200 36010 39 0 0 200 41011 54 1 0.02 230 31012 56 0 0 200 31013 50 2 0.04 190 31014 49 1 0.02 200 36015 47 2 0.04 230 36016 55 1 0.02 220 31017 35 1 0.03 200 41018 53 0 0 210 31019 48 0 0 220 36020 55 1 0.02 170 31021 45 1 0.02 190 360______________________________________
TABLE 2______________________________________ Treating Content Speed Flowrate Time For of [N] of [N]-- of Ar SecondaryNo. Ar Gas Pick-up Pick-up Gas Voltage______________________________________1 51 23 0.45 300 3102 50 13 0.26 300 3103 45 26 0.58 280 3604 46 19 0.41 290 3605 52 17 0.33 280 3106 55 16 0.29 280 3107 49 35 0.71 280 3608 48 34 0.71 310 3609 51 32 0.63 300 31010 42 21 0.50 290 360______________________________________
In the above Tables 1 and 2, the treating time in AP is expressed in units of minutes; the [N] pick up content in units of ppm; the rate of [N] pickup in units of ppm/min.; the flowrate of Ar gas in units of Nl/min.; and the level of secondary voltage in units of volts. Further, the ladle has a volume of 250 tons; the electrode has a diameter of 18 inches; and the maximum rate at which the temperature of molten steel is raised is 4.5° C./min.
The results of the above mentioned examples and comparative examples are shown in FIG. 5 in which the treating time in AP is plotted on the abscissa and the [N] pick up content (ppm) on the ordinate. As apparent from Tables 1 and 2 and the graph shown in FIG. 5, according to the examples of the invention, the speed of [N] pickup is as low as 0 to 0.05 ppm/min. and the increase in [N] content per treatment is as small as 0 to 2 ppm. In contrast, according to the comparative examples, the speed of [N] pickup is as high as 0.25 to 0.75 ppm/min. and the increase in [N] content per treatment is as large as 13 to 35 ppm.
A second embodiment of the invention will now be described. This second embodiment differs from the preceding first embodiment in that the direction of ejecting a seal gas is so set as to cause the flow thereof to rotate around the electrode; about the lengthwise axis thereof. This enables the enhancement of the sealability and, at the same time, enables a reduction in the amount of the seal gas used. FIGS. 6 and 7 show an arc-heating type extra-furnace refining apparatus in accordance with the second embodiment of the invention. In these figures, the same parts or portions and members as those used in FIGS. 3 and 4 (first embodiment) are denoted by like reference numerals, and description thereof is omitted.
Base seal 42 is formed on the interior with a pair of gas flow passages 44 along the half circles using electrode 20 as their center. The gas flow passages 44 being connected to an external gas supply source via gas supply passages 46. Each gas flow passage 44 is formed with a plurality of horizontal injection nozzles 48 extending in the horizontal direction, as well as a plurality of vertical injection nozzles 50 extending in the vertical direction. From horizontal injection nozzles 48, the gas is purged in the horizontal direction, thereby to intercept the flame rising upwards from inside the ladle. On the other hand, from vertical injection nozzles 50, the gas is purged in the vertical direction, thereby to prevent the molten steel from being splashed over, and clinging to insertion hole 24. This prevents sparking from electrode 20.
Each horizontal injection nozzle 48 is inclined at a specified angle with respect to the direction extending from gas flow passage 44 toward the center of electrode 20, whereby the gas discharged from horizontal injection nozzle 48 into the gap between base seal 42 and electrode 20 can flow in the same direction in such a manner as to rotate around electrode 20, about the lengthwise axis thereof. This rotational flow of the gas cuts off the upward flow of gas from inside the ladle. In order to form a sufficient rotational flow of gas around electrode 20, horizontal discharge bore 48 preferably is provided at least four in number along the half circles. FIG. 8 is a graphic diagram showing the relationship between the direction of discharge of the horizontal discharge bore 48 and the sealing characteristic, which holds true where the flowrate of inert gas is 100 Nm 3 /hour. In FIG. 8, the abscissa represents the angle at which the discharging direction of the horizontal discharge bore 48 is inclined with respect to the direction extending toward the center axis of the electrode 20 while, on the other hand, the ordinate represents the speed of [N] pick-up as expressed in terms of (×10 -2 ppm/min.). That is, where the angle of inclination of the horizontal discharge bore 48 is 0°, the flow of the gas ejected therefrom advances toward the electrode 20. As the angle of inclination increases, the flow of gas is greatly inclined from the direction extending toward the center axis of the electrode 20. As clear from FIG. 8, while the speed of [N] pick-up is as high as 0.1 to 0.2 ppm/min. in case where the angle of inclination is 0°, the speed of [N] pick-up becomes lower as the angle of inclination increases to cause the formation of a stronger rotational flow of inert gas. As seen in FIG. 8, if the horizontal discharge bore 48 is inclined at an angle of 10° or more with respect to the direction extending toward the electrode 20, then the rate of pick-up of [N] can be greatly slowed down as compared with a case where the flow of the gas discharged is directed toward the electrode 20.
With the arc-heating type extra-furnace refining apparatus having the above-mentioned construction, molten steel is arc heated using an arc formed between electrode 20 and the molten steel, flame rises from inside the ladle toward electrode insertion hole 24 the molten steel is splashed toward electrode hole 24. However, inert gas is being supplied into gas flow passages 44 via gas supply passages 46 connected with the external gas supply source, the inert gas being discharged on and around electrode 20 via horizontal injection nozzles 48 and vertical injection nozzles 50. The inert gas discharged from vertical injection nozzles 50 is vertically discharged downwards, thereby to prevent the molten steel from splashing toward electrode insertion hole 24 and from clinging in the neighbourhood of insertion hole 24. On the other hand, the inert gas which is discharged from horizontal nozzles 48 into the annular gap between electrode 20 and base seal 42 flows in such a manner as to rotate in one direction (in the counterclockwise direction in FIG. 6) around electrode 20. This horizontal rotational flow of inert gas acts to cut off the flame rising upwards from inside the ladle, thereby preventing any upward flow of gas passing through insertion hole 24. Accordingly, the interior of the ladle is kept under positive pressure due to the Ar gas and any atmospheric air is prevented from being sucked into the ladle from between the covering and the ladle. For these reasons, the molten steel is prevented from being reoxidated and, at the same time, from undergoing the pickup of [N].
FIG. 9 is a graphic diagram showing the effect of the invention, showing the relationship between the amount of inert gas discharged and the rate of pickup of [N] in the case of using the gas sealing means described hereinabove in connection with the second embodiment of the invention. Measurement data was obtained when molten steel was heated at a maximum molten-steel temperature raising rate of 4.5° C./min. by using an arc-heating type extra-furnace refining apparatus in which the ladle has a capacity of 250 tons; the transformer has a capacity of 35,000 kVA; the secondary voltage has a level of 310 to 510 V; and the electrode has a diameter of 18 inches. In the graph of FIG. 9, the circles represent the measurement data which have been obtained when the gas discharging direction is inclined with respect to the direction extending toward the electrode in accordance with this second embodiment, while the dots represent the measurement data which have been obtained by blowing the gas toward the gap between the electrode and the covering as in conventional method. The arc heating time is 40 to 55 minutes with respect to each measurement. As clear from FIG. 9, when the gas discharging direction is in conformity with the direction extending toward the center axis of the electrode, the discharging flow of gas collides directly against the surface of the electrode, so that the gas flow loses most of its force. For this reason, the sealing inert gas is pushed upwards by the flow of gas rising from inside the ladle, failing to check the intra-ladle flow of gas advancing toward the insertion hole. For this reason, as seen in FIG. 9, conventionally, the rate of [N] pickup is high and in order to decrease the [N] pickup rate down to a value of 0.05 ppm/min., it is necessary to supply and discharge the inert gas at the rate of 300 Nm 3 /hour. In contrast, according to the invention, when the discharging amount of inert gas is 100 Nm 3 /hour or more, the [N] pickup rate is 0.05 ppm/min. or less. That is, according to the invention, it is possible to suppress the [N] pickup rate below the quite small value of 0.05 ppm/min. This is because, in the present invention, the inert gas discharged from horizontal injection nozzles 48 forms a strong rotational flow around electrode 20 to thereby effectively cut off the flame and upward gas flow occurring from inside the ladle.
As stated above, according to this second embodiment, a strong rotational flow of inert gas is formed around the portion of the electrode in the vicinity of the insertion hole. For this reason, it is possible to maintain high sealability between the electrode and the covering to be to thereby effectively cut off the flame and upward gas flow occurring from inside the ladle. Accordingly, it is possible to maintain the interior of the ladle under positive pressure to thereby prevent and atmospheric air from being sucked into the ladle. Accordingly, it is possible to effectively prevent the pickup of [N] in the molten steel as well as the reoxidation of the same. Accordingly, it is also possible to decrease the amount of inert gas intended for use in sealing and thereby to reduce the refining cost.
Next, a third embodiment of the invention will be described with reference to FIGS. 10 and 11. In this third embodiment, the base seal member designed to eject the seal gas is made into a water-cooled structure with the aim of lengthening its service life. Base seal 52 is formed with cooling water passages 56. These passages are formed in such a manner as to pass through almost all of the central region of base seal 52 (as viewed in the thickness wise direction) without crossing gas passages 44 and 48. Further, cap seal 54 also is formed with cooling water passage 58.
In the arc process (AP), after the covering is set on the ladle in which molten steel is received, cooling water is caused to flow through cooling-water passages 56 and 58, thereby cooling base seal 52 and cap seal 54. Subsequently, while base seal 52 and cap seal 54 are thus being cooled by water, seal gas is caused to flow through gas passages 44 and 48 to thereby seal the electrode, thus facilitating the arc process. Due to the water cooling procedure base seal 52 and cap seal 54 are prevented from being impaired or damaged from the heat of the molten steel and arc. That is, where the refining apparatus has no water-cooled structure, the base seal and cap seal are thermally damaged to a comparatively large extent and must actually be replaced after 150 to 200 charges. According to this third embodiment, however, the rate at which the base seal and cap seal are thermally worn is very low, enabling their use in up to approximately 1000 charges. FIG. 12 shows the relationship between the frequency of uses of the base seal and cap seal and the [N] pickup rate, by comparing the use of the base seal and cap seal in accordance with this third embodiment with the use of the base seal and cap seal having no water-cooled structure. As seen in FIG. 12, according to this embodiment, it is possible to stably maintain the [N] pickup rate at small values and any measurable increase in the [N] pickup rate was not recognized until after approximately 1000 charges was completed. Similarly, it is also possible to simultaneously suppress the reoxidation of the molten steel.
Next, a fourth embodiment of the invention will be described. This fourth embodiment is directed toward improving the dust collection hood installed above the ladle so as to decrease the pickup of [N] in the molten steel. That is, as shown in FIG. 1, a conventional dust collection hood is provided on ladle 2 in such a manner as to cover the ladle. This hood, however, is opened at the bottom and is mounted directly on covering 12. For this reason, when the amount of suction air intended for dust collection is increased, a negative pressure is produced within the ladle which promotes the attraction of atmospheric air into the ladle. As a result, the rate of pickup of [N] in the molten steel is increased. The fourth embodiment is intended to eliminate this problem. Referring to FIGS. 13 and 14 showing the fourth embodiment of the invention, dust collection hood body 60 is shaped like a box and is installed above ladle covering 22 with specified gap S being provided between hood body 60 and covering 22. This gap is constituted of a layer of atmospheric air. Electrodes 20 are passed through body 60. Electrode holes 62 are formed at the upper side of the body 60 and electrode holes which serve as suction holes 64 are formed at the lower side. Accordingly, suction holes 64 are provided above insertion holes 24 of ladle covering 22. Body 60 can have any given height H which permits any upward flow of exhaust gas to be sufficiently trapped inside the body. Body 60 is formed at the side periphery with joint ports 66 to which dust collection ducts are connected. Joint ports 66 are provided in the number equal to that of suction holes 64. Since, in this embodiment, the number of electrodes 20 or suction holes 64 is three, the number of joint ports 66 is also three.
With the above-mentioned construction, the exhaust gas containing dust therein which is discharged from insertion holes 24 is sucked into body 60 via suction holes 64. Since body 60 can have any given height large enough to permit the exhaust gas to be sufficiently trapped inside body 60, the exhaust gas is effectively trapped inside body 60 and is sent from joint ports 66 to the dust collection ducts. Since joint ports 66 are provided in number equal to that of suction holes 64, the dust collection is also effectively performed.
Body 60 is box-shaped and therefore has excellent airtightness, so that the suction is performed efficiently. Further, body 60 is mounted above ladle covering 22 in such a manner that it is spaced away from the latter without making contact thereto. As a result, the interior of ladle 2 is prevented from having a negative pressure, so that the attraction of air into the ladle is impossible.
Consequently, it is possible not only to enhance the dust collection efficiency but also to prevent nitrogen gas from being picked up by the molten steel.
According to the experiments performed by the present inventors, it has been proved that, in the case of the prior art dust collection hood 15 (FIG. 1), even when the dust collection damper has an opening of 100%, dust escapement is considerable. In the case of the above-mentioned present dust collection hood, however, sufficient dust collection is possible with the dust collection damper having an opening of only 70 to 80%. Further, the dust collection hood is also followed by a remarkable power reduction required by the dust collector blower involved. Furthermore, the use of this dust collection hood made it possible to reduce the (N) pickup speed from 0.30 ppm/min., which is a conventional value, down to 0.10 ppm/min. which is approximately 1/3 of the former value.
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The gap between an insertion hole formed in a covering of a ladle and an electrode inserted through the insertion hole is sealed by sealing means. The sealing means has a cap seal longitudinally and slidably fitted over the electrode. A base seal is hermetically disposed between the cap seal and the covering in such a manner that a gap is provided between the electrode and the base seal. The base seal has a gas injection nozzle intended to discharge a gas toward the electrode and another gas injection nozzle intended to discharge the gas downwardly. The use of the base and cap seals enables securing the sealing functions thereof despite any movement of the electrode, thus preventing the pickup of [N] as well as the reoxidation of molten steel. When a gas seal is effected by the formation of a flow of gas rotating around the electrode about the axis thereof, the sealing performance can be more enhanced. Further, when the base seal is cooled by causing cooling water to be circulated therethrough, its durability can also be enhanced.
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FIELD OF THE INVENTION
[0001] For thin-film displays incorporated with an element spontaneously emitting light, an organic electroluminescence device, in which electroluminescence (EL) emitted by an organic compound material is utilized, has been expected to find various practical purposes. At present, however, conventional organic electroluminescence devices are low in a light extraction efficiency at 20% or less, and need specific measures to improve the efficiency. Therefore, submicron- or nanometer-size microstructures have been proposed to improve light extraction efficiency of organic electroluminescence devices. Some of these proposals are described below.
BACKGROUND OF THE INVENTION
[0002] For example, prior arts of Patent Documents 1 and 2 discuss that aerogel containing 3 to 10 nm thick silica particles and pores of the order of 10 to 50 nm in size, when included between a board and light-emitting layer in an organic electroluminescence device, increases photoluminescence intensity and current efficiency of the element almost 2 times and 1.6 times, respectively. Prior art of Non-patent Document 1 discusses that aerogel, when included between a thin-film transistor board and transparent electrode in an organic electroluminescence device, increases current efficiency of the device by almost 60%.
[0003] Another prior art of non-patent Document 2 discloses an attempt to improve light extraction efficiency of an organic electroluminescence device based on a photonic crystal layer with a silicon nitride (SiN) film provided on a glass board and below a transparent electrode, and 7 to 400 nm deep patterns provided in the interface between the glass board and SiN film at intervals of 200 to 900 nm. It discusses that increasing depth of the pattern grooves can improve its light extraction efficiency by up to 50%.
[0004] Patent Document 1: JP-A-2001-202827
[0005] Patent Document 2: JP-A-2003-201443
[0006] Non-patent Document 1: Hiroshi Yokogawa, 9 th Symposium, Organic Molecules and Bioelectronics Section, JSAP, 2001
[0007] Non-patent Document 2: Yong-Jae Lee, et. al, Appl. Phys. Lett., 82, 3779 (2003)
BRIEF SUMMARY OF THE INVENTION
[0008] Conventional light-emitting elements involve problems of decreased proportion of light emitted to the outside, because light emitted from a light-emitting layer partly turns into reflected light or light of guided wave, resulting from limitations set by total reflection angle on the plane from which light is emitted. As disclosed by the above documents, the submicron- or nanometer-size microstructures have been studied to improve light extraction efficiency of organic electroluminescence devices. It is however hard to say that these techniques have realized the sufficient effects. Moreover, these techniques need special processes and sophisticated, precision controlling techniques, are hard to stably secure sufficient refractive index, diffraction intensity and scattering intensity, and should be improved with respect to stability and controllability of light-emitting intensity at the plane from which light is emitted. Viewed from production technology, in particular, they are low in productivity resulting from insufficient throughputs, and are considered to leave much to be improved.
[0009] The inventors of the present invention have developed, based on novel techniques, an optical thin film highly efficient and stably controllable for light extraction, simple in structure and applicable to production techniques, and attempted to solve the above problems by utilizing its functions and characteristics. It is an object of the present invention to provide an organic electroluminescence device which uses the optical thin film of low refractive index and capable of being produced simply from commercial starting materials, in order to improve its light extraction efficiency and, at the same time, to improve its light-emitting efficiency and reduce the required operational current and power consumption as a result of the improved light extraction efficiency.
[0010] Described hereunder are the optical thin film of low refractive index incorporated in the organic electroluminescence device of the present invention, and procedures for improving light extraction efficiency of the device and reducing the required operational current and power consumption.
[0011] First, the optical thin film of low refractive index incorporated in the present invention is described. FIG. 1 ( a ) outlines a cross-section of the optical thin film provided on a glass board for the present invention. FIG. 1 ( b ) presents a schematic diagram of a photograph observed by a scanning electron microscope (SEM) of the actual cross-sectional structure. The optical thin film for the present invention was prepared by a procedure which used silica-dispersed sol, colloidal silica and alcohol as the starting materials for the film. As shown in FIGS. 1 ( a ) and ( b ), it is found that the procedure for the present invention can produce the optical thin film composed of a dielectric material as the base material which contains nanometer-size pores having a nanometer-order thickness. It is also found that proportion of the nanometer-size pores gradually increases upwards to the surface, and that their size also increases upwards to the surface. The electron microscopic analysis, carried out selectively for the pore inside, detected carbon (C), oxygen (O) and hydrogen (H) derived from the alcohol in the pores, and only silicon (Si) and oxygen (O) derived from silica (SiO 2 ) around the pores.
[0012] The average refractive index of the film as a whole can be set at a level lower than that of the dielectric material as the base by controlling film thickness, or proportion or size of the pores. The film has an average refractive index lower than that of silica by itself, as revealed by an optical analysis. It can be changed in a range from 1.09 to 1.5 (refractive index of film of solid silica) by controlling the film-making conditions. FIG. 2 shows the relationship between refractive index and thickness of the optical thin film, prepared under certain conditions, where these properties were determined by ellipsometry. The film prepared to be pore-free, i.e., solid silica film, had a refractive index of 1.5. It is found that refractive index of the film can decrease as its thickness decreases by forming nanometer-size pores in the film and controlling its thickness. It is also found, however, that it has a tendency that a refractive index does not lower and no longer depends significantly on thickness even when the film thickness decreases to below a certain level. As illustrated in FIG. 2 , the film prepared under specific conditions shows limited dependence on thickness when it is 140 to 150 nm or below. This conceivably results from the pores distributed throughout the film to leave little changes in pore proportion and hence in refractive index. The film shown in FIG. 2 has a refractive index controlled almost constant at 1.22 to 1.26 essentially irrespective of film thickness when it is 140 nm or below, indicating that film thickness is an important parameter for controlling refractive index of an optical thin film.
[0013] The detailed analysis of the electron microgram for the pore distribution indicates that both proportion and size of the pores increase towards the upper region near the surface, by which is meant that a refractive index distribution in which it decreases in the thickness direction can be realized, although the average refractive index of the film as a whole is determined by its thickness. In other words, the film can have a refractive index distribution in which it smoothly changes in the thickness direction, and the distribution can be controlled by the film-making conditions to control film thickness and pore proportion. That the distribution of smoothly changing refractive index in the thickness direction can be realized in an optical thin film means that the film can transmit light without greatly decaying its transmittance, because of lack of the interface which massively receives light while it is transmitting light. Therefore, the optical thin film for the present invention, in which proportion of the pores gradually changes in the thickness direction and increases towards the surface, provides important effects of realizing a smooth distribution of refractive index, tapering off the proportion towards the surface and, at the same time, giving a high scattering light intensity in the vicinity of the surface. Moreover, the optical thin film for the present invention, when formed on a glass board, can keep a refractive index difference low between the film and board at their interface to minimize reflection-caused loss, because the region essentially free of the pores serves as the interface.
[0014] Moreover, shape and size of the pores are widely varying in the optical thin film, with spherical to flat, elliptic shapes randomly distributed, as observed by an electron microscope. Size of the pores is almost in a range from 50 to 400 nm, which corresponds to, or is shorter than, a wavelength of bluish purple color in visible light (wavelength: 400 to 700 nm), i.e. which is less than or about a visible light wavelength. When the pores of the above size transmit light, Mie scattering, which occurs when light hits an object having a size of light wavelength, can be utilized. The optical thin film for the present invention is structurally characterized by the pores whose size is controlled to positively utilize the conditions under which scattering of visible light wavelengths of transmitted light (i.e., Mie scattering) occurs.
[0015] The organic electroluminescence device of the present invention is structured to enhance light extraction efficiency, i.e., to emit light from the light-emitting layer in the device to the outside as far as possible. In order to emit light to the outside, it is necessary to keep angle of incident light on the plane from which light is emitted smaller than total reflection angle. According to classic optics, even a light component which cannot be emitted to the outside, because it is kept at an angle equal to or larger than total reflection angle as a result of common light reflection, can have a decreased incident angle on the plane, when light scattered by the pores in the optical thin film is utilized. Therefore, light scattering at the pores can increase light components which can be emitted to the outside. The intensity distribution of Mie scattering light is characterized by a radial pattern, with light scattered after it hits an object greatly extending it the radial directions. Therefore, it is considered to be more advantageous with respect to light extraction efficiency than light scattered after it hits an object smaller than light wavelengths, i.e., Rayleigh scattering light, whose intensity distribution is characterized by a spherical pattern.
[0016] It is necessary, when incident light hits an object, to minimize reflection or loss of Mie scattering light. In order to avoid reflection or decay of light as far as possible and thereby to keep scattered light intensity at a high level, an object having a light wavelength size is needed for the scattered light distribution, although a suitable size is in a limited range. The object preferably has a size smaller than light wavelengths to avoid reflection or decay of light. When size of the object is considered to an extent of around half of light wavelength as a measure to prevent reflection or decay of light from occurring greatly, it will be in a range from 50 nm (which is a demarcation wavelength between Mie scattering and Rayleigh scattering) to around half of incident light wavelength, in order to effectively utilize Mie scattering light. The above discussion leads to a conclusion that nanometer-size of the pores to be introduced into the optical thin film for the present invention is in a range from about 50 to 200 nm for visible light wavelengths.
[0017] Next, significance of utilizing light scattering for light extraction efficiency of a light-emitting element is described. Referring to FIG. 3 ( a ), when the glass board 4 is regarded as the plane from which light is emitted, the critical angle θ c , at an incident light angle above which no light can be emitted to the outside, is given by the formula θ c =sin −1 (1/n glass ), where n glass is refractive index of the glass board and that of air is assumed to be 1. This means that emission of light to the outside is limited by the critical angle on the plane. Light extraction efficiency can be estimated from solid angle of light emitted from the plane at the critical angle. More specifically, light emitted from the plane at the critical angle has a solid angle given by the formula 2π(1−cos θ st ), where θ st is angle at which light is emitted from a light-emitting point in the organic layer 7 , when light reaches the point after being transmitted by the optical thin film 5 as a layer of low refractive index and transparent electrode 6 . Therefore, its light extraction efficiency η ext is given by the formula η ext =1−cos θ st . The efficiency remains unchanged even in the presence of the optical thin film 5 of low refractive index, because reflection of light in a film is determined only by its refractive index, as taught by classic optics.
[0018] On the other hand, the optical thin film 5 for the present invention, illustrated in FIG. 3 , is not only of a low refractive index layer but also has nanometer-size pores, which is equivalent to or shorter than visible light wavelengths, and can emit Mie scattering light to the outside. The pore region in the optical thin film 5 , illustrated in FIG. 3 , scatters incident light entering at an angle lager than the incident angle determined by the glass board plane from which light is emitted, thus changing incident angle in practice. Consequently, part of scattered light can be emitted from the plane to the outside as the light component having an incident light angle smaller than the critical angle. The pore region in the optical thin film 5 can scatter a light to enhance a light extraction efficiency and hence expands a solid angle effective for a light extraction. This shows that a solid angle θ st contributive to a light extraction can be made larger to be able to make a light extraction efficiency η ext (1−cos θ st ) larger. The above discussion can explain the improved light extraction efficiency of the present invention by introducing the optical thin film having nanometer-size pores.
[0019] The optical thin film for the present invention has a nanometer-order thickness. However, they may be stacked in layers to have a micron-order thickness. It is possible, by stacking the optical thin films 5 to have a thicker film, to control refractive index of the film as a whole or to set thickness of the low refractive index layer for specific purposes, because of increased thickness of the pore region, as illustrated in FIG. 3 ( b ). It is also applicable when the thicker region for utilizing scattered light is needed. Stacking the films, therefore, allows the optical thin film for the present invention for specific purposes. The resulting film can be controlled to have a desired refractive index or thickness, and is highly versatile.
[0020] As discussed above, the light-emitting element of the present invention, incorporated with the stacked optical thin films, is characterized by improved light extraction efficiency brought by the nanometer-size pores which utilize Mie scattering light of visible wavelengths. The improved light extraction efficiency leads to emission of light of high luminance at a reduced current or voltage. FIGS. 4 to 6 show the quantitatively calculated results, FIG. 4 plotting relative luminance intensity against operational current with light extraction efficiency as a parameter, FIG. 5 plotting relative current against light extraction efficiency, and FIG. 6 plotting relative power consumption against light extraction efficiency. FIG. 4 shows the luminance-current characteristics, illustrating to what extent the characteristics can be improved by increasing light extraction efficiency from 20% as the base. Doubling a light extraction efficiency of 20%, which is a level of a common organic electroluminescence device, to 40% and tripling to 60% doubles and triples luminance at the same current, respectively. Doubling a light extraction efficiency of 20% to 40% and tripling to 60% reduce required current to half and one-third at the same luminance, respectively, as illustrated in FIG. 5 . Doubling a light extraction efficiency of 20% to 40% and tripling to 60% reduce power consumption to around one-third and one-fourth, respectively, as illustrated in FIG. 6 . Therefore, improving light extraction efficiency not only improves luminance but also reduces device operational current or voltage, and contributes to reduced power consumption of the display as a whole.
[0021] Moreover, the optical thin film for the present invention is highly moisture-absorptive and efficiently absorbs moisture from the surface, and exhibits a function of gettering moisture in an atmosphere for sealing the organic electroluminescence device. A common insulating film has a high surface resistivity of 10 15 to 10 16 Ω/cm 2 . Therefore, charges of the ionic molecules which it absorbs tend to accumulate locally, and concentration of the ions which can be absorbed tends to be saturated in that region. By contrast, the optical thin film for the present invention is found to be highly antistatic, because of its low surface resistivity of 10 10 to 10 11 Ω/cm 2 . It prevents local accumulation of charges to keep a high ion saturation concentration, because of prevented local accumulation of the ionic molecules adsorbed, which is another characteristic of the thin film. Therefore, the optical thin film for the present invention exhibits an effect of preventing deterioration of an organic film and electrode, which are sensitive to moisture or the like, and can be said to be a film of high resistance to ambient conditions. As such, it can play an important role for securing reliability of the device in which it is used.
[0022] As discussed above, the optical thin film can realize a light-emitting element and display, high in efficiency and reliability, and stably serviceable for extended periods.
[0023] The means for solving the problems include the followings:
[0024] The first means is a light-emitting element comprising:
a board; a first electrode; a second electrode; a light-emitting layer placed between the first electrode and second electrodes; and an optical thin film, wherein the optical thin film is composed of a dielectric material as a base material and has a pore, of which proportion based on the optical thin film is changing in a film thickness direction of the optical thin film. The first and second electrodes constitute a pair of electrodes holding the light-emitting layer in-between.
[0031] Another means is the above-described light-emitting element wherein the optical thin film has a refractive index distribution in the thickness direction, or wherein the pores have a size of a major axis changing in the thickness direction of the optical thin film and the size of the major axis increases towards a plane from which a light is emitted from the optical thin film. The “plane from which a light is emitted” (i.e., a light extraction plane) is the one from which a light radiated from the light-emitting layer is emitted to the outside, by which is meant that it is the uppermost surface of the light-emitting element in contact with air. The size of the major axis of the pore means nearly the longest diameter of the pore.
[0032] Still another means is the above-described light-emitting element wherein the pores have a major axis running in parallel to a plane from which a light is emitted from the optical thin film, and a length of the major axis increases in the thickness direction towards the plane.
[0033] Still another means is the above-described light-emitting element wherein the optical thin film has a surface resistivity of 10 10 to 10 11 Ω/cm 2 , inclusive.
[0034] Still another means is the above-described light-emitting element wherein the pores have a diameter of 5 to 700 nm, inclusive, and are structured to emit a light due to Mie scattering, which is generated when a light emitted from the light-emitting layer hits the pores, to an outside of the element.
[0035] Still another means is the above-described light-emitting element wherein a thickness of the optical thin film is half or less of a peak wavelength of visible light transmitted by the film.
[0036] Still another means is the above-described light-emitting element wherein the optical thin film is composed of plural films stacked in layers, each layer having a thickness of 10 to 700 nm, inclusive.
[0037] Still another means is the above-described light-emitting element which is composed of an organic material, e.g., an organic low-molecular-weight or high-molecular-weight material, and contains the optical thin film stacked towards a light extraction plane of the light-emitting layer, from which electroluminescence is emitted.
[0038] Still another means is the above-described light-emitting element wherein the first electrode or the second electrode is transparent electrode and is provided in contact with the optical thin film.
[0039] Still another means is the above-described light-emitting element, wherein a sealing plate, which is transparent in a visible wavelength region, is provided in contact with the transparent electrode.
[0040] Still another means is the above-described light-emitting element wherein the sealing plate is provided by laminating a single layer or multiple layers of the optical thin film.
[0041] Still another means is the above-described light-emitting element wherein the optical thin film is composed of a metal oxide of SiO 2 , Al 2 O 3 or TiO 2 , or a metal nitride of SiN or AlN as a base material.
[0042] Still another means is a light-emitting display device which uses the above-described light-emitting element with the above-described optical thin film(s) provided towards a plane from which a light is emitted.
[0043] Other objects, features and advantages of the invention will become apparent from the following description of the embodiments of the invention taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] FIG. 1 ( a ) outlines the cross-section of an optical thin film of low refractive index provided on a board for the present invention, and FIG. 1 ( b ) presents a schematic diagram of a scanning electron microgram showing the cross-sectional structure of the optical thin film of low refractive index for the present invention.
[0045] FIG. 2 shows the relationship between refractive index and thickness of the optical thin film of low refractive index for the present invention.
[0046] FIG. 3 ( a ) shows one example of the cross-section of the organic light-emitting device of the present invention, incorporated with the optical thin film, and traces of light emitted from a light-emitting point, and FIG. 3 ( b ) shows another example of the cross-section of the organic light-emitting device of the present invention, incorporated with the optical thin film, and traces of light emitted from a light-emitting point.
[0047] FIG. 4 shows the calculated relative luminance-current characteristics with light extraction efficiency as a parameter.
[0048] FIG. 5 shows the calculated relationship between relative operational current and light extraction efficiency.
[0049] FIG. 6 shows the calculated relationship between relative power consumption and light extraction efficiency.
[0050] FIG. 7 ( a ) is a cross-sectional view illustrating a top-emission type organic electroluminescence device free of optical thin film, to be compared with one embodiment of the present invention, and FIG. 7 ( b ) is a cross-sectional view illustrating a top-emission type organic electroluminescence device as one embodiment of the present invention, provided with an optical thin film.
[0051] FIG. 8 shows the effect of optical thin film on the luminance-current characteristics of a device as one embodiment of the present invention.
[0052] FIG. 9 shows the effect of optical thin film on the current efficiency-current density characteristics of a device as one embodiment of the present invention.
[0053] FIG. 10 shows the effect of optical thin film on the electroluminescent spectral pattern of a device as one embodiment of the present invention.
[0054] FIG. 11 shows the relative luminance-current characteristics of a device as one embodiment of the present invention with light extraction efficiency as a parameter, showing the effect of optical thin film.
[0055] FIG. 12 shows the relationship between relative operational current and light extraction efficiency of a device as one embodiment of the present invention.
[0056] FIG. 13 shows the relationship between relative power consumption and light extraction efficiency of a device as one embodiment of the present invention.
[0057] FIG. 14 is a cross-sectional view illustrating a top-emission type organic electroluminescence device as another embodiment of the present invention, provided with an optical thin film.
[0058] FIG. 15 is a cross-sectional view illustrating a bottom-emission type organic electroluminescence device as still another embodiment of the present invention, provided with an optical thin film.
[0059] FIG. 16 is a cross-sectional view illustrating a top-emission type organic electroluminescence R, G and B pixels as another embodiment of the present invention, provided with an optical thin film.
[0060] FIG. 17 is a cross-sectional view illustrating a top-emission type organic electroluminescence R, G and B pixels as another embodiment of the present invention, provided with an optical thin film.
[0061] FIG. 18 is a cross-sectional view illustrating a bottom-emission type organic electroluminescence R, G and B pixels as another embodiment of the present invention, provided with an optical thin film.
[0062] FIG. 19 illustrates a display incorporated with the device of the present invention.
[0063] FIG. 20 illustrates a liquid-crystal display incorporated with the organic luminescence device as one embodiment of the present invention for emitting white back light.
[0064] FIG. 21 illustrates a liquid-crystal display incorporated with the organic luminescence device as another embodiment of the present invention for emitting white back light.
DESCRIPTION OF REFERENCE NUMERALS
[0000]
1 , 4 , 54 : Transparent glass board
2 , 5 : Optical thin film of low refractive index, containing pores
3 : Nanometer-size pores
6 : transparent electrode
7 : Organic layer
8 , 18 , 28 : Glass board or board having a thin-film transistor and circuit
9 , 19 , 39 : Electrode of LiF/AlNd
10 : Organic electron transport layer
11 : Organic light-emitting layer
12 , 22 , 32 : Organic hole transport layer
13 , 23 , 31 : Organic hole injection layer
14 , 24 : Transparent electrode of indium zinc oxide
15 , 26 , 36 , 41 : Sealing glass plate
16 , 27 , 37 , 43 , 57 : Sealing agent
17 , 25 , 29 , 42 : Optical thin film
20 , 34 : Organic electron transport layer
21 , 33 : Organic light-emitting layer
30 , 44 : Transparent electrode of indium tin oxide
35 : Electrode of LiF/Al
38 : Board having a thin-film transistor and circuit
40 : Bank layer
45 : Panel screen
46 : circuit interconnection
47 : Drive power source
48 : Liquid-crystal display panel
49 A, 49 B: Polarizer plate
50 A, 50 B: Transparent board
51 : Liquid-crystal layer
52 : Sealing/fixing column
53 : Organic electroluminescence device panel of the present invention for emitting white light
55 : Organic electroluminescence layer for emitting white light
56 : Transparent sealing plate
DETAILED DESCRIPTION OF THE INVENTION
[0097] The specific embodiments for carrying out the present invention are described below.
EXAMPLE 1
[0098] EXAMPLE 1 is described by referring to FIGS. 7 ( a ) and ( b ). EXAMPLE 1 prepares an organic electroluminescence device of top-emission type, provided with the optical thin film 17 of low refractive index and containing pores (illustrated in FIG. 7 ( b )), to compare it with a common device free of porous optical thin film (illustrated in FIG. 7 ( a ).
[0099] Referring to FIGS. 7 ( a ) and ( b ), the organic electroluminescence device comprises the board 8 (glass board or board having a thin-film transistor and circuit), which supports patterns of the electrode 9 of LiF/AlNd, organic electron transport layer 10 , organic light-emitting layer 11 , organic hole transport layer 12 , organic hole injection layer 13 and transparent electrode 14 of indium zinc oxide, where all of the layers except the indium zinc oxide electrode are provided by deposition. The sealing plate of the optical thin film 17 formed on the sealing glass plate 15 is prepared, where the optical thin film is prepared from silica-dispersed sol, colloidal silica and alcohol as the starting materials, and contains nanometer-size pores. The optical thin film is designed to contain nanometer-size pores, equivalent to or shorter than visible wavelengths, and have a refractive index of 1.3 or less in a range from 1.09 to 1.3, inclusive. Thickness of the optical thin film is set at around λ/4, where λ is the central peak around the spectral peak of light emitted from the light-emitting layer. For the common organic electroluminescence device illustrated in FIG. 7 ( a ), the sealing glass plate 15 , free of optical thin film, is prepared and fixed by the sealing agent 16 . In the organic electroluminescence device illustrated in FIG. 7 ( b ), the sealing glass plate 15 of the optical thin film is fixed by the sealing agent 16 to contain the device in such a way to bring the optical thin film and transparent electrode 14 of indium zinc oxide (IZO) into contact with each other. The organic electroluminescence device of the present invention, illustrated in FIG. 7 ( b ), is prepared by incorporating the optical thin film containing nanometer-size pores. The effects of the optical thin film for the present invention can be clarified by comparing the characteristics of these devices prepared in the same manner for the organic layer and electrode, which were deposited simultaneously.
[0100] The structure of the organic electroluminescence device prepared in EXAMPLE 1, illustrated in FIG. 7 ( b ), provides the following improved characteristics and effects by virtue of the optical thin film incorporated therein. First, the optical thin film prepared in EXAMPLE 1 is designed to have a thickness of 150 nm or less, equivalent to or shorter than visible wavelengths, and refractive index in a range from 1.20 to 1.25 (refer to FIG. 2 ). The film has a reflectance of 3 to 4% (transmittance: 96 to 97%). On the other hand, the sealing glass plate has a reflectance of 8 to 9% (transmittance: 91 to 92%). The optical thin film can work as an antireflective film, because of its low refractive index, and has a 7% higher transmittance than the sealing glass plate. Moreover, the optical thin film can not only enlarge a transmittance intensity, but also generates Mie scattered light because of containing nanometer-size pores and can effectively work to emit part of scattered light to the outside. It is found that the optical thin film can effectively reduce device operational current and power consumption by the tests carried out for estimating light extraction efficiency of these devices. The test results are described below. FIG. 8 shows the relationship between luminance and current for each device. As shown, the device incorporated with the optical thin film containing nanometer-size pores produces a higher luminance than the device free of optical thin film, 33% higher luminance at a current level of 2 mA. It should be noted that these devices exhibit exactly the same current-voltage characteristics. It is therefore concluded, based on these results, that the device incorporated with the optical thin film has a higher light-emitting efficiency than the device free of optical thin film at the same current and voltage levels. FIG. 9 shows the relationship between current efficiency and current density. As shown, the device incorporated with the optical thin film has an at least 30% higher current efficiency over the current density range tested. FIG. 10 compares the spectral patterns of light emitted from these devices at the same current level, plotting emitted light intensity against wavelength. As shown, no peculiar effect of the optical thin film on the spectral pattern is observed as a whole, although the pattern of light emitted from the device incorporated with the optical thin film shits to the long wavelength side to some extent.
[0101] FIGS. 11 to 13 show the test results for dependence of light extraction efficiency on luminance-current characteristics, operational current and power consumption, and compare the calculated results shown in respective FIGS. 4 to 6 . Referring to FIG. 11 , the test results are first fitted for the device free of optical thin film at a base light extraction efficiency of 20%. Based on these results, relative light extraction efficiency is calculated for the device incorporated with the optical thin film from the luminance-current characteristics as a function of light extraction efficiency. The results shown in FIG. 11 indicate that the optical thin film improves light extraction efficiency of the organic electroluminescence device to 26%, which is an increase to 1.3 times. FIGS. 12 and 13 plot relative operational current and power consumption against light extraction efficiency at an device luminance of 1000 cd/cm 2 , to investigate the effects of the optical thin film for the tested devices. These results indicate that the optical thin film can reduce operational current by 25% and power consumption by 27% at the same luminance level. It is found that the results shown in FIGS. 11 to 13 are in good agreement with the calculated results, and that the effects of improved light extraction efficiency on reduction of required current and power consumption can be quantitatively estimated.
[0102] Moreover, the optical thin film prepared in EXAMPLE 1 is highly moisture-absorptive and efficiently absorbs moisture from the surface, and exhibits a function of gettering moisture in an atmosphere for sealing the organic electroluminescence device. Still more, it is highly antistatic because of its low surface resistivity of 10 10 to 10 11 Ω/cm 2 . A common insulating film has a high surface resistivity of 10 15 to 10 16 Ω/cm 2 . Therefore, charges of the ionic molecules which it absorbs tend to accumulate locally, and concentration of the ions which can be absorbed tends to be saturated in that region. By contrast, the optical thin film for the present invention is highly resistant to ambient conditions, as described above, and exhibits an effect of preventing deterioration of an organic film and electrode, which are sensitive to moisture or the like. As such, it can play an important role for securing reliability of the device in which it is used.
[0103] The optical thin film for the present invention may be of a single layer or laminate of 2 or more layers to adjust required properties, e.g., reflectance and moisture absorptivity, for specific purposes. Moreover, it may be formed on both sides of the sealing plate for the organic electroluminescence device to work as an antireflective film.
[0104] The top-emission type organic electroluminescence device of EXAMPLE 1 exhibits a higher current efficiency and around 30% higher light extraction efficiency for emitting light to the outside than the common device by virtue of the optical thin film, which draws scattered light out of light emitted by the light-emitting layer. EXAMPLE 1 also has demonstrated to what extent operational current and power consumption can be reduced, based on extent of improved light extraction efficiency.
EXAMPLE 2
[0105] EXAMPLE 2 describes another embodiment of the present invention by referring to FIG. 14 . EXAMPLE 2 also prepares an organic electroluminescence device of top-emission type, where the optical thin film containing nanometer-size pores is provided at a different position. More specifically, the organic electroluminescence device comprises, similar to that prepared in EXAMPLE 1, the board 18 (glass board or board having a thin-film transistor and circuit) which supports the electrode 19 of LiF/AlNd, organic electron transport layer 20 , organic light-emitting layer 21 , organic hole transport layer 22 , organic hole injection layer 23 and transparent electrode 24 of indium zinc oxide, where all of the layers except the indium zinc oxide electrode are provided by deposition. Then, the optical thin film 25 for the present invention, prepared from silica-dispersed sol, colloidal silica and alcohol as the starting materials, is provided on the transparent electrode of indium zinc oxide, where the optical thin film is designed to contain nanometer-size pores, equivalent to or shorter than visible wavelengths, and have a refractive index of 1.3 or less in a range from 1.09 to 1.3, inclusive. Thickness of the optical thin film is set at around λ/4, where λ is the central peak around the spectral peak of light emitted from the light-emitting layer. Then, the sealing glass plate 26 is fixed by the sealing agent 16 to contain the device in such a way to bring the sealing plate 26 and optical thin film into contact with each other.
[0106] The top-emission type organic electroluminescence device prepared in EXAMPLE 2 directly transmits light emitted from the light-emitting layer into the optical thin film to draw Mie scattering light upwards. This structure improves light extraction efficiency for emitting light to the outside from that of the device free of optical thin film, to an extent similar to that attained by the device prepared in EXAMPLE 1. The improved light extraction efficiency leads to reduced device operational current and power consumption.
EXAMPLE 3
[0107] EXAMPLE 3 describes still another embodiment of the present invention by referring to FIG. 15 . EXAMPLE 3 prepares an organic electroluminescence device of bottom-emission type, where the optical thin film 29 containing nanometer-size pores, prepared from silica-dispersed sol, colloidal silica and alcohol as the starting materials, is provided on the board 28 (glass board or board having a thin-film transistor and circuit). Then, the board 28 is coated with the transparent electrode 30 of indium tin oxide, organic hole injection layer 31 , organic hole transport layer 32 , organic light-emitting layer 33 , organic electron transport layer 34 and electrode 35 of LiF/AlNd. This structure is characterized by the optical thin film 29 coming into contact with the transparent electrode of indium tin oxide. Then, the sealing glass plate 36 is fixed by the sealing agent 37 to contain the device.
[0108] The bottom-emission type organic electroluminescence device prepared in EXAMPLE 3 directly transmits light emitted from the light-emitting layer into the optical thin film to draw Mie scattering light downwards. This structure improves light extraction efficiency for emitting light to the outside from that of the device free of optical thin film, to an extent at least equivalent to that attained by the device prepared in EXAMPLE 1. The improved light extraction efficiency leads to reduced device operational current and power consumption.
EXAMPLE 4
[0109] EXAMPLE 4 describes still another embodiment of the present invention by referring to FIGS. 16 to 18 . Referring to FIGS. 16 and 17 , R, G and B pixels are formed by top-emission type organic electroluminescence devices for a display. The electrode 39 of LiF/AlNd is provided for each of the R, G and B pixels on the board 38 having a thin-film transistor and circuit, and the bank layer 40 is provided to form each of the R, G and B pixels and separate them from each other. Then, an organic layer as the light-emitting layer, composed of a material selected to emit wavelengths for red, green or blue light, is provided by deposition in a manner similar to that for EXAMPLE 1 or 2, to form the R, G or B pixels, as illustrated. Then, the sealing plate of the optical thin film 42 formed on the sealing glass plate 41 is prepared in a manner similar to that for EXAMPLE 1, as illustrated in FIG. 16 , where the optical thin film is prepared from silica-dispersed sol, colloidal silica and alcohol as the starting materials, and contains nanometer-size pores. The sealing glass plate 41 on which the optical thin film 42 is formed is fixed by the sealing agent 43 to contain the device in such a way to bring the optical thin film and transparent electrode of indium zinc oxide into contact with each other. In FIG. 17 , the optical thin film 42 containing nanometer-size pores is provided on the transparent electrode of indium zinc oxide in a manner similar to that for EXAMPLE 2, and the sealing glass plate 41 is fixed by the sealing agent 43 to contain the device in such a way to bring the sealing glass plate 41 and optical thin film 42 into contact with each other.
[0110] FIG. 18 illustrates R, G and B pixels formed by bottom-emission type organic electroluminescence devices for a display. Referring to FIG. 18 , the optical thin film 42 containing nanometer-size pores, prepared from silica-dispersed sol, colloidal silica and alcohol as the starting materials, is provided on the board 38 having a thin-film transistor and circuit. Then, the board 38 is coated with the transparent electrode 44 of indium tin oxide, and the bank layer 40 is provided to form each of the R, G and B pixels and separate them from each other. Then, an organic layer as the light-emitting layer, composed of a material selected to emit wavelengths for red, green or blue light, is provided by deposition in a manner similar to that for EXAMPLE 3, to form each of the R, G or B pixels, as illustrated, and the sealing glass plate 41 is fixed by the sealing agent 43 to contain the device.
[0111] Each of the R, G and B pixels, composed of the top-emission type or bottom-emission type organic electroluminescence device directly transmits light emitted from the light-emitting layer into the optical thin film to draw Mie scattering light. This structure improves light extraction efficiency for emitting light to the outside from that of the device free of optical thin film, to an extent at least equivalent to that attained by the device prepared in EXAMPLE 1. The improved light extraction efficiency leads to reduced operational current and power consumption at each pixel, producing an effect of reducing power consumption of the display. Therefore, it can realize a display, high in efficiency and reliability, and stably serviceable for extended periods.
EXAMPLE 5
[0112] EXAMPLE 5 describes still another embodiment of the present invention by referring to FIG. 19 . The panel screen 45 is prepared using the organic electroluminescence device prepared in one of EXAMPLES 1 to 4 as the pixel for the display, where each pixel is driven by the drive power source 47 via the circuit interconnection 46 . Each of the R, G and B pixels improves light extraction efficiency from that of the device free of optical thin film. The improved light extraction efficiency leads to reduced operational current and power consumption at each pixel, producing an effect of reducing power consumption of the display. Therefore, it can realize a display, high in efficiency and reliability, and stably serviceable for extended periods.
EXAMPLE 6
[0113] EXAMPLE 6 describes still another embodiment of the present invention by referring to FIGS. 20 and 21 . EXAMPLE 6 applies the optical thin film for the present invention to the light-emitting layers which produce white light by mixing different light colors for an organic electroluminescence device. This makes the organic electroluminescence device emitting white light applicable to a back light for liquid-crystal displays.
[0114] Referring to FIG. 20 , EXAMPLE 6 prepares a display panel module comprising the panel 48 for a liquid-crystal display is put on the organic electroluminescence panel 53 emitting white light, where the optical thin film for the present invention is used in the panel 53 . The liquid-crystal display panel 48 comprises the liquid-crystal layer 51 set between the transparent boards 50 A and 50 B, which are coated with the respective polarizer plates 49 A and 49 B, in a space defined by the sealing/fixing column 52 . It controls transmission of light, when a voltage is applied to the liquid-crystal layer 51 . The organic electroluminescence panel 53 emitting white light, in which the optical thin film for the present invention is used, comprises the organic electroluminescence layer 55 , provided on the transparent glass board 54 , and transparent sealing plate 56 fixed by the sealing agent 57 . The organic electroluminescence panel 53 may be directly put on the liquid-crystal display panel 48 by the sealing agent 57 with the transparent sealing plate 56 removed, as illustrated in FIG. 21 . A thin-film transistor as the switch for applying an electric field to the liquid-crystal layer 51 and interconnections for voltage supply are not shown. It is needless to say that color display can be realized when a color filter is provided inside of the board.
[0115] The organic electroluminescence device of EXAMPLE 6 for emitting white light can be structured to illuminate the entire liquid-crystal display panel surface with white back light. It provides an unprecedentedly thin back light source and liquid-crystal display incorporated therewith. A liquid-crystal display panel of a conventional technique is illuminated with back light from a point light source of an inorganic diode emitting white light. However, it needs a space of certain distance between the white back light source module and liquid-crystal display panel to help radiate light from the point source. The organic electroluminescence panel of EXAMPLE 6 for emitting white light, capable of illuminating the entire surface, can be directly put on the liquid-crystal display panel, thus dispensing with the above-described space. An inorganic diode by a conventional technique for emitting white light uses wave-guided light, and needs a wave-guiding plate, reflective plate and optical sheet. As a result, the back light source becomes 1.0 to 2.0 mm thick. By contrast, the organic electroluminescence panel 53 can have a thickness reduced to 0.6 to 0.9 mm ( FIG. 20 ), or to 0.3 to 0.6 mm ( FIG. 21 ).
[0116] When used for emitting back light for liquid-crystal displays, the organic electroluminescence device of EXAMPLE 6 for emitting white light can reduce power requirement from that consumed by a conventional inorganic diode. Moreover, the electroluminescence device, incorporated with the optical thin film for the present invention, improves light extraction efficiency and can enhance light output for illuminating the entire surface at a lower current than that of a device free of optical thin film. Therefore, it realizes device characteristics of improved light-emitting efficiency and current efficiency. It can reduce operational current and power consumption at the organic electroluminescence device for emitting white light, and consequently reduce power consumption at the back light source. As such, it can reduce total power consumption at the device in which it is incorporated, e.g., cellular phone, information terminal or digital video camera. Therefore, it can realize a display, serviceable for extended periods stably and reliably.
INDUSTRIAL APPLICABILITY
[0117] The present invention is applicable to an organic electroluminescence device and illuminator of high efficiency and low power consumption, light source, e.g., diode emitting white light and back light device for liquid crystals, and display of high reliability and wide viewing angle.
ADVANTAGES OF THE INVENTION
[0118] The device of the present invention is incorporated with an optical thin film of low refractive index and containing nanometer-size pores. It is found that it can realize a higher light extraction efficiency than a conventional device, because the optical thin film scatters part of light it receives from a light-emitting layer by Mie scattering upwards and then to the outside, where Mie scattering occurs in its pores having a size equivalent to wavelengths of light which they transmit. The optical thin film is confirmed to improve light extraction efficiency by around 30%, thereby reducing required operational current and power consumption by 25 and 27%, respectively. Moreover, the optical thin film of low refractive index for the present invention is optically stable, stably realizes the above-described optical characteristics, and hence exhibits an effect of efficiently improving electrical characteristics. Still more, the optical thin film applied to the present invention is highly moisture-absorptive, antistatic to prevent local accumulation of charges, and hence resistant to ambient conditions. As such, it can exhibit a function of preventing deterioration of an organic film and electrode as the device components, and hence contribute to improved device reliability.
[0119] The optical thin film for the present invention may be of a single layer or laminate of 2 or more layers, as illustrated in FIG. 3 , to adjust required properties, e.g., reflectance and moisture absorptivity, for specific purposes. Moreover, it may be formed on both sides of the sealing plate for an organic electroluminescence device to work as an antireflective film.
[0120] The optical thin film for the present invention is also effective, when applied to an organic luminescence device emitting white light, and also to a blue-emitting layer incorporated with a layer for emitting yellowish brown color and to a layer emitting blue, green and red colors as the three primary colors.
[0121] The embodiments of the present invention describe the optical thin film prepared from silica (SiO 2 ) as one of the starting materials. However, other oxides or nitrides may be used so long as they are dielectric and insulating. The dielectric materials useful for the present invention include metal oxides represented by Al 2 O 3 and TiO 2 , and metal nitrides represented by SiN and AlN.
[0122] It should be further understood by those skilled in the art that although the foregoing description has been made on embodiments of the invention, the invention is not limited thereto and various changes and modifications may be made without departing from the spirit of the invention and the scope of the appended claims.
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Conventional light-emitting elements, in particular an organic electroluminescence devices, involve problems resulting from a low light extraction efficiency of 20% or less, because of limitations on light emission set by total reflection angle on an organic layer or transparent electrode as the component, and are demanded to have improved luminance and other optical characteristics which depend on viewing angle. The present invention provides an organic electroluminescence device which can improve a light extraction efficiency and thereby reduce operational current and power consumption by incorporating a laminate of optical thin films of low refractive index and having pores whose size is controlled at a level equivalent to or shorter than visible wavelengths, because the light components totally reflected to become wave-guided or reflected light in a common device can be extracted as light scattered by the pores.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is in the field of pile driving and pulling. More particularly, the invention relates to a method, system and apparatus for driving and pulling pilings utilizing intense vibrations. The method, system and apparatus allows the operator to drive pilings using a linear hydraulic vibrator supplied with hydraulic fluid at high pressure from a high pressure, large volume, hydraulic pump through suitable hydraulic hoses. The pile driving system may be "tuned" to take into consideration soil conditions and site requirements to obtain a high degree of driving efficiency, utilizing vibration sensing pickup units on the ground and/or on the pile driving system apparatus to feed information of driving frequency and driving rate to an electronic control unit which controls the vibration frequency of the pile driving apparatus.
2. Description of the Prior Art
The use of machines for driving elements into the ground has widespread applications in the formation of foundations for structures of all types, the elements which can be driven into the ground may vary in shape depending upon the particular purpose.
Pile driving has traditionally been done using hammers powered by steam, compressed air, or hydraulic power and more recently methods using vibrations have been employed. It has been found that when a pile is subjected to intense linear vibrations along the axis of the pile, and when the weight of the vibratory pile driver apparatus is added to the weight of the pile, (usually a steel pile), and where the soil conditions are suitable for this method of pile driving, the rate of penetration is most frequently found to be considerably faster than would be obtained using hammer methods and apparatus.
The conventional rotary vibratory pile driver has a heavy housing provided with at least two shafts which carry eccentric weights. Typically, slugs of heavy metal are set, off-center, into gears. Other eccentric mass rotors are also used. The weight of the eccentric masses are typically measured in tens or hundreds of pounds as compared to the weight of the mass of the remaining frame and support system of rotary vibratory drivers being measured thousands of pounds. Thus there is an inherent disfavor against the reaction mass, i.e., the eccentric rotor weights, which may be as high as about 1 to 10. I.e., the ratio of the weight of the reaction mass to the mass being vibrated should preferably be greater than one.
The shafts of the rotary vibrator are rotated at high speed, typically 1200 rpm (20 Hz), thereby vibrating the housing assembly which is clamped to the pile to be driven or set. This vibration, combined with the weight of the driver, causes the pile to sink into the ground or conversely pulled out of the ground when tension is applied by use of a crane or like machine. Typically, the housing is suspended from the cable of a crane by means of an elastomeric vibration damper so that the vibration is transferred to the pile and not back up the cable to the crane. These known vibratory drivers cannot be used to both hammer and vibrate.
The rotary vibratory type of pile drivers have the disadvantages of generating the linear vibrations to the pile by using heavy eccentric weighted masses which must be rotated synchronously using a substantial amount of energy to do so. There are inherent inefficiencies related to the conversion of the rotational energy to linear vibratory energy. To vary the frequency of the linear vibrations, the synchronous rotary speed of the eccentric masses must be altered at a substantial energy cost and because of the size of the masses being driven into sychronous rotation, there is substantial inertia to overcome when either increasing the frequency or decreasing the frequency. The rotary units need to be "run up" through a range of frequencies to arrive at the desired frequency. When they "run up" as they are put into use, they may run thru frequencies which could momentarily damage sensitive nearby structures. These pile drivers also have an ideal speed of rotation and consequently an ideal frequency of vibration. Lower frequency requires less hydraulic fluid to the hydraulic motors driving the eccentric rotors. With the lowering of frequency and less hydraulic fluid there is produced a corresponding lower energy output. Increasing the frequency results in an increased flow of hydraulic fluid from the power supply and an increased risk of gear and bearing wear or burn-out.
The following is a brief description and discussion of patents defining the most closely related inventions.
U.S. Pat. No. 5,088,565, "Vibratory Pile Driver" to Evarts, Kingsley S., Issued Feb. 18, 1992 discloses a vibratory pile driver having a clamping means for clamping onto a pile, hydraulic gear motor having two oppositely rotatable shafts and a pair of semicurcular weights aligned in the same vertical plane and each is secured to a shaft parallel to the motor shafts. There are drive and driven pulleys, sprockets or the like connected by toothed timing belts, chains or the like for driving the weights synchronously.
U.S. Pat. No. 4,625,811, "Hydraulic Vibratory Pile Driver" to Tuenkers, Josef-Gerhard, Issued Dec. 2, 1986 discloses a vibratory pile driver with a rigid housing, a pair of parallel and horizontally spaced shafts journaled for rotation wholly independently of each other about respective parallel and horizontally spaced axes in the housing, respective generally equally massive and eccentrically mounted weights on the shafts, respective hydraulic drive motors on the housing connected to the shafts for oppositely rotating the shafts and the weights.
U.S. Pat. No. 4,819,740, "Vibratory Hammer/Extractor" to Warrington, Don C., Issued Apr. 11, 1989 discloses a vibratory hammer/extractor for use with elongated pilings and the like. The vibratory exciter includes, among other elements, one pair of eccentric weights mounted on shafts for rotation about an axis transversely of the clamped piling for imparting vibratory forces to the piling as the eccentrics are driven in rotation.
Clearly, none of these Patents disclose the invention taught and claimed herein.
Applicant has some familiarity with seismic vibrators which operate without the use of rotary eccentric masses. The seismic vibrators are useful for imparting vibration energy into the earth but have no use in the field of construction and particularly in the field of driving and extracting pilings.
It would be desirable to have a vibratory pile driver apparatus, system and method for driving pilings which overcomes many of the deficiencies and disadvantages of the prior art pile drivers. The present invention disclosed and claimed herein has the particular objectives, features and advantages of: 1) a low height, which is advantageous for application under bridges and in buildings; 2) producing a linear vibration without the need to convert from rotary motion to linear motion; 3) compatibility with a wide range of power units, from about 50 to 300 gpm; 4) providing a constant level of energy over a wide range of frequencies; 5) capable of rapid and simple control of a wide range of frequencies; 6) may be started at a set frequency, particularly advantageous where sensitive nearby structures can be damaged by certain frequencies; 7) may be used for jarring or hammering up or down while vibrating; and 8) having a reaction mass to vibratory load ratio substantially greater than one (1), i.e., having the reaction mass being substantially heavier than the vibratory load rather than ratio of reaction mass to vibratory load ratio being substantially less than one (1), i.e., the vibratory load being substantially heavier than the reaction mass.
SUMMARY OF THE INVENTION
Basically the present invention in its most simple form or embodiment is directed to a linear vibratory pile driver apparatus and the method for using the apparatus to drive or to pull pilings. The apparatus is comprised of a lifting shaft isolated from but slideably mounted within a piston assembly which is attached to a frame assembly, a cylinder assembly attached to a reaction mass, the piston assembly is vibratorily positioned within the cylinder assembly and vibratorily driven by hydraulic fluid at a selectable frequency thereby vibrating the piston/frame assembly (the piston assembly and the attached frame assembly) relative to the cylinder/reaction mass assembly (the cylinder assembly and the attached reaction mass). A clamp device is attachable to a clamp-end of the frame assembly and the lifting shaft is attachable to a cable of a lifting apparatus such as a crane. Collectively, the piston/frame assembly and the cylinder/reaction mass assembly may be referred to as the vibratory assembly.
The frequency of the vibration and the power of the vibration, which power is related to the stroke length of the piston, i.e., the vibration amplitude, may be varied independently. By positioning the piston toward either the clamp-end or the cable end, and by adjusting the power, i.e., the stroke length, the linear vibratory pile driver may function as a hammer and a vibrator concurrently. Lowering the frequency of the vibrations and with the position of the piston toward one end or the other will result in the apparatus functioning as a hammer for either driving or pulling a pile.
It is a primary object of the present invention to provide a linear vibratory pile driver apparatus to drive and to pull pilings comprising: a lifting shaft vibration isolated from, but slideably mounted within, a piston assembly. The piston assembly is attached to a frame assembly and the frame assembly restricts sliding movement of the lifting shaft within the piston assembly. A means for vibration isolating (a vibration isolator) the lifting shaft from the piston assembly is positioned within the inside cavity of the piston assembly. The vibration isolator acts to dampen or isolate the vibration of the piston and frame assembly from the lifting shaft and further limits sliding movement of the lifting shaft within the piston inside cavity. A cylinder assembly is attached to a reaction mass and the piston assembly is vibratorily positioned within the cylinder assembly. There is also a means for vibratorily driving the piston assembly by hydraulic fluid at a selectable frequency thereby vibrating the piston assembly and the attached frame assembly, i.e., the piston/frame assembly relative to the cylinder assembly attached to the reaction mass assembly, i.e., the cylinder/mass assembly.
It is another primary object of the present invention to provide a linear vibratory pile driver apparatus to drive and to pull pilings comprising: means for vibration isolating the cable from vibration of the pile driver. The means for isolating also limits movement of the lifting shaft relative to a vibratory assembly. The vibratory assembly comprises: a piston assembled and positioned concentrically around and in sliding association with the lifting shaft; a piston ring member extending radially from an outer surface of the piston; a frame assembly rigidly affixed to the piston. The frame assembly has a cable-end member, a clamp-end member and at least one connecting member connecting the cable-end member and the clamp-end member of the frame assembly. The frame cable-end member and the clamp-end member each cooperate with the means for isolating the cable and each are configured to limit sliding movement of the lifting shaft. The clamp-end attaches to the means for clamping (jaws). Further there is a reaction mass which has a cylinder wall member configured and assembled concentrically around and in sliding association with the piston. The cylinder wall member to define, in combination with the piston and the piston ring member a cylinder head cavity with two portions, a cylinder head cable-end cavity and a cylinder head clamp-end cavity. The linear vibratory pile driver further comprising: means for providing fluid into the cylinder head cavity; and means for relative pressurizing at a determined and controlled frequency, each the cylinder head cable-end cavity and the cylinder head clamp-end cavity relative each to the other.
It is another primary object of the present invention to provide the linear vibratory pile driver apparatus as above where there may also be provided combination of the additional elements such as 1) a plurality of means for fluid-tight sealing of the fluid within the cylinder head cavity between the sliding association of the cylinder wall member and the piston; 2) a plurality of cylinder wall member bearing devices to make substantially frictionless the sliding association of the cylinder wall member and the piston; 3) a plurality of lifting shaft bearing devices to make substantially frictionless the sliding association of the piston with the lifting shaft; 4) means for indicating a position of the valve spool member within the spool valve; 5) means for determining location of the reaction mass relative to the frame assembly; 6) means for controllably varying the determined and controlled frequency of the relative pressurizing; and 7) means for controlling a magnitude of pressure of the fluid into the cylinder head cavity.
It is yet another primary object of the present invention to provide the linear vibratory pile driver apparatus as above wherein the piston ring member extends radially from an outer surface of the piston and may be substantially at an axial mid-point of the piston and wherein the means for isolating is a form of spring or springs such as dished washers, compression springs and elastomers. The means for providing fluid into the cylinder head cavity comprises: 1) at least one cable-end fluid port in fluid flow communication with the cylinder head cable-end cavity and in fluid flow communication with at least one first fluid channel; 2) at least one clamp-end fluid port in fluid flow communication with the cylinder head clamp-end cavity and in fluid flow communication with at least one second fluid channel. The means for relative pressurizing at a determined and controlled frequency, both the cylinder head cable-end cavity and the cylinder head clamp-end cavity relative each to the other comprises preferably a spool valve having a valve spool member and a spool controller; 3) a manifold block positioned adjacent to the spool valve to provide the proper porting configuration between each of the first fluid channels and each of the second fluid channel; 4) at least one bumper pad fixedly attached to the frame clamp-end member; 5) at least one bumper pad fixedly attached to the frame cable-end member for protecting the frame assembly from said reaction mass; and 6) a bumper cushion disposed between the lifting shaft clamp end and the frame clamp-end member.
It is still another primary object of the present invention to provide a method of driving a pile using the linear vibratory pile driver as above described. The method comprises the steps of: attaching and suspending, at a cable-end, the linear vibratory pile driver to a cable of a crane; clamping a pile between gripper jaws at a clamp-end of the pile driver; placing the pile where it is to be driven; providing means for isolating the cable from vibration of the pile driver; imparting linear vibration to the pile, at the clamp-end by means of a vibratory assembly. The vibratory assembly comprises: a piston portion positioned concentrically around and in sliding association with a means for attaching and suspending the pile driver, the piston portion having a piston ring member; a frame rigidly affixed to the piston, the frame having a cable-end member, a clamp-end member and at least one connecting member connecting the cable-end member and the clamp-end member. The cable-end member and the clamp-end member each cooperate with the means for isolating the cable and each configured to limit sliding movement of the means for attaching and suspending. The clamp-end is attachable to the means for clamping. A reaction mass is positioned concentrically around and in sliding association with the piston portion and the reaction mass has a cylinder wall member configured to define, in combination with the piston ring a cylinder cavity having a cylinder cable-end cavity and a cylinder clamp-end cavity. Each of the cable-end cavity and clamp-end cavity are in fluid flow communication with a source of pressurized fluid and a means for cyclically providing each of the cylinder cable-end cavity and cylinder clamp-end cavity with pressurized fluid. The pressurized fluid is provided into the cylinder head cavity. Each of the cavities is cyclically pressurized relative to each other at a predetermined frequency. The frequency of relative pressurizing is controllable frequency. The magnitude of relative pressure is also controllable independent of the controlled frequency and without effecting the controlled frequency.
It is a further primary object of the present invention to provide the method of driving and pulling pilings as above wherein the following additional steps may be provided: 1) implanting at least one transducer in the ground; and 2) controlling the frequency of the vibration of the pile by integrating, in an electronic control unit, the output from each of the transducers implanted in the ground and the output from each of the transducers attached to the pile driver.
These and further objects of the present invention will become apparent to those skilled in the art after a study of the present disclosure of the invention and with reference to the accompanying drawings which are a part hereof, wherein like numerals refer to like parts throughout, and in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front partial section view showing concentric relationship of piston, isolator, cylinder, cylinder cavity, piston rings, seals and bearings;
FIG. 2 is a partial left side view of the device of FIG. 1 showing reaction mass position indicator attachment in cross section along with mass/frame slide alignment bearing;
FIG. 3 is a top partial view showing some of the bolt patterns needed for assembly of the pile driver, the cable-end frame member is not shown so as to improve clarity;
FIG. 4 is a top section view of an alternate embodiment using rods as the frame connecting members but having the same concentric relationship between elements;
FIG. 5 is a schematic sketch of the spool valve and valve spool member along with the spool valve position sensor and the control box; and
FIG. 6 is a sketch representing the linear vibratory pile driver in use attached to a cable of a crane, a pile attached to the driver and a hydraulic power unit along with vibration sensors and control of the driver based upon input from the sensors.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The construction and the design of the linear vibratory pile driver 10 will be described with reference to FIGS. 1-6 collectively. Clearly, it is obvious that many sizes, power capabilities and forms and varieties of geometric configurations of the various basic parts of the pile driver such as the shape of the reaction mass, the shape of the frame assembly (the frame connecting members could be rods instead of plates of material) and the surface geometry may be used. However, the basic structure of the apparatus and the basic method of using the apparatus remains the same and the objectives and the advantages are clearly, lower cost, lower maintenance, more effective and efficient, constant vibratory power at different frequencies, an advantageous greater than one ratio of reaction mass to frame mass and no rotory eccentric rotors.
Linear Vibratory Pile Driver Apparatus
The linear vibratory pile driver 10 is comprised of two fundamental and basic assemblies--a lifting assembly, and a vibrator assembly. The two ends of driver 10 are designated as the cable-end and the clamp-end. The driver cable-end is the end of the driver attachable to the cable 3 of a crane 2. The driver clamp-end is the end of the driver attachable to a piling 9 to be driven or pulled. Cylinder/reaction mass assembly 50, during operation, is stable relative to piston/frame assembly 40 and consequently pile 9, if attached by jaws 23a, is caused to vibrate.
Generally, for linear vibratory pile driver 10, lifting shaft 12 is within piston 16, piston ring portion 16c is within cylinder member 17 (preferably a machined sleeve 17 which inner wall 17c cooperates with piston rings 16d to create a seal) which is within a reaction mass central portion 25c. Frame 20 is connected to piston 16 at both the cable end and the clamp end. Cylinder 17 is positioned within or connected to reaction mass central portion 25c. Toward the cable end and around piston 16 is piston/cylinder cable-end bearing 18a and toward the clamp end and around piston 16 is piston/cylinder clamp-end beating 18b Piston/reaction mass bearing and seal retainers 18 keeps bearings 18a and 18b positioned within mass 25 and against cylinder sleeve 17 thereby keeping cylinder 17 positioned within mass 25 at both the cable end and the clamp end. Reaction mass first side member 25a and second side member 25b lie within frame 20. Located on and within reaction mass first side member 25a is means 29 for relative pressurizing at a determined and controlled frequency including means for providing fluid to each cylinder cable-end cavity 17a and cylinder clamp-end cavity 17b relative each to the other. I.e., the fluid under pressure is frequency controllably alternated between cable-end fluid conduit 17d to cable-end port 17c' and clamp-end fluid conduit 17e to clamp-end port 17c", i.e., the means for providing fluid to each cylinder. Means 29 is preferably a spool valve 29a and a manifold block 29b, and is attachable to reaction mass 25.
The lifting assembly is made up of a lifting shaft 12 having a lifting shaft cable-end 12a, a lifting shaft middle portion and a lifting shaft clamp-end 12b. Lifting shaft clamp-end 12b is configured with a flange portion below which may be a cushion pad 13c and on the flange surface rests a clamp-end of vibration isolator 14. Vibration isolator 14 also limits the movement of lifting shaft 12 within a piston inner cavity defined by piston inner wall 16a because the cable-end of isolator 14 is retained by isolator and lifting shaft cable-end bearing retainer 13 which is attached to frame cable-end member 21. Isolator 14 is further held in place by a cable-end frame member 21 and a clamp-end frame member 23 in addition to piston inner wall 16a. Vibration isolator 14, which may be dished washers, compression springs an elastomer material, gas springs or any other material suitable for the purpose of vibration isolating. There is a lifting shaft cable-end bearing or bushing 13a and a lifting shaft clamp-end bushing 13b. These beating or bushings permit the smooth movement of lifting shaft 12 relative to clamp-end of piston 16 and a lifting shaft cable-end bearing retainer and isolator retainer 13.
Vibrator assembly is comprised of piston 16 attached to a frame assembly 20, and a cylinder assembly or member 17 which cylinder member 17 is attached to or held within reaction mass 25. The piston/frame assembly 40 is in slideable relation with cylinder/reaction mass assembly 50. Lifting shaft 10 of the lifting assembly is contained substantially within piston 16 and in slideable relation with piston 16. There is also means for vibratorily driving piston/frame assembly 40, by hydraulic fluid, at a selectable frequency thereby vibrating piston/frame assembly 40 relative to cylinder/reaction mass assembly 50. Such mean for vibratorily driving includes piston ring portion 16c, rings 16d, cylinder cavities 17a and 17b, fluid ports 17c' and 17c", conduits 17d and 17e and means 29 for relative pressurizing at a determined and controlled frequency.
Lifting Assembly
In the present and preferred embodiment of the invention, lifting assembly comprises a lifting shaft 12 which is preferably in the form of a rod. Lifting shaft 12 has a cable-end portion 12a, a middle portion, and a clamp-end portion 12b. Clamp-end portion 12b has a diameter which is less than the inside diameter of piston 16 preferably by an amount which permits use of lifting shaft clamp-end bearing 13c. The lifting shaft middle portion and cable-end portion have a diameter around which will fit isolator 14 and isolator 14 has an outer diameter which fits inside the inner cavity of piston 16. Cable-end portion 12a may be fitted with a bale which connects to a lifting cable 3 of a crane 2. Lifting shaft 12 is fitted within the inner cavity of piston 16 on top of a cushion pad 13c. Cushion pad 13c rests on or is attached to a clamp-end frame member 23. On the lifting shaft clamp-end portion 12b there is a flange 12c. On a surface of flange 12c opposed from the surface on which lifting shaft 12 rests on cushion pad 13c there rests concentrically configured vibration isolator 14 which isolator 14 is sufficiently long to reach the lifting shaft cable-end portion 12a. A lifting shaft retainer 13 is attached to cable-end frame member 21. Lifting shaft retainer 13 also limits the movement or excursion of lifting shaft 12 relative to frame 20. Preferably, a cable-end and a clamp-end bearing or bushing 13a and 13b respectively is provided to reduce sliding friction between lifting shaft cable-end portion 12a and frame 20 and between clamp-end portion 12b and piston inner wall 16a defining the lifting shaft/isolator cavity i.e., the inner cavity of piston 16.
Vibration isolator 14 in the preferred embodiment as shown, utilizes dished spring washers which start to flatten out when strain is put on lifting cable 3 from crane 2 thus acting as a spring to lessen the amplitude of vibration going from pile driver apparatus 10 up cable 3 to crane 2. To give isolator 14 a broader spring range, some of the disc springs may be thicker than others, the thinner ones flattening out first and the thicker ones taking over as more strain is exerted by hoisting cable 3. The spring members instead of dished spring washers may be made from an elastomer such as synthetic rubber or polyurethane as a yet different embodiment, the spring member may be a gas spring or any other suitable form of compression spring.
Vibrator Assembly
Piston Assembly
Piston 16 of piston assembly is preferably a thick walled tube. Within the inner cavity of piston 16 is located lifting shaft 12, the bushings 13a and 13b and cushion pad 13c along with isolator 14. In the present preferred embodiment there is a piston ring portion 16c about centrally located between the cable-end and the clamp-end of the piston 16 and which extends radially outward from the outer wall 16b of piston 16. At least one means for sealing but preferably a plurality of piston rings 16d are attachable to piston ting portion 16c. Piston 16 is attached to frame assembly 20 at cable-end frame member 21 and at clamp-end frame member 23. Piston ting portion 16c also defines a piston ting cable-end cavity wall 16c' and a piston ring clamp-end cavity wall 16c". These cavity walls 16c' and 16c" define, along with other defining walls, cylinder head cable-end cavity 17a and cylinder head clamp-end cavity 17b.
Cylinder Assembly
The cylinder assembly comprises a cylinder 17 having an inner cylinder wall 17c. Cylinder 17 is attached to and concentrically located inside reaction mass 25, particularly inside of reaction mass center portion 25c and the piston assembly is vibratorily positioned within cylinder assembly 17. Cylinder inner wall 17c cooperates with piston outer wall 16b, piston ring portion 16c and the surfaces or walls of the piston ring portion, cable-end cavity wall 16c' and 16c" and one end of piston/reaction mass cable-end beating 18a and one end of piston/reaction mass clamp-end bearing 18b to define respectively cylinder cable-end cavity 17a and cylinder clamp-end cavity 17b. Cable-end fluid port 17c' and clamp-end fluid port each respectively admit fluid into cavity 17a and 17b which fluid is provided via a cable-end fluid conduit 17d and a clamp-end fluid conduit 17e the fluid conduit being within reaction mass 25 and particularly reaction mass first side member 25a. The cylinder attached to the reaction mass forms cylinder/reaction mass assembly 50.
Piston/reaction mass cable-end seal 18a', and piston/reaction mass clamp-end seal 18b' provide a means for sealing cavities 17a and 17b preventing the loss of pressurized fluid from these cavities when the apparatus 10 is operating. Each of the bearings and seals 18a, 18a' and 18b, 18b' are held in place by retainer 18 which is attachable to cylinder/reaction mass assembly 50.
Frame Assembly
Frame 20 is attached to piston 16 at both the cable-end and the clamp-end. Frame cable-end member 21 attaches to the cable end of piston 16 and frame clamp-end member 23 attaches to the clamp-end of piston 16. Between frame members 21 and 23 is frame connecting member 22. In the embodiment illustrated in FIGS. 1-3 connecting member 22 is shown in the form of a plate. There are four (4) such plates connecting frame members 21 and 23. Between the plates is reaction mass 25. On a first side of apparatus 10 is reaction mass first side member 25a which lies between two (2) of the plates 22. On a second side of apparatus 10 is reaction mass second side member 25b which lies between two (2) of the plates 22. Alignment bearing 19, shown in FIG. 3, may be provided to keep aligned the parts of means 27 for indicating reaction mass location since means 27 connects between reaction mass second side member 25b and frame cable-end member 21. This bearing 19 keeps the reaction mass 25 aligned between frame connecting member plates 22 or rods 22a particularly so that a means 27, when used, will remain properly aligned and functioning.
The frame connecting members may have other forms such as rods 22a as illustrated in FIG. 4. Preferably at least four frame connecting member rods 22a would be used. Alignment of reaction mass 25 relative to frame 20 would be maintained using similar type bearings as bearings 19.
Linear Vibratory Pile Driver System and Method of Use
Hydraulic power is supplied to the pile driver by hydraulic power unit 6 by way of hydraulic power supply and return lines 6a. Hydraulic power supply and return lines 6a are connected to manifold block 29c which is positioned relative to servo valve/spool valve 29a to provide the proper configuration for alternating/switching the relative pressure between the input hydraulic fluid conduits 17d and 17e formed in reaction mass 25.
The servo valve/spool valve 29a cyclically alternates the application of hydraulic pressure to cylinder cable-end cavity 17a causing movement of piston/frame assembly 40 downward toward clamp-end and then the application of hydraulic pressure to cylinder cable-end cavity 17b causing movement of piston/frame assembly 40 upward toward cable-end, thus causing piston/frame assembly 40 to vibrate relative to cylinder/reaction mass assembly 50. The rate of the cyclic application of hydraulic pressure is preferably controlled by controlling servo valve 29a through signals transmitted from operator control 30 by a control cable attached to servo valve 29a. Preferably, the hydraulic fluid passes to cable-end and clamp-end cavities 17a and 17b respectively through cable-end fluid conduit 17d and clamp-end fluid conduit 17e formed in the reaction mass 25.
It is important to note that the relative difference of the hydraulic fluid pressure within cavities 17a and 17b is substantially independent of the frequency of the vibration. Thus power and frequency are controllable independent of each other.
FIG. 6 illustrates pile driver 10 connected to a crane 2 by hoisting cable 3. As discussed above, hoisting cable 3 is attachable to the lifting bale which is attachable to lifting shaft 12. The hydraulic power unit 6 is connected to pile driver 10 by hydraulic power supply and return lines 6a. Means for operator control 30 (control box 30) of driver 10 is shown to include as inputs, a vibration sensing transducer 7 affixed to pile driver 10 and a vibration sensing transducer 8 implanted in ground 5. Control cables communicate the control signal from control box 30 to means 29 for frequency controlling the vibration of driver 10.
To drive a pile using the present invention, the following steps may be followed. Pile 9 should be gripped between the gripper jaws 23a. Highly pressurized hydraulic fluid from a hydraulic power supply 6 should be supplied from hydraulic power unit 6 through hydraulic power supply and return lines 6a to servo valve 29a. Pile 9 should be placed in the location where it is to be driven. Pile 9 should then be vibrated using linear vibratory pile driver apparatus 10 at a predetermined and selected frequency and power.
The method of the present invention may also include the step of adjusting the frequency of vibration by adjusting the frequency control of servo valve 29a using control means 30. Further, the method may also include attaching at least one vibration sensing transducer 7 to pile driver 10 and monitoring the frequency of the vibration. Additionally, the method may include implanting at least one vibration sensing transducer 8 in ground 5 and monitoring the frequency of the vibrations transmitted through the ground. Or transducer 8 may be place on nearby structures for the purpose of monitoring the vibrations transmitted in the ground by the pile driving process. The sensing of these vibrations is essential to the ability of the operator to "tune out" those frequencies which may resonate the surrounding ground in a harmful way without impeding the progress of the pile driving operation.
Preferably, when vibration sensing transducers 7 and 8 are employed, the vibration rate of pile driver apparatus 10 and consequently the vibration of pile 9 may be automatically controlled by using the output of transducers and using or integrating this output to determine optimum frequency and power.
Vibration sensing transducers 7 and 8 may be accelerometers. The frequency of vibration and the progression of the pile may be both monitored and controlled by control means/box 30.
Control device 30 is employed so that the operator may start, stop and control the vibration frequency of pile driver apparatus 10 at will. Also, control box 30 may be programmed to seek the ideal vibration frequency for the apparatus to run at, depending on the soil and site conditions. The optimal driving frequency may be employed and undesireable frequencies may be excluded.
Within certain constraints, unit 6 is a "constant" power vibratory pile driving power source. I.e. at a given power unit pressure, where the frequency of vibration is lowered as controlled by electronic control unit 30, the amplitude (distance traveled by each stroke of the vibration) increases. When the frequency is raised, the amplitude of each vibration decreases. The main constraint being the ability of a servo valve to deliver hydraulic fluid efficiently as the commanded frequency is increased. Most large size servo valves start to lose fluid delivery efficiency around 100 Hz. Obviously, the other constraint is the ability of the hydraulic power unit and hoses and drilled passages such as those in the manifold block and the passages drilled in the reaction mass, to supply hydraulic fluid with a minimum of pressure drop.
Thus, to drive a pile using the present invention the following steps are to be followed:
1. The hydraulic power unit 6 is started and high pressure hydraulic fluid is supplied thru the delivery hose 6a to servo valve 29a thru manifold block 29c.
2. Pile 9 is placed between pile gripper jaws 23a and the gripper jaw piston (not shown). The clamping assembly is pressurized by controls and hoses (not shown), to clamp the pile in place in line with the axis of the linear vibratory pile driver 10.
3. Pile 9 with pile driver apparatus 10 is lowered by crane 2 to the point where the weight of the pile driver and the pile are bearing on the ground (the pile and pile driver may be guided by the use of "leads" which attached to can hold in proper position guide the pile driver and pile to the specific place where the pile is to be driven,) or the pile may be locked into engagement with a previously driven pile as is the practice when driving "sheet" pilings which are used for building either permanent or temporary retaining walls. Sometimes piles are "started" by carefully positioning the pile and driver at the spot where the pile is to be driven and skillfully lowered as the vibratory is turned on and lowered slowly until the pile has penetrated the ground sufficiently enough so that it will stand on its own, then the crane may slack the hoisting cable and allow the full weight of the pile driver to bear on the top of the pile, this facilitating the driving of the pile as the vibratory is turned up to full power.
4. Once pile 9 has started to be driven by linear vibratory driver 10, the operator may "tune" the apparatus to the most desirable frequency for speed of driving by manually adjusting the frequency control settings on the electronic control unit to the point where he observes that the pile is being driven fastest. Once he sets the control unit at a given frequency, it will stay there unless he changes the adjustment. In places where it is unsafe to use certain frequencies of vibration, for instance where they might cause damage to a structure or even be a nuisance, the electronic control unit may be set to specifically exclude those frequencies, and the operator may then use either above or below the critical frequencies.
5. Electronic control unit 30 may be programmed to either exclude certain frequencies or not, but also it may be set up to sense the rate of driving by the use of an accelerometer attached to apparatus 10, by which it will automatically seek the frequencies which will drive the pile at the fastest rate for the given driving site. The electronic control unit may also monitor the vibrations being transmitted through the ground from the pile being driven, utilizing ground implanted accelerometer 8. If the vibrations reach a level deemed to be harmful to nearby structures for instance, the control unit may automatically turn the pile driver to a frequency which does not shake the ground as much. The electronic control unit may be programmed to integrate the input from the accelerometer transducer attached to the pile driver which monitors driving speed and frequency, as well as the ground implanted accelerometer transducer which monitors frequency and amplitude of the vibrations being transmitted through the ground using the data from both transducers, the monitor can automatically seek the best driving frequency and at the same time make sure that no unwanted frequency amplitudes are emanating from the pile driving site.
FIG. 6 illustrates pile driver 10 connected to a crane 2 by hoisting cable 3. As discussed above, hoisting cable 3 is attachable to the lifting bale which is attachable to lifting shaft 12. The hydraulic power unit 6 is connected to pile driver 10 by hydraulic power supply and return lines 6a. Means for operator control 30 (control box 30) of driver 10 is shown to include as inputs, a vibration sensing transducer 7 affixed to pile driver 10 and a vibration sensing transducer 8 implanted in ground 5. Control cables communicate the control signal from control box 30 to means 29 for frequency controlling the vibration of driver 10.
It is also thought that linear vibratory pile driver 10 and its use, and manner of use and many of its attendant advantages will be understood from the foregoing description and it will be apparent that various changes may be made in the form, construction and arrangement of the parts thereof without departing from the spirit and scope of the invention or sacrificing all of its material advantages, the form hereinbefore described being merely a preferred or exemplary embodiment thereof.
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A linear vibratory pile driver apparatus, system and method for using the apparatus to drive or to pull pilings. The apparatus is comprised of a lifting shaft isolated from but slideably mounted within a piston assembly which piston assembly is attached to a frame assembly. There is a cylinder assembly attached to a reaction mass and the piston assembly is vibratorily positioned within the cylinder assembly and vibratorily driven by hydraulic fluid at a selectable frequency thereby vibrating the piston/frame assembly (the piston assembly and the attached frame assembly) relative to the cylinder/reaction mass assembly (the cylinder assembly and the attached reaction mass). A clamp device such as jaws is attachable to a clamp-end of the frame assembly and the lifting shaft is attachable to a cable of a lifting apparatus such as a crane. The frequency of the vibration and the power of the vibration, which power is related to the pressure and the amount of hydraulic fluid and thus to the stroke length of the pistion, may be varied independently. By positioning the piston toward either the clamp-end or the cable end, and by adjusting the power, i.e., the stroke length, the linear vibratory pile driver may function as a hammer and a vibrator concurrently. Lowering the frequency of the vibrations and with the position of the piston toward one end or the other will result in the apparatus functioning as a hammer for either driving or pulling a pile.
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This application is a continuation-in-part of application U.S. Ser. No. 08/962,717 filed Nov. 17, 1997, and now U.S. Pat. No. 5,974,720.
BACKGROUND OF THE INVENTION
This invention relates to an apparatus for moving a decoy or decoys to attract animals by moving the decoys to stimulate various motions of live animals and more particularly to a clutch system which is workable on an automated drive motor system which allows for easy mobility of the decoys.
Most conventional decoys do not move or are designed for limited movement; however, the present invention not only attracts animals, but maintains their interest due to the control and deliberate movement of the decoy by the user.
Conventional decoys are stationary or move a portion of the body, pivot or turn; however, the movement is repetitious and restricted so that prolonged exposure to the animal causes a loss of attraction. Contrary to conventional decoys, the decoy moving apparatus of the present invention is capable of moving decoys hundreds of yards if necessary in irregular patterns at various speeds.
Often the target animal will approach a still decoy, but will be lured off by other live animals. The present invention provides an important tool for both hunters and photographers for attracting animals to them by mobilizing the decoy and controlling the movement.
The movable decoy mounting base provides a means for luring the animal to the viewer. The movement of the decoy keeps the animal's attention and aids in camouflaging the activities of the viewer so that the animal is less likely to spot the viewer.
SUMMARY OF THE INVENTION
The decoy apparatus for attracting animals includes a winding apparatus and a set of reels having a line or string extending to, through or around at least one fixed reference point, wherein the line is attached to a decoy pulled between the winding apparatus and/or one or more anchors, whereby winding the string with the decoy apparatus moves the decoy back and forth and/or rotates the decoy on its axis.
A preferred embodiment of the decoy moving device includes a frame which is typically composed of one or more vertical tubular members which can be pushed into the ground or mounted from a base. A means for rotatably supporting at least a first takeon/takeoff reel and at least a second takeon/takeoff reel are supported by the frame. A preferred means for rotatable support includes a rotatable shaft in cooperative engagement with both reels supported within a sleeve mounted horizontally to the frame. A means for rotating the first takeoff reel and said second takeon reel consists of a hand crank or small electric motor. The reels may be turned in the same direction at the same time or in an opposite direction independent of one another. A means for anchoring a line extending from the reels is movably held by a stationary object such as stake, rock, tree, anchored decoy or other means which allows the line to move slidably therethrough or around so that the line can be unwound from one reel and wound onto another. The stationary object for ground applications is preferably a stake having a loop or reel attached therethrough for passage of the line. A movable decoy such as a deer, rabbit, duck, fawn, turkey, etc. is attached to a line extending from the takeoff reel through the anchor object to the takeon reel for moving the decoy back and forth from the anchor to either one of the reels. Of course, several decoys may be attached to the line at several points between a plurality of anchors.
The winding apparatus provides a means of alternating the direction of movement of the decoy by simply sliding the shaft to one side or the other of the sleeve to engage or disengage a selected reel letting the opposing reel “freewheel” while rotating the crank. This method of engaging the reels permits the winding reel or unwinding reel to be engaged by turning the crank in the same direction when the line is attached so that it feeds from both reels at either the top or bottom. By threading the line onto the reels so the line is taken on or off at the bottom of one reel and the top of the other reel, the crank will be turned in opposite directions for winding or unwinding the line. Of course, both reels may be locked together for winding and unwinding at the same time; however, when one reel becomes full of line and the other reel has most of the line removed, the slack causes the line to fall on the ground, providing an area of entanglement.
To use the decoy moving apparatus, push the legs of the winding mechanism into the ground or secure to a base. Take the end of a first line from one of the reels and thread it through the pulley of the anchor pulley and place shaft of the anchor pulley into the ground or anchor it in the water. Secure the end of the first line to the decoy base sled. Repeat the procedure with the second reel and second line. The shaft of the decoy mechanism can be moved back and forth to engage or disengage the first or second reel to determine the direction of movement of the decoy.
It is contemplated that a plurality of reels may be used in pairs to control additional decoy lines. The reels would be designated first reel, second reel, etc., starting from the position closest to the crank handle. As described heretofore, the preferred embodiment is using feed and take-up reels rotating in the same direction. The first reel disengages the opposing second reel so that the first reel of the engaged side is winding the string in while the opposing disengaged second reel free-wheels, “spinning freely on the sleeve,” thereby releasing string from the spool as needed for movement of the decoy. In order to reverse the direction of the decoy, the shaft is moved through the sleeve or supporting means, by pulling or pushing, to disengage the engaged first reel and engage the prior disengaged second reel. The crank is then turned in the same direction so that the second reel is winding in the string and the first reel is unwinding string, thereby causing the decoy to pivot and move in the opposite direction. Moreover, the engagement mechanism allows the user to change the direction of movement of the decoy very quickly in order to make the decoy turn back and forth and “dance” in accordance with the desired method of enticing animals to the decoy.
The preferred embodiment of the winding mechanism comprises one or more pairs of reels or reels rotatably mounted on a single horizontal shaft; however, it is contemplated that the reels could be mounted on a vertical shaft as well, or one above the other on the same side of the frame support. Moreover, the reels of the preferred embodiment are round; however, it is contemplated that the reels could be formed in elliptical shape forming cams to vary the speed of movement of the decoy. A transmission such as a belt drive or gears may also be utilized to vary the speed of the decoy or provide greater power to pull heavy decoys.
A brake may also be used with the preferred embodiment by using a spring wrapped coaxially around the sleeve and engaging each reel with a slight tension to assist in control of the amount of string being reeled off of the freewheeling reel. The brake mechanism may also be mounted at any position between the reels by an arm or other support means just so long as the reels are engaged by the brake. Of course, other means of braking utilizing friction means on the reels or on the string being taken off of the reel can also be substituted for the braking system of the preferred embodiment.
An important feature is that the disengagement of the opposing reel allows the right amount of string to be removed from the pulley or reel, yet keep at least some tension on the string in order to keep the string from falling over the ground and becoming entangled or knotted and interfering with the movement of the decoy. The reels are not directly linked together mechanically as with gears because the amount of string on a full reel provides a circumference of a larger diameter than an almost empty reel, and would tend to cause the string to gather on the ground due to the difference in rate of rotation of the smaller reel in comparison with the larger reel.
Accordingly, it is an object of the present invention to provide a decoy moving apparatus utilizing a line of string or wire to pull a decoy or a decoy mounted onto a base.
Another important advantage and object of the present invention is to provide a decoy moving apparatus which is quiet.
Another object of the present invention is to provide a means of using as many anchor pulleys as desired in order to move the decoy in selected patterns, such as zigzag patterns.
It is another object of the present invention to provide each anchor with a pulley or loop in order that the decoy line is capable of moving back and forth between the winding mechanism and one or more anchor pulleys and that the decoy be pulled from the decoy winding apparatus to an anchor, or from one anchor to another anchor in a selected motion.
It is another object of the present invention to color or paint portions of the winding apparatus and/or decoy holding sled in a camouflage color.
Another important advantage and object of the present invention is that the decoy moving apparatus can be operated with one hand.
It is another object of the present invention to be able to place the anchor pulleys in position and to move the decoy around corners or objects which the user cannot see around, such as a large tree, bend of the road or over hills.
It is another object of the present invention to provide a decoy moving apparatus which can be used for moving targets in different locations, on land, in the water or even from a tree stand wherein the decoy can be suspended in the air, so that the user may operate the winding mechanism from a convenient vantage point behind objects, in a tree stand or from the bank of a body of water.
It is another object of the present invention to provide for using a scent, or taped sound device, or mouth calls in combination with the decoy moving apparatus.
It is another object to provide a decoy moving apparatus which is compact enough to fit into a backpack or bag.
It is yet another object of the present invention to provide a winding apparatus whereby the decoy can be pulled to or away from the frame of the winding apparatus while cranking in a single direction by using a shaft/reel engaging/disengaging mechanism.
It is yet another object of the present invention to provide a base forming a sled.
It is another object of the present invention to provide a winding mechanism comprising a pair of reels independently rotatably engaged with a manual crank.
It is another object of the present invention to provide a means of energizing the reels of the winding mechanism using a motor powered by a battery or electric motor.
It is another object of the present invention to utilize line selected from the group consisting of clear fishing line, nylon, cotton cord, string, metal wire and cable, or other polymers.
It is another object of the present invention to utilize clear line for deer, crows, owl, ducks and geese.
It is another object of the present invention to provide a method for the user to rotate the decoy and change the direction of movement of the decoy very quickly in order to make the decoy turn back and forth and “dance” in accordance with the desired method of enticing animals to the decoy.
It is another object of the present invention to provide a decoy moving apparatus which cannot only be used when hunting or observing wildlife, but also used in other manners such as providing a tool for target practice of various types.
Finally, it is an object of the present invention to provide a support means for the decoys mounted onto the base sled whereby different types of decoys may be utilized with the sled.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the present invention will be had upon reference to the following description in conjunction with the accompanying drawings in which like numerals refer to like parts throughout the several views and wherein:
FIG. 1 is a perspective view of the winding mechanism of the present invention showing a pair of reels mounted to a shaft of a support frame wherein the reels are engaged and rotated in the same direction independently by a hand crank, and showing a line wrapped around the reels in the same direction and through the guide eyelets with a shaft tension spring exerting light pressure on the reels;
FIG. 2 is a cross-sectional view of FIG. 1 along line 1 — 1 showing the sleeve, reels, shaft, spring brake, shaft tension spring and frame, wherein the first reel is engaged and the second reel is disengaged and free wheeling;
FIG. 3 is a cross-sectional view of FIG. 1 along line 1 — 1 showing the sleeve, reels, shaft, spring brake and frame, wherein the first reel is disengaged and free wheeling and the second reel is engaged;
FIG. 4 is a perspective view of the winding mechanism of an alternate embodiment of the present invention showing a pair of reels mounted to a shaft of a support frame wherein the reels are engaged and rotated in the opposite direction independently by a hand crank, and showing a line wrapped around the reels in opposite directions and through the guide eyelets with a shaft tension spring exerting light pressure on the reels;
FIG. 5 is a front view of FIG. 4 showing the shaft tension springs;
FIG. 6 is a front view of FIG. 4 showing the shaft tension springs replaced by a spring brake;
FIG. 7 is a cross-sectional view of FIG. 5 along lines 5 — 5 showing the sleeve, reels, shaft, shaft tension spring and frame, wherein the first reel is engaged and the second reel is disengaged and free wheeling;
FIG. 8 is a cross-sectional view of FIG. 6 along lines 6 — 6 showing the sleeve, reels, shaft, spring brake and frame, wherein the first reel is disengaged and free wheeling and the second reel is engaged;
FIG. 9 is a left-side view of FIG. 4;
FIG. 10 is a perspective view of an alternate embodiment wherein both of the reels are engaged at the same time for unwinding and winding the line;
FIG. 11 is a cross-sectional view of FIG. 10 along lines 10 — 10 showing the sleeve, reels, shaft, spring brake, shaft tension spring, frame and locking pins extending through and engaging both reels;
FIG. 12 is a perspective view of an anchor pin and pulley for use with the invention;
FIG. 13 is an exploded view of a spring brake;
FIG. 14 is a plan view of a crank handle and shaft showing the reel engaging pins;
FIG. 15 is a shaft sleeve for supporting the shaft therethrough and reels thereon;
FIG. 16 is a perspective side view showing a decoy mounted onto a sled base having a plurality of positioning points therein;
FIG. 17 is a perspective side view showing an alternate embodiment of the decoy sled base showing the means for holding formed extending uniformly across the top surface of the sled and having a recessed area to accommodate the line holding means;
FIG. 18 is a base mounting unit for the frame of the winding mechanism shown in FIG. 1 providing means for rotatably mounting the unit on a hard surface such as a tree stand.
FIG. 19 shows the decoy sled base being pulled along a path from left to right;
FIG. 20 shows the decoy sled base being rotated at a right angle with respect to the path of travel;
FIG. 21 shows the decoy turned around 180 degrees for movement in the opposite direction;
FIG. 22 is a schematic representation showing the winding mechanism connected to a single anchor pulley for moving a decoy back and forth in between;
FIG. 23 is a schematic representation showing the winding mechanism connected to a pair of spaced apart anchor pulleys for moving one or more decoys back and forth in between wherein the decoys are floating on water and the anchors are weights attached to immovable decoys and moveable decoys are pulled back and forth in between the anchored decoys to the winding mechanism;
FIG. 24 is a schematic representation showing the decoy moving between a pair of anchor pulleys from the first reel to the second reel of the winding mechanism;
FIG. 25 is a schematic representation showing a different pattern or path of the decoy layout;
FIG. 26 is a schematic representation showing a plurality of decoys moving between a plurality of anchor pulleys from the first reel to the second reel of the winding mechanism;
FIG. 27 is a schematic representation showing a different pattern or path of the decoy layout of the decoys of FIG. 26;
FIG. 28 shows a claw anchor pulley for use with the present invention;
FIG. 29 shows a top view of the decoy sled having partitions formed for holding weights therein;
FIG. 30 is a front view of the sled mounting base;
FIG. 31 is a side view of the sled mounting base; and
FIG. 32 shows an overhead support assembly.
FIG. 33 is a front view of the winding mechanism of an alternate embodiment of the present invention showing a pair of reels mounted on the shaft of a support frame with a clutch attached to each reel, also mounted on the shaft and a reversible motor mounted to the shaft and supported by an adapter plate also attached to a support frame. FIG. 34, is a schematic representation showing stops placed on a line used to reverse directions of a reversible motor with a current sensor attached to the power supply.
FIG. 35 is a front view of the winding mechanism of an alternate embodiment of the present invention showing a pair of reels mounted on a first shaft of a support frame with a clutch attached to each reel and also mounted on the first shaft and an adapter plate attached to a support frame with a motor attached to the underside of the adapter plate extending out from the frame with the motor connected to a second shaft which is connected to a pulley system used to rotate the first shaft.
FIG. 36 is a front view of an alternate embodiment of the present invention showing a motor with a shaft extending from the head of the motor and with two reels with clutches attached, both mounted on the shaft.
FIG. 37 is a front view of a deep water concealer.
FIG. 38 is a front view of the deep water concealer cooperatively engaged with the legs of the frame and the support base.
FIG. 39 is a front view of an alternate embodiment of the present invention showing a plurality of reels, clutch assemblies and a motor attached to a shaft.
FIG. 40 is front view of the guiding loop of the deep water concealer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The decoy base and winding apparatus 10 of the present invention is manufactured from readily available materials and simple in design. The preferred embodiment is comprised of metal, more particularly steel; however, it is contemplated that aluminum, wood, fiberglass, plastic, polymer composite materials or combinations thereof could be used in combination with or substituted for the steel components of the present invention.
Referring now to the drawings, FIGS. 1-11 show the decoy moving winding and unwinding apparatus 10 comprising a frame 12 which is typically composed of a one or more vertical tubular members which can be pushed into the ground or mounted from a base. The frame 12 of the preferred embodiment utilizes a first front leg 14 vertical tubular member and a second rear leg 16 as a vertical tubular member. The distal ends 18 of the first leg 14 and second leg 16 are pointed to facilitate easy insertion into the ground or for cooperative engagement into a holding member 19 such as shown in FIG. 18 . The frame 12 of the preferred embodiment utilizes three cross members for stability. The first cross member 20 connects the first leg 14 and second leg 16 together near the central area of the frame 12 . The second cross member 22 is located between the first cross member for providing lateral stability and supporting a reel holding means, and a third top is cross member 24 which is often formed in a shape having a generally flattened appearance to provide a good grip of carrying and a smooth surface for pushing the legs 14 , 16 , into the ground.
As shown in FIG. 18, a winding apparatus mounting base 19 may be attached to fixed objects such as a tree stand for support thereof. The base includes a longitudinal member for attachment to a surface having cylinders extending upward therefrom sized for and spaced apart for cooperative engagement with the legs of the winding apparatus. A cross member may be attached to one end of the longitudinal support member by a pin providing a pivoting point and additional vertical stability therefor.
A pair of reels 36 , 38 are formed having flat sidewalls; however, the sidewalls may be formed curving outwardly toward the outer edge to guide the line 48 into the reel 36 , 38 . It is contemplated that additional reels may be added and operated with the same crank to move additional decoys 86 .
The reel holding means is supported on and normal to the second cross member 22 . The reel holding means in the preferred embodiment is a horizontal tubular member or sleeve 26 ; however, it is contemplated that rings, loops, or one or more sections of tubing could be utilized therefore. Within the sleeve 26 is a shaft or axle 28 rotatably supporting at least a first takeoff reel 36 and at least a second takeon reel 38 . Washers 34 positioned on each side of the reels 36 , 38 are held in place by means for holding such as retainer rings or spring clips 54 which may engage a groove 52 as shown in FIG. 15 . Thus, the reels 36 , 38 are held in position upon the sleeve 26 by the spring clips 54 .
In the preferred embodiment the shaft 28 cooperatively engages both reels 36 , 38 separated by the frame 12 and supported within the sleeve 26 mounted horizontally to the frame 12 . A means for rotating the first reel 36 and said second reel 38 consists of a hand crank having a handle 30 . A small electric motor 39 powered by electricity or batteries could also be utilized for power to rotate the reels 36 , 38 (see FIG. 6 ). Moreover, a remote control unit could be used to actuate the electric motor and provide forward motion, reverse motion, and variable speed. It is also contemplated that a worm gear assembly could be mounted onto the frame so that a shaft 28 aligned normal to the reels 36 , 38 and powered by hand or an electric motor could be used to rotate the reels 36 , 38 so that the crank can be positioned behind the reels 36 , 38 rather than extending from the side as shown in the preferred embodiments.
Means for guiding the line 48 comprising loops 46 extend from the frame 12 normal thereto in front of and in alignment with each of the reels 36 and 38 . The loops 46 shown in the figures extend outwardly from horizontal arms 44 affixed to the sides of the frame 12 at a selected position; however, the loops may be removably attached to the frame 12 or rotatably and/or slidably attached thereto for adjustment. Typically the loops 46 are mounted near the top or bottom of the reels 36 , 38 depending upon the point of takeon or takeoff of the line 48 .
In the preferred embodiments the reels 36 , 38 may be turned in the same direction at the same time or in an opposite direction independent of one another depending upon whether the line is wrapped on the reels 36 , 38 clockwise or counterclockwise. The line 48 may be attached to the first reel 36 and second reel 38 so that the line 48 feeds, and takes off, from the bottom of the reels 36 , 38 so that the crank handle 30 is turned in the same direction when feeding and winding the line 48 . The line 48 may be fed at the top of one reel and taken up at the bottom of the other reel whereby the crank handle 30 may be rotated in opposite directions depending upon which direction the decoy is moved back and forth.
A means for biasing and applying tension on one or both of reels 36 , 38 provides a means to control free-wheeling of the unengaged reel 36 , 38 . As shown best in FIGS. 2 and 3, the biasing means may comprise a spring brake 50 as shown in FIGS. 2 and 13. The spring brake 50 comprises a tubular longitudinal member 62 having a spring 58 inserted within and a pair of spacer means such as cylindrical sections 60 having end surfaces which abut the distal ends of the spring 58 . The length of the spring brake 50 and tension of the spring 58 are designed positioning between the reels 36 and 38 in order to provide slight pressure thereto and limit the amount of free-wheeling of one or both reels 36 and 38 .
As shown in FIGS. 1 and 2, an alternate means of exerting tension and limiting free-wheeling of one or both of the reels 36 , 38 is to insert a tension spring 32 coaxially around the shaft 26 and in between the washer 34 and the second cross member 22 so that the tension spring 32 abuts the frame 12 and side of the reels 36 , 38 .
It should be noted that neither the tension spring 32 nor the spring brake 50 are required for operation of the present invention and that the invention may be used with a tension spring 32 , a spring brake 50 , or combination thereof.
As shown in FIGS. 1-3, the winding apparatus utilizes a shaft 28 of a length sufficient to extend outwardly past the end of the reel 36 , 38 whereby the reels 36 , 38 rotate about and slide along the shaft 28 . The shaft 28 slides back and forth to engage and disengage opposite reels, 38 making disengaged reel 36 , 38 free wheeling. The washer 34 of the reel 36 , 38 abut the frame to limit lateral movement inwardly and the pins 42 limit lateral movement of the reels 36 , 38 outwardly. As shown best in FIG. 14, a first pin 42 extends through the shaft 28 on the proximal end of the shaft 28 end near the crank handle 30 and is slidably engageable with a first ring coupling member 40 having a groove or notch 41 formed in the outer surface thereof opposite the reel 36 , 38 . The ring coupling member 40 may be formed integrally with the reel or it may abut and be affixed to the outer wall of the reel 36 , 38 . A second ring coupling member 40 is positioned against the exterior wall of the opposing reel 38 extending outwardly having a cooperative groove and second pin 43 extending through the shaft 28 at the distal end thereof. As shown in FIGS. 7 and 8, the pins 42 , 43 are spaced apart from one another and the reels 36 , 38 so that when the shaft 28 is pushed inwardly toward the second reel 38 , the first pin 42 cooperatively engages the first ring coupling member 40 and the first reel 36 . When the shaft 28 is pulled out toward the crank 30 the first pin 42 is disengaged from the first ring coupling 40 and the second pin 43 is pulled into and cooperatively engages the second ring coupling 40 or the second reel 38 .
As shown in FIG. 11, the first pin 42 and second pin 43 are spaced to engage the first ring coupling member and the second ring coupling member simultaneously providing a means for feeding line 48 and taking up line 48 . This arrangement tends to produce slack line which gathers on the ground depending upon the amount of line used due to the change of circumference of the line 48 remaining on the reels 36 , 38 .
FIG. 12 shows a typical anchor pin 64 consisting of a spike 66 having a cross member 68 forming a handle attached to the distal end opposite the point 70 . One or more spacer members 72 such as a washer are securely positioned at a selected point to provide the desired ground clearance. A pulley 74 is attached to the anchor pin 64 by a hook 76 or other means. The spike 66 of the preferred anchor pin 64 is comprised of metal; however, other durable materials may be used as well. The spike 66 may also be formed having flights or formed in corkscrew shape to facilitate placement into the ground. It is contemplated that other types of anchor devises may be used with the present invention.
Of course the line 48 could be mounted to a tree, rock or other immovable object depending on the terrain and type of movement desired for the decoy 86 . In a water environment, the line is connected to an anchor decoy or other camouflaged object which may be anchored by a weight or holding means so that the decoy 86 can be moved to the anchor decoy back and forth between the first and second reel, 36 and 38 , respectively.
“U-shaped” members may be placed into the ground at various points to aid in holding the line close to the ground in uneven terrain.
FIGS. 16, 17 and 29 - 31 show a movable decoy mounting base 19 for use with the winding apparatus 10 . The preferred embodiment comprises a sled 78 , which is oval in shape and substantially flat. The side edges 79 are angled upwardly to facilitate sliding over grass or irregularities of the ground surface. The upper surface 80 includes at least one and preferably a plurality of apertures 82 extending a selected distance into the base surface 80 for cooperatively engage one or more holding members or legs 84 of the decoy 86 . Usually two legs 84 are used to prevent rotation of the decoy 86 ; however, on leg 84 may be used if fastened securely into the aperture 82 or if the aperture is formed having a cross-sectional having a particular shape being square, octagon, etc.. In the preferred embodiment, a hole 88 is formed at a selected location in the sled 78 spaced apart from the front, back, or center points so that the line 48 is run in-under the sled 78 and extends upwardly through the surface 80 where it is tied to an eyelet 90 . In the preferred embodiment the eyelet 90 is formed in a recessed area of the sled 78 to maintain a low center of gravity and be less noticeable. As shown in FIG. 29 the sled may include webbing to increase strength and reduce weight and provide a section to hold weights 92 . As shown in FIGS. 19-21, the position of the hole 88 provides a means for the user to control the pivoting of the decoy 86 with the winding device 10 .
The movable decoy mounting base or sled 74 of the preferred embodiment is fabricated in various sizes depending upon the size and weight of the decoy 86 to be supported thereon. For instance, a 12 inch by 18 inch sled can be used for lightweight decoys 86 consisting of polyurethane foam, styroforma, plastic, or shell type decoy animals such as turkeys, geese, ducks, rabbits, or fawn deer. Larger sleds 74 of approximately 24 inches by 30 inches are used for coyotes, adult deer, moose, or elk. It is contemplated that the decoys 86 may be integrally formed having a sled base of runners thereon or that a cart supported by wheels or rollers could by utilized as a movable decoy base. Weights may be used on the sled or formed integrally therewith to provide a stable base for large or heavy decoys in adverse environmental conditions.
FIGS. 22-27 illustrate various schematic representations using the sled 78 and winding apparatus 10 of the present invention. FIG. 22 is a schematic representation showing the winding mechanism 10 connected to a single anchor pulley 64 for moving a decoy 86 back and forth thereinbetween. FIG. 23 is a schematic representation showing the winding mechanism 10 connected to a pair of spaced apart decoy anchor pulleys 65 for moving one or more decoys 86 back and forth thereinbetween wherein the decoys 86 are floating on water and the decoy anchor pulleys 65 consists of immovable decoy anchor pulley 65 having weights attached thereto whereby movable decoys 86 are pulled back and forth in between the decoy anchor pulleys 65 to the winding mechanism 10 . FIG. 24 is a schematic representation showing the decoy 86 moving between a pair of anchor pulleys 64 from the first reel 36 to the second reel 38 of the winding mechanism 10 . FIG. 25 is a schematic representation showing another triangular pattern or path of the decoy 86 path. FIG. 26 is a schematic representation showing a plurality of decoys 86 moving between a plurality of anchor pulleys 64 from the first reel 36 to the second reel 38 of the winding mechanism 10 in a diamond pattern. FIG. 27 is a schematic representation showing a different decoy layout wherein the decoys 86 are traveling in a row.
As shown in FIG. 28, a claw anchor pulley 94 includes a shaft having a first end connected to an anchor pulley and a second end connected to a cross member extending outwardly on both sides therefrom wherein the distal ends of the cross member are connected normal to hook members formed having a bend at about a right angle. The string can be threaded through the reel of the claw anchor pulley which van be thrown from a concealed position near the animal to be attached so that decoy can be moved between claw anchor pulley and the first and second reels 36 , 38 .
An overhead support cable system 100 attached to stationary objects may also be used to support large animal decoys and used in combination with the decoy moving winding apparatus 10 of the present invention. A first top line 102 supports a swivel pulley 104 having one or more decoy suspension lines 106 attached to the decoy 86 . The line 48 from the winding apparatus 10 is anchored to the stationary objects by pulleys 108 . The line 48 is fastened to an eyelet or other holding means on the decoy 86 to provide the means for moving the decoy 86 between the stationary objects.
FIG. 33 is a frontal view of an alternative embodiment of the present invention. In this Figure, attached to the first reel 36 and second reel 38 are coupling/decoupling clutches 109 , 110 and a reversible motor 111 . Clutches are utilized to transfer the rotational drive of the drive shaft to the reels. Since the reels will be potentially at rest while the drive shaft has a significant rotational velocity, a clutch device is necessary to provide a smooth transition to bring the reels to the same speed as the input shaft. Thus, when the reels are brought up to speed of the drive shaft, the clutch is utilized to transfer energy from the shaft to the reels. As the reels are brought up to speed, slipping must occur until the reels have the same rotational speed as the drive shaft. Kinetic energy is thus absorbed by the clutch systems and released as slight heat when the clutch is engaged to fully rotate the reels. Either frictional contact clutches or positive contact clutches may be utilized, as well as other standard methods of coupling such as freewheeling, magnetics or overrunning. It is understood that such coupling and decoupling of the clutches may be appropriately selected by one of ordinary skill in the art. A reversal of the input direction to the drive shaft and hence the reels either momentary or continuous, causes the output clutch to decouple. The output is fully decoupled after the input has displaced approximately 20 degrees in the reverse direction. Additional reverse rotation of the input does not have any further effect on the decoupling action. In the decoupled state, the output and thus the decoupled reel, is free to rotate in either direction.
One of the clutches 109 , 110 should be a clockwise oriented clutch 109 and the other a counterclockwise oriented clutch 110 . In FIG. 33, the clutches 109 , 110 are coupling/decoupling in nature. These clutches consists of an input drum, and output drum, a spring for coupling the two, and a stationary member. The clutches 109 , 110 are mounted on the output shaft 26 with set screws 112 , 113 . A anti-rotation pins 116 , 117 prevent rotation of the stationary member of the clutch structure.
A reversible motor 111 is attached to an end of the shaft 26 . The motor is further supported by a motor mount 114 which is attached to an adapter plate 115 . Stationary pins 116 , 117 attached to the clutches 109 , 110 are engaged by the adapter plate 115 to prevent rotation of the clutch 109 , 110 structures, and the line 48 take-on and take off. When the reversible motor 111 rotates in the clockwise direction, the clockwise oriented clutch 109 engages and drives the reel 36 connected to the clockwise oriented clutch 109 in the take-on direction, thus taking on the line 48 . The counterclockwise oriented clutch 110 decouples and allows the reel connected to the counterclockwise clutch 110 to be freely rotated in a supply direction at a speed demanded by the line 48 . When the reversible motor 111 reverses, thus reversing the direction of the shaft 26 , the clockwise oriented clutch 109 decouples and the counter clockwise clutch 110 engages reversing the direction of the reel 36 , 38 rotation.
A coupling/decoupling clutch may be utilized like the one manufactured by Machine Components Corporation, CDC series and shown in FIG. 41 ( a ), 41 ( c ), 42 ( a ) and with slight modifications applicable to the design of the decoy moving apparatus. Each of these clutch assemblies has a portion which attaches to a shaft connected to the output of a motor and in the decoy moving apparatus, would couple the output of the motor to the reels 36 , 38 to produce the rotation to create the takeon/take-off of the line 48 .
The reversible motor 111 utilized is operable on DC current with provision for an adapter that would enable a motor to operate on an AC current alternatively. Actuation of the motor would be accomplished by means of manual operation, either direct or remote or by timer mechanism or both.
Reversal of the motor 111 direction can optionally be achieved by use of a current sensor within the motor or attached at the power supply and by affixing stops 118 to the line 48 , as seen in FIG. 34, which would prevent further take up of the line 48 when the line 48 encounters a fixed point. The current sensor present in the reversible motor 111 detects the resistance imposed upon the reversible motor 111 and actuates a reversal of direction of the motor 111 .
FIG. 35 shows another alternative embodiment utilizing a belt 121 and pulleys 119 , 120 . The motor 111 , is attached to the underside of the adaptor plate 115 and has an second output shaft 122 engaged with one of the pulleys 120 . The other pulley 119 is attached to the first shaft 26 . The motor 111 rotates the second output shaft 122 which in turn rotates the pulley system 123 and activates the clutches 109 , 110 and the take-on and take off of the line 48 on the reels 36 , 38 . It is contemplated that a gear motor can also be utilized with this invention.
An alternative embodiment of the invention is in FIG. 36 and includes a reversible motor 124 that supports the shaft 26 . In this embodiment, the stationary pins 116 , 117 attached to the clutches 109 , 110 are mounted to the reversible base motor 124 by mounting plates 131 and with mounting screws 125 .
It is contemplated that a plurality of reels may be used in pairs to control additional decoy lines. FIG. 37 shows this alternative embodiment which has a third reel 132 and fourth reel 133 with a third clutch assembly 134 attached to the third reel 132 and a fourth clutch assembly 135 attached to said fourth reel 133 . The first clutch assembly 109 and the third clutch assembly 134 would be clockwise oriented clutches and when these clutches engaged, they would drive the reels 36 , 132 connected to the clockwise oriented clutches 109 , 134 in the take-on direction, thus taking on line 48 . The counterclockwise oriented clutches, 110 , 135 decouple and allows the reels 38 , 133 connected to the counterclockwise clutches 110 , 135 to be freely rotated in a supply direction at a speed demanded by the lines 48 . When the reversible motor 111 reverses, thus reversing the direction of the shaft 26 , the clockwise oriented clutches 109 , 134 decouples and the counter clockwise clutch 110 , 135 engages reversing the direction of the reels 36 , 38 , 132 , 133 rotation.
An additional feature that can be used with the present invention is the deep water concealer 126 shown in FIGS. 38 and 39. When utilizing the decoy moving device in deep water, a means to keep the line that is moving the decoys underwater is needed to prevent the wildlife from seeing the line and also to prevent the lines from rippling the water.
The concealer 126 includes two cylinders 127 , 128 connected with a longitudinal member 129 and spaced apart for cooperative engagement with the legs of the winding apparatus. Extending perpendicular from one of the cylinders is a metal arm 130 . The metal arm angles downward at an approximate 45 degree angle. Shown in FIG. 40 is a guiding loop 131 which is located at the end of the angled portion of the arm and allows for a line to be placed in the guiding loop 131 after the decoy moving apparatus has been set up. The preferred embodiment is made of metal, more particularly steel; however, it is contemplated that aluminum, wood fiberglass, plastic, polymer composite materials, or combinations thereof could be used in combination with or substituted for the steel components of the concealer.
The foregoing detailed description is given primarily for clearness of understanding and no unnecessary limitation are to be understood there from, for modifications will become obvious to those skilled in the art based upon more recent disclosures and may be made without departing from the spirit of the invention and scope of the appended claims.
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A decoy moving apparatus for attracting animals including a set of reels attached to a clutch system which is workable on an automated drive motor system. The clutch system works to engage and disengage the reels to takeon/take-off line which is extending from the reels to at least one stake or decoy anchor reference point, wherein the line is attached to a decoy pulled between the reels and one or more anchors, whereby the takeon/take-off of the line with the decoy apparatus moves the decoy back and forth and/or rotates the decoy on its axis. The decoy may float in water, mounted to a sled type mounting base, or suspended from a wire, depending upon the habitat of the animal to be attracted to the viewer.
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FIELD OF THE INVENTION
The present invention is directed generally toward fire starting assemblies and, more particularly, toward a portable fire starting assembly having easy lighting and long burning characteristics.
BACKGROUND OF THE INVENTION
Outdoor recreational activities are common in today's society. Such outdoor recreational activities include activities such as camping, fishing, hunting, sledding, and virtually any other activity that can be performed outdoors. Various of these activities, e.g., sledding, are not performed during the summer months when the weather is warm. Many individuals engage in such outdoor activities when the outdoor temperature is on the colder side. For example, the rifle deer season in the Commonwealth of Pennsylvania typically occurs from late November to mid-December. At such times, the outdoor temperature can be fairly cold, potentially reaching frigid temperatures with and without factoring in wind chill. Also, the opening day of trout season in the Commonwealth of Pennsylvania typically occurs in mid-April. At this time, the weather is often on the colder side, requiring individuals to take appropriate precautions to keep themselves warm. Even during the summer months, the temperature at night may drop considerably from the temperature during the daylight hours. This is especially true in the mountainous areas of the country where individuals typically go camping.
Many individuals engaging in outdoor activities in the colder months of the year will be become just that, cold. Unless these individuals can find a way to warm themselves, even if only for a short period of time, the fact that they are cold may cause them to cut short the outdoor activity in which they are engaging. At such times, many individuals desire to light a fire, such as a campfire, to warm themselves. However, campfires are fairly difficult to light, requiring an individual to take the time to gather wood and kindling, and also requires the individual to have on their person, or readily available, a flammable starting material in order to get the fire started. Further, simply gathering wood and kindling in general is not enough to build a campfire, as the wood and kindling must be sufficiently dry in order to burn properly. Since an individual by this time is normally already cold, he or she may not wish to take the time to search for and gather sufficiently dry wood and kindling, and simply forego in continuing to engage in the particular outdoor activity.
Even after searching for and gathering sufficiently dry burning materials, an individual may find it difficult or impossible to start a campfire due to windy conditions. The wind may continue to extinguish the fire before it has a chance to sufficiently burn and “catch”. Thus, even though an individual has taken the time to gather the appropriate wood, kindling, etc., a windy day may simply prevent the individual from being able to light a fire for warmth. This can be particularly frustrating and, when faced with such problems, often cause an individual to simply quit the outdoor activity and return to a car, house, etc., where heat is available.
The present invention is directed toward overcoming one or more of the above-mentioned problems.
SUMMARY OF THE INVENTION
A fire starting assembly is provided in accordance with the present invention for easily lighting and maintaining a fire in an outdoor environment. The inventive fire starting assembly includes, in its simplest form, a combustible container defining an interior, and intermixed layers of flammable and combustible materials in the container interior having first and second burning points, respectively. To provide oxygen for the fire, the container includes holes for admitting air into the container interior, thus fueling the fire within the container interior.
The first burning point of the flammable material is at a temperature less than the second burning point of the combustible material. The combustible container typically has a third burning point at a temperature between the first and second burning points.
In a preferred form, the combustible container includes a cardboard box having top, bottom and side surfaces, the flammable material includes shredded paper, and the combustible material includes elongate pieces of wood. The intermixed layers accordingly include intermixed layers of shredded paper and pieces of wood. The pieces of wood in each respective wood layer are preferably spaced from one another, with the shredded paper additionally provided in the spaces between the pieces of wood in the wood layers.
In one form, the elongate pieces of wood include spaced first and second ends, with the elongate pieces of wood oriented vertically in the container interior such that their first and second ends lie generally adjacent the container top and bottom surfaces, respectively.
In another form, the elongate pieces of wood are oriented in row and column format within the container interior, such that adjacent members in each row are spaced from one another and adjacent members in each column are spaced from one another.
In a further form, the shredded paper defines pores formed in between, and by, the shredded paper material, with the pores permitting air to flow therethrough for fueling the fire within the container interior.
It is an object of the present invention to provide a fire starting assembly that is easy to light and long burning.
It is an additional object of the present invention to provide a fire starting assembly that is easy to light in windy conditions.
It is a further object of the present invention to provide a fire starting assembly that is easily transportable.
It is yet a further object of the present invention to provide a fire starting assembly made completely of burnable material.
It is still a further object of the present invention to provide a fire starting assembly that gives off enough heat such that it may be utilized as a fire in and of itself.
Other objects, aspects and advantages of the present invention can be obtained from a study of the specification, the drawings, and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a fire starting assembly according to the present invention in an open position;
FIG. 2 is a perspective view of the fire starting assembly according to the present invention in a closed position;
FIG. 3 is a perspective view of a combustible member incorporated within the inventive fire starting assembly; and
FIG. 4 illustrates a flammable material incorporated within the inventive fire starting assembly.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, a fire starting assembly according to the present invention is shown generally at 10 . The fire starting assembly 10 , in its simplest form, includes a combustible container 12 defining an interior 14 , with a flammable material 16 generally filling the container interior 14 and having a plurality of combustible members, or material 18 , intermittently dispersed in the flammable material 16 in the container interior 14 . As shown in FIG. 1, the flammable 16 and combustible 18 materials are provided in intermixed layers within the container interior 14 .
The combustible container 12 , the flammable material 16 and the combustible members 18 are all made from burnable material. In order to facilitate lighting and burning of the fire starting assembly 10 , the flammable material 16 includes an easy ignitable material having a burning point at a relatively low temperature. The combustible container 12 is made of a material that is longer burning than the flammable material 16 , and has burning point at a temperature higher than the burning point temperature of the flammable material 16 . The combustible members 18 are made of a material that is even longer burning than the combustible container 12 , and each has a burning point at a temperature higher than that of the burning point temperatures of either the combustible container 12 or the flammable material 16 . In a preferred form, the combustible container 12 includes a cardboard box, the flammable material 16 includes shredded paper, and the combustible members 18 includes pieces of wood, and these elements will hereinafter be referred to as such. However, it should be understood that other burnable materials having appropriately related burning point temperatures for at least the flammable 16 and combustible 18 materials may be implemented without departing from the spirit and scope of the present invention.
Referring to FIGS. 1-2, the cardboard box 12 is preferably rectilinear in shape, having top 20 , bottom 22 , and four side surfaces 24 . To facilitate opening of the cardboard box 12 for lighting purposes, the top surface 20 is defined by flaps 26 which may be folded as shown in FIG. 2 to define the top surface 20 , thus closing the cardboard box 12 . To maintain closure of the cardboard box 12 , a strip of tape 28 , or other adhesive means, may be provided along the top surface 20 along the seam formed by the closed flaps 26 . The tape 28 , or other adhesive means, should maintain the cardboard box 12 in a closed position, but be removable so that the flaps 26 may be opened for lighting of the fire starting assembly 10 .
To facilitate burning of the shredded paper 16 and the wood pieces 18 within the container interior 14 , air holes 30 are provided in the side surfaces 24 . Preferably, the air holes 30 are approximately 1.25″ in diameter, with two air holes 30 formed in each of the side surfaces 24 generally near the bottom surface 22 . However, any number of air holes 30 having virtually any diameter may be formed in the fire starting assembly 10 in any of the surfaces 20 , 22 or 24 without departing from the spirit and scope of the present invention. To facilitate carrying of the fire starting assembly 10 to a remote location, handles 32 are provided in opposing side surfaces 24 . Preferably, the handles 32 typically include cut-out handles formed in the opposing side surfaces 24 , however, other handle configurations may be implemented.
As shown in FIGS. 1 and 3, the pieces of wood 18 are preferably elongate, having first 34 and second 36 spaced ends. The wood pieces 18 are intermittently disposed in the container interior 14 , such that a space is provided around each of the wood pieces 18 . As shown in FIG. 1, the wood pieces 18 are preferably oriented in row and column format within the container interior 14 , such that adjacent wood pieces 18 in each row are spaced from one another, and adjacent wood pieces 18 in each column are spaced from one another. The wood pieces 18 are preferably vertically oriented, such that the first end 34 of the wood pieces 18 lies generally adjacent the top surface 20 of the cardboard box 12 , and the second end 36 of the wood pieces 18 lies generally adjacent the bottom surface 22 of the cardboard box 12 . The shredded paper 16 fills the remainder of the container interior 14 completely surrounding each of the wood pieces 18 . It should be understood that the orientation shown in FIG. 1 is a preferred embodiment only, and the wood pieces 18 may be sized, dispersed and/or oriented in the container interior 14 randomly or in any other manner without departing from the spirit and scope of the present invention.
As shown in FIGS. 1 and 4, the shredded paper 16 defines pores 38 which are formed between, and by, the paper material. The pores 38 permit air to flow between the paper material, thus providing oxygen to the fire started and burning within the container interior 14 .
In operation, a user simply opens the flaps 26 of the top surface 20 to the position shown in FIG. 1 . Since the shredded paper 16 is a highly flammable material having a low burning point, upon touching a match or other lighting element to the shredded paper 16 it will almost immediately begin to burn. The user may then close the flaps 26 to the position shown in FIG. 2, to prevent wind from blowing out the fire which has been started within the container interior 14 . Oxygen is provided to the fire started and burning in the container interior 14 via the air holes 30 formed in the side surfaces 24 and the pores 38 defined by the shredded paper 16 . As the shredded paper 16 within the container interior 14 catches fire, it burns all around each of the wood pieces 18 , eventually heating the wood pieces 18 , to a burning point such that the wood pieces 18 , will ignite and begin to burn. Since the cardboard box 12 is also burnable, it will also catch fire, typically before the wood pieces 18 and will help to ignite the wood pieces 18 . Thus, simply by touching a match to the shredded paper 16 , a user can have a small fire readily before them in a matter of minutes, with little or no clean-up since all of the material included in the fire starting assembly 10 is burnable.
The fire starting assembly 10 can be used in a variety of outdoor activities, such as, but not limited to, camping, fishing along a lake or stream, hunting, sledding, working outdoors, or any outdoor activity in general. Preferably, as shown in FIG. 2, the cardboard box 12 has a length 1 equal to 14″, a width w equal to 14″, and a height h equal to 12″. With this particular size, the fire starting assembly 10 may be easily transportable to a variety of outdoor locations. Also, as shown in FIG. 3, the wood pieces 18 preferably have a height h′ equal to 11.5″, a width w′ ranging from 0.5″-2.0″, and a length 1′ between 0.5″-2.0″. Preferably, the wood pieces 18 have a square 1′×w′ cross-section, however, the present invention is not limited thereto. It will be appreciated that the smaller cross-sectional wood pieces 18 will “catch” and burn faster, while the larger cross-sectional wood pieces 18 , will “catch” and burn at a slower rate. Since the wood pieces 18 will be standing upright in the cardboard box 12 , there is room to place shredded paper 16 both below and on top of the wood pieces 18 in the container interior 14 . It should be understood that the above-recited dimensions of the cardboard box 12 and the wood pieces 18 are for exemplary purposes only to provide a fire starting assembly that is sufficiently light-weight to be readily transportable; any dimensions may be utilized without departing from the spirit and scope of the present invention.
The size of the cardboard box 12 and the wood pieces 18 will dictate the number of wood pieces 18 that may be positioned within the container interior 14 . Sufficient shredded paper 16 , or other flammable material, should be positioned in the container interior 14 surrounding the wood pieces 18 such that sufficient heat will be generated by the burning of the shredded paper 16 to ignite the wood pieces 18 . Testing was performed on a number of samples made in accordance with the above-recited dimensions, and each time the fire and heat generated by the fire starting assembly 10 lasted approximately 35-40 minutes without adding wood to the fire. Thus, the fire starting assembly 10 according to the present invention acts as a campfire in and of itself generating sufficient heat to temporarily warm individuals from the cold. Once the fire starting assembly 10 has been ignited and is readily burning, a user can easily add wood or other burnable material to the fire and keep it going for as long as it the user desires.
Virtually any type of wood, or combustible material, may be implemented for the wood pieces 18 , including, but not limited to, wood types such has pine, oak, cherry, poplar, maple, walnut, etc. Further, compressed particle board pieces may be utilized, and the wood pieces 18 may or may not include bark on the outer surfaces thereof. Still further, other combustible materials, such as, but not limited to, charcoal pieces, may be utilized in conjunction with, or in place of, the wood pieces 18 if so desired without departing from the spirit and scope of the present invention.
Similarly, any type of paper product or other flammable material having a sufficient burning point may be utilized in place of, or in conjunction with, the shredded paper 16 without departing from the spirit and scope of the present invention. For example, wood chips, saw dust, burnable wax-type material, etc., may be added to the shredded paper 16 for burning purposes. The only requirement being that the material utilized in place of the shredded paper 16 be easily ignitable in order to start the fire within the container interior 14 . Similarly, the wood pieces 18 may be provided with a flammable wax material to aid in the ignition process. Still further, a flammable accelerate may be provided in the container interior 14 to aid in ignition and burning.
If desired, advertising media may be printed on the side surfaces 24 of the cardboard box 12 , providing a non-exhaustive list of uses the fire starting assembly 10 , or simply for decorative purposes.
While the present invention has been described with particular reference to the drawings, it should be understood that various modifications could be made without departing from the spirit and scope of the present invention.
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A fire starting assembly is provided in accordance with the present invention for easily lighting and maintaining a fire in an outdoor environment. The inventive fire starting assembly includes, in its simplest form, a combustible container defining an interior, and intermixed layers of flammable and combustible materials in the container interior having first and second burning points, respectively. To provide oxygen for the fire, the container includes holes for admitting air into the container interior, thus fueling the fire within the container interior.
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REFERENCE TO RELATED APPLICATION
This application is a division of co-pending application Ser. No. 08/840,065, filed Apr. 24, 1997.
BACKGROUND OF THE INVENTION
This invention relates to housings for electric motors and, more particularly, a motor housing having reduced weight and vibration transmission and improved mechanical damping, improved corrosion resistance and improved motor performance.
Conventional housings for electric motors are typically formed from fabricated cast or forged metal. The metals used in the housings include steel or corrosion resistant alloys. The damping properties, weight and other characteristics of the housing are a function of the materials used to construct the housing as well as the geometry of motor construction.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to provide an electric motor housing which has reduced weight and reduced vibration transmission.
It is also an object of the invention to provide an electric motor housing which absorbs or dampens vibration.
It is a further object of the invention to provide an electric motor housing which provides improved corrosion resistance and improves motor performance.
These and other objects of the invention are obtained by providing an electric motor housing including a substantially cylindrical housing member formed from a nonmetallic material having an inner metal cylinder or hub.
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and advantages of the invention will be more fully appreciated from a reading of the detailed description when considered with the accompanying drawings wherein:
FIG. 1 is a perspective view of the front end of a representative embodiment of a composite motor housing in accordance with the invention;
FIG. 2 is a longitudinal sectional view of a composite motor housing and rotor shaft arranged according to the invention;
FIG. 3 is a cross sectional view of the front end part of the motor housing taken along line III--III of FIG. 1 and looking in the direction of the arrows;
FIG. 4 is a side view of the front end part of the motor housing showing the side opposite from that shown in FIG. 1;
FIG. 5 is an end view of a pulley end housing the motor assembly shown in FIG. 2;
FIG. 6 is a cross-sectional view of the pulley end part shown in FIG. 5, taken along the line VI--VI of FIG. 5 and looking in the direction of the arrows;
FIG. 7 is an edge view of the front end part of the motor housing shown in FIGS. 5-6 and FIG. 8 is a sectional view of composite material laid around a metal cylinder and between two metal plates, respectively, in accordance with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in the representative embodiment illustrated in the drawings, the front end part 2 of an electric motor housing according to the invention is substantially cylindrical in shape and has a wall 4 which is formed from a composite material. The end part 2 includes a main bearing support for the motor drive shaft consisting of a metal hub sleeve 6 embedded in the composite wall 4 and bolt holes for assembly of the end part 2 into the motor housing.
In order to provide air cooling of the motor, vents or apertures 10 are provided in the composite wall 4. In addition, metal lifting lugs 12 in the end part 2 provide attachment points for lifting and rigging of the electric motor and pump assembly. Threaded metal inserts 14 are provided in the end wall 2 for a cover guard (not shown). Through holes 16, contain metal sleeves embedded in the composite wall, to act as a bearing surface for hold down fasteners (not shown in FIG. 1) for connecting the front end part 2 to the stator frame housing. A metal bottom plate 18 aligns the front end housing to the stator frame housing.
As shown in the upper portion of FIG. 2, which is a section view of the motor assembly, the front end housing part 2 is attached to a stator frame part 20 of the motor assembly which may be composed of metal and/or composite material. The stator frame part 20 is formed with vents 22 which, in cooperation with vents 10 in the front end housing, permit air to circulate through the motor housing. A metal bearing cap 24 is attached to the metal hub sleeve 6 to retain the rotor shaft thrust bearing 7. A rotor 26 for the motor is supported on a shaft 28 which is received in the metal hub 6. The shaft 28 contains both metal and composite resin material. Stator windings 30 are located within the stator frame part 20 to produce rotation of the rotor when energized. The output end of the motor housing has a pulley end housing 32 mounted on the other end of the stator frame which may also be made of composite material. The pulley end of the stator frame is equipped with a metal or composite mounting flange 34.
As shown in the sectional view of FIG. 3, the front end of the motor housing consists of a relatively large proportion of composite material, i.e. more than 50 percent, thereby making it lighter and easier to fabricate.
As best seen in FIG. 4, the front end housing part 2 of the motor assembly includes eight air inlet passages 10, which provide a cooling flow path for the motor.
A cut-away view taken along line VI--VI of FIG. 5 is shown in FIG. 6. Metal bushings 17 provide a bearing surface for the housing closure bolts. A main bearing hub sleeve 38 receives the metal hub sleeve 6. The hub sleeve 6 is mounted in to the composite material 4 with a threaded insert 40.
An edge view of the pulley end section of the motor housing is shown in FIG. 7. As can be seen from FIG. 7 the air vents 10 are located between the gussets 44.
A motor housing in accordance with the invention may be prepared by providing a metal cylinder 42, bonding composite plates 48 around the metal cylinder so as to form a metal within composite cylinder and then curing between metal plates 46 under full vacuum at a temperature of 300° F. for 360 minutes. Thereafter, the air passages are machined into the composite material.
The metal parts used in the motor housing can be formed of any suitable metal, preferably steel or corrosion resistant metal alloy. Suitable nonmetallic composite material includes but is not limited to composites made from resin with or without high strength, high modulus fiber such as fiberglass, graphite, carbon, boron, quartz and aramid fibers, i.e. aromatic polyamide fibers characterized by excellent high temperature, flame resistance and electrical properties.
The nonmetallic portions of the motor housing reduce weight and vibration transmission as compared to housings made of metal. The increased damping provided by the nonmetallic portions results in damping of vibrations. This damping minimnizes the detrimental forces imparted by a motor on the driven component as well as forces imparted by the driven component on the motor. The changes in stiffiness and inertia of the housing by the incorporation of nonmetallic materials results in increased absorption of vibratory energy.
Moreover, the motor housing according to the invention has improved corrosion resistance since nonmetallic composite material is inert in most environments, while housings made of steel or other metals arc subject to corrosion in certain environments.
The use of composite materials in a motor housing facilitates the fabrication of a motor with complex geometries and allows variation of motor damping along the length of the motor to further attenuate vibratory energy. Varying the thickness and fiber laying geometry in the composite housing may be used to control motor housing strength, stiffness and damping characteristics.
Although the invention has been described herein with respect to specific embodiments, many modifications and variations therein will readily occur to those skilled in the art. Accordingly, all such variations and modifications are included with the intended scope of the invention.
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An electric motor housing is made by press-forming a composite material on a metal cylinder and machining passages in the press-formed material. This reduces weight, reduces motor vibration transmission, increases mechanical damping, improves corrosion resistance and improves electrical performance.
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RELATIONSHIP TO OTHER APPLICATIONS AND PATENTS
[0001] The present invention draws priority from a U.S. Provisional Patent Application Ser. No. 60/503,436, filed Sep. 17, 2003.
BACKGROUND OF INVENTION
[0002] 1. Field of Invention
[0003] The present invention relates in general to marine pier systems which are resistant to damage caused by wave, wind or tidal action during violent storm events, and in particular to pier systems which may be partially disassembled during violent storm events to prevent damage thereto and may be reassembled after the storm event.
[0004] 2. Description of the Prior Art
[0005] One of the most common problems with piers used for marine pleasure craft and marine recreation is damage related to violent storms. A number of different storm-related damage problems can occur, including crushing and buckling of piers due to wind and wave action, that is, as high waves and wind continue to act against the pier the pier can be forced to move horizontally and vertically. As wave heights increase, the wave action can exert an upward force on the pier and result in the decking sections being separated from the support piles and/or deck planks separated from the decking. Such wave force can even exert enough upward force to cause the piles to be pulled free of the bottom. Floating debris can cause damage and destruction of property when wave and wind action drive floating debris into the pier. Also, as damage and destruction to the pier occurs, various pieces of the pier such as lumber, piles, decking section, etc. become separated from the pier. The pieces of debris then become hazards to humans and property as wind and waves continue to propel this debris throughout the vicinity.
[0006] A number of remedies are known in the art to avoid or at least minimize such storm-related damage. These include at least (1) heavy reinforcement of a pier to the extent that a storm is not capable of damaging the pier; (2) partial or complete removal of the pier from the water in advance of a storm; and (3) the installation of protection systems. The first option is inordinately expensive, and often aesthetically unacceptable. It is also sometimes environmentally unacceptable for large, bulky objects to be constructed in environmentally sensitive areas. The partial or complete removal of a pier from the water is also not completely acceptable in many instances. First, the removal of a pier and subsequent reinstallation of a pier into a body of water can be expensive and/or time consuming and could be a recurring unacceptable disturbance to environmentally sensitive areas. A third alternative for protecting piers from storm related damage is to install protective systems such as bumpers. However, in many instances these protective measures are inadequate to prevent storm-related damage.
[0007] U.S. Pat. No. 6,663,322 issued Dec. 16, 2003 to Listle discloses a pier system constructed of steel reinforced concrete piles with additional concrete footers and also includes embedding railing and deck support structures into the concrete piles. The pier system of Listle is fairly complex and does not easily lend itself to construction by those skilled in the art. In addition, the construction methods required to construct such a structure in a marine environment would require specialized construction skill and methods and would necessarily increase the cost far beyond what would normally be expected.
[0008] U.S. Pat. No. 6,128,880 issued Oct. 10, 2000 to Meenan, Jr. discloses a removable modular decking system that incorporates deck sections comprising decking planks that, by means of removable clamps, can be removed from the support structures of the pier. The decking planks are attached to rails that are located on the under side of the decking planks. When the clamps are disengaged the decking planks can then be rolled up and transported away from the pier. A major drawback, however, of the modular decking system of Meenan, Jr. is that the decking planks are inter-connected on the underside of the decking by means of the rail. This being the case, the decking sections would need to be removed from the pier and then turned up side down in order to facilitate rolling the sections up. A further disadvantage of the modular decking system of Meenan, Jr. is difficulty inherent in rolling up the modular decking sections if handrails are present on the dock. The presence of such handrails, if not constructed an adequate distance away from the decking sections, would prevent the decking sections from being rolled up. The construction of such a handrail would require detailed and difficult construction methods not normally employed in the construction of marine piers. In addition, another disadvantage of the modular decking system of Meenan, Jr. is that the rolling up, handling and transporting of decking sections would necessarily be difficult to accomplish and might easily require more effort and experience than most pier owners and users are capable of. In addition, the storage of so many large and bulky decking sections away from the pier may not be possible due to limited space. And, finally, unless the rolled up decking sections are either adequately anchored or otherwise protected, the storm surge typically associated with violent storm events near water may cause unwanted movement of the rolled up decking sections thereby causing unnecessary hazard to human health and wellbeing as well as potential damage to property.
[0009] In light of the foregoing problems, it is a principal object of the present invention to provide a pier system which is substantially immune to storm related damage and can be used year after year without the need to re-build the pier after each significant storm event.
[0010] It is a further object of the present invention to provide an economical pier system which is substantially immune to storm damage by allowing a plurality of decking sections to be automatically deployed, or disengaged, from the pile supports during storm events, and can be easily and quickly reassembled when the storm is gone.
[0011] It is a still further object of the present invention to provide a pier system that is easy to manufacture, install, operate and reassemble.
[0012] It is a still further object of the present invention to provide a pier system which employs tethers between decking sections and pile bents to prevent decking sections from being transported away from the pier during storm events.
[0013] It is a still further object of the present invention to provide a pier system that employs damage control systems to prevent damage to pile bents and decking sections while the decking sections are in the water.
[0014] It is a still further object of the present invention to provide a pier system which is made up of many substantially identical or modular parts, for economy of manufacture, and which can be constructed of different dimensions and materials for various locations and application of uses.
[0015] It is a still further object of the present invention to provide a pier system that will minimize damage to property by preventing or minimizing debris associated with destructive storm forces.
[0016] It is a still further object of the present invention to provide a pier system that will minimize hazard to human life during storm events by preventing or minimizing debris associated with destructive storm forces.
[0017] It is a still further object of the present invention to provide a pier system that will minimize insurance rates for insuring such pier systems by preventing or minimizing the need to re-construct piers after storm events.
SUMMARY OF THE INVENTION
[0018] Briefly described, a pier system in accordance with the invention comprises a plurality of decking sections mounted upon a plurality of pile bent sections and removably attached thereto by a plurality of selectively detachable attachment mechanisms. The system incorporates construction methods normally utilized for building marine piers. When in normal use mode, the pier system is equivalent in appearance and function to prior art conventional piers. When desired, as ahead of violent storm events, the decking sections may be intentionally unlatched from the pile bent sections by opening the attachment mechanisms and allowed to separate from the pile bent sections and float by way of wave, wind or tidal action. While in such deployed mode, the decking sections remain tethered to and near to the pile bent sections, and after the storm event has passed the deck sections may be easily placed back upon the pile bent sections and reattached using the original attachment mechanisms so that the pier is again in its normal use mode.
[0019] The selectively removable attachment mechanisms are for keeping the decking sections rigidly supported above the waterline by the pile bent sections when the system is in the normal use mode so that no movement of the decking sections, vertically or horizontally, is allowed. The attachment mechanisms, when unlocked, allow the deck sections to move relative to the pile bent sections so that the decking sections are free to move when influenced by tidal, wave or wind action, yet remain connected to the pile bent sections by a plurality of tethers. The tether means preferably include mechanisms or apparatus to connect one end of a tether to one decking section and the other end of the tether to a pile bent section or other anchor mechanism.
[0020] A currently-preferred method for making a pier system in accordance with the invention uses a plurality of substantially identical components. For example, ten or more substantially identical pile support systems and ten or more substantially identical decking sections are utilized. Each horizontal decking section is installed onto a pair of adjacent pile supports until the required length of structure is obtained. A plurality of substantially identical attachment mechanisms is then attached to the pile supports and decking sections as described above to secure the decking sections to the pile supports.
[0021] The specifics of my preferred method of making the pier system are described in detail below. These and other aspects, features, and objects and advantages of the present invention will become apparent to those skilled in the art upon studying the detailed description presented below along with the accompanying drawings and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The drawings form an integral part of the description of the preferred embodiments and are to be read in conjunction therewith. Like reference numerals designate the same or similar components or features in the various drawings, wherein:
[0023] FIG. 1 is a perspective view of two pile bents and one deck section of the new and improved pier system in deployed mode;
[0024] FIG. 2 is a perspective view of three pile bents and two deck sections of the new and improved pier system in normal use mode;
[0025] FIG. 3 is a front elevational view of a pile bent and deck section in normal use mode;
[0026] FIG. 4 is a front elevational view of a pile bent and deck section in deployed mode;
[0027] FIG. 5 is a side elevational view of two pile bents and a deck section in normal use mode;
[0028] FIG. 6 is a side elevational view of two pile bents and a deck section in deployed mode;
[0029] FIG. 7 is a detailed elevational front view of a currently-preferred embodiment of a selectively removable attachment mechanism in normal use mode;
[0030] FIG. 8 is a detailed side elevational view of the attachment mechanism shown in FIG. 7 ; and
[0031] FIGS. 9 through 12 are detailed side elevational views of the attachment mechanism shown in FIGS. 7 and 8 , showing a progression of attachment stages between fully engaged ( FIG. 8 ) and fully disengaged, or deployed, ( FIG. 12 ).
DETAILED DESCRIPTION OF THE INVENTION
[0032] With reference now to the drawings, and in particular to FIGS. 1 through 5 , there is shown a currently-preferred embodiment 14 of a new and improved tethered sectional pier system in accordance with the invention.
[0033] Pier system 14 comprises a plurality of components that in their broadest context include a plurality of pile bents 1 , a plurality of deck sections 5 , a plurality of tethers 8 , and a plurality of attachment mechanisms 9 . As described below, such components are individually configured and correlated with respect to each other so as to attain the desired objective.
[0034] First provided are a plurality of pile bents 1 which preferably are fabricated on-site from suitable materials, for example, steel pipe or treated wooden piling. Pilings 2 are installed into the lake or ocean bottom 20 as by driving, jetting, or other means. One or more, preferably two, horizontal support cross members 3 are then attached to and near the top of the pilings 2 . The horizontal support members 3 are attached to the pilings 2 by bolts, lag screws or other means 4 . The tops of the pilings are cut off at a height that will allow the decking section stringers 7 to rest on the top of the horizontal support members 3 .
[0035] Next provided is a plurality of decking sections 5 which may be fabricated on- or off-site and comprise two or more horizontal stringers 7 and a plurality of transverse planks 6 . The planks 6 are attached to the tops of the horizontal stringers 7 by nails, screws, or other means of attachment.
[0036] Next provided is a plurality of attachment mechanisms 9 that may be fabricated of metal, plastic, cable, wire, rubber webbing, binders or any other materials suitable to function as a means to rigidly but removably attach the deck sections 5 to the pile bents 1 and further function in normal use mode to prevent the deck sections 5 from being removed from the pile bents 1 by wave action, wind action, or tidal action. The attachment mechanism also prevents movement of the deck sections in any direction. The attachment mechanisms 9 are fabricated and installed in such a way as to allow the user of the tethered sectional pier system 14 to easily and quickly detach or unlock the deck sections 5 from the pile bents 1 in the event of an approaching storm. The attachment mechanisms preferably are fabricated off-site and are attached to the pilings 2 by means of an attachment anchor 13 . Such attachment anchors 13 are fabricated of metal, plastic or other materials. After attaching the attachment anchor 13 to the pilings 2 the opposite end of the attachment mechanism 9 is attached to the ends of two (2) adjacent deck sections 5 by means of additional attachment anchors 12 .
[0037] Next provided is a plurality of tethers 8 which preferably are fabricated off-site of cable, webbing, cord, rope or similar strong, flexible, durable material and can also include shock damping devices. The tethers 8 function to prevent the decking sections 5 from being carried away from the pile bents 1 by wave action, wind action or tidal action when system 14 is in deployed mode. Preferably, one end of each tether 8 is connected to a pile bent 1 by means of an attachment anchor 10 . Such anchor is fabricated of metal pins, eyebolts or other means installed on any part of the pile bent 1 such as a piling 2 or horizontal support member 3 . This end of the tether may also be connected to a seabottom-anchor device (not shown) that is separate from the pile bent. Such anchor device may be a conventional fluked anchor or it can be fabricated on or off-site of concrete, pilings, pipes or any configuration of materials that will provide sufficient anchorage into sea bottom 20 to achieve the objectives of the present invention. The opposite end of each tether 8 is connected to the end of a decking section 5 by means of an additional attachment anchor 11 .
[0038] With reference now to FIGS. 6 through 12 , a currently-preferred exemplary embodiment of a selectively detachable attachment mechanism generally designated by the reference numeral 9 is described. Other selectively detachable attachment means, of course, are fully comprehended by the invention.
[0039] Attachment mechanism 9 comprises a metal hold down bar 15 having two or more circular cut-outs 22 formed in bottom edge 24 to allow for positive and secure placement on the adjacent decking sections attachment points 12 . Attached to the metal hold down bar 15 is a top attachment cable 16 . The top attachment cable 16 can be fabricated of metal, plastic, rubber or other suitable materials capable of providing sufficient tensile strength to achieve the objectives of the present invention. The opposite end of the top attachment cable 16 is attached to the body of a lever binder 17 . The lever binder can be fabricated of metal, plastic, composites or any combination thereof, to achieve the objectives of the present invention. The lever binder 17 incorporates a handle 18 and is connected to a bottom attachment cable 19 similar to top attachment cable 16 . The bottom cable 19 is attached to an attachment anchor 13 installed on the pile. The pile attachment anchor 13 can be fabricated of metal, plastic or other materials.
[0040] Once the decking sections 5 have been placed onto the pile bents 1 , the attachment mechanisms 9 are installed and locked in normal use mode, as shown in FIG. 8 . While in this mode, the attachment mechanism 9 holds the decking sections rigidly in place by applying tension to the top attachment cable 16 and the bottom attachment cable 19 via a conventional over-center locking mechanism, thereby preventing vertical and horizontal movement of the decking sections.
[0041] Referring now to FIGS. 8 through 12 , upon the approach of a violent storm event each attachment mechanism 9 may be placed by an operator into deployed mode by rotating the lever binder lever 18 . When the lever binder lever 18 is rotated upward, tension is released on the bottom attachment cable 19 and top attachment cable 16 . Once the lever binder lever is fully rotated enough slack is created in the bottom attachment mechanism 19 and top attachment mechanism 16 to allow the metal hold down bar 15 to be completely removed from decking section attachment points 12 . Once the metal hold down bar 15 is removed from the decking section attachment points 12 the entire attachment mechanism 9 is then allowed to hang free while remaining connected to the pile 2 by attachment anchor 13 , as shown in FIGS. 1, 4 , and 12 . When the attachment mechanism 9 is hanging free of decking section 5 , the Tethered Sectional Pier 14 is deemed to be in a deployed mode. While in deployed mode, the decking sections 5 are free to move horizontally and vertically by means of wave, tidal or wind action while remaining contrained from loss by tethers 8 .
[0042] During a sufficiently violent storm event, the decking sections 5 will be lifted from the pile bents 1 by wave, tidal or wind forces, but decking sections 5 will remain tethered to the pile bents 1 by mean of tethers 8 described above. Once the storm event has passed, the decking sections 5 may be retrieved and placed back onto their respective pile bents 1 and the attachment mechanisms 9 returned to the normal use mode by placing the metal hold down bar 15 onto the adjacent decking sections attachment points 12 as in original assembly. The lever binder lever 18 is then rotated to its closed position to once again place the bottom attachment cable 19 and the top attachment cable 16 in tension. Once the attachment mechanism 9 is placed in the rigid or normal state and, therefore, tension is applied to the bottom attachment cable 19 and top attachment cable 16 the Tethered Sectional Pier 14 is said to be in the normal use mode.
[0043] With respect to the above descriptions then, it should be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function, and manner of operation, assembly, and use, will be readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are encompassed by the present invention. Therefore, the foregoing should be considered as illustrative only of the principle of the invention.
[0044] Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all modifications and equivalents as may be resorted to are to be considered as falling within the scope of the invention.
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A pier system having tethered deck sections that are selectively separable from supporting pile bents to prevent damage to the pier system during storm events. The pier system includes a plurality of deck sections supported above water by pile bents and engaged therewith in normal use mode by selective attachment mechanisms. In deployment mode, the attachment mechanisms are disengaged to allow the deck sections to be removed from the pile support systems by storm action. The tethers allow the decking sections to float free but remain close to the pile bents. The system may be reassembled into normal use mode following the storm event.
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BACKGROUND AND SUMMARY OF THE INVENTION
The use of high-dose methotrexate therapy with citrovorum factor, 5-formyl-5,6,7,8-tetrahydrofolic acid, (5-CHO-THF rescue is under active investigation for the treatment of a number of solid tumors and hematologic malignancies. The development of successful protocols will result in the need for larger amounts of citrovorum factor (5-CHO-THF).
By the present invention, there are provided improved methods for the preparation and purification of citrovorum factor. In one aspect of the invention, formylation of folic acid (FA) gave 10-CHO-FA, which was hydrogenated in trifluoroacetic acid to give high yields of (5, 10-CH-THF) + , the dehydration product of the initially formed 10-CHO-THF. In another aspect of the invention, the reduction of folic acid with borohydride followed by treatment of the resulting THF with formic acid gave good yields of (5, 10-CH-THF) + , isolated as the chloride. The effect of base concentration, temperature, and time of reaction on the conversion of (5, 10-CH-THF) + Cl - to 5-CHO-THF was determined. These methods led to the preparation of the calcium salt dihydrate of 5-CHO-THF in high yields, which was about 78% pure. The identification of the impurities in these 5-CHO-THF samples was determined by high-pressure liquid chromatography, and the removal of the impurities was effected by Florisil chromatography. The discovery of a nonchromatographic method for the removal of most of the impurities from crude samples of 5-CHO-THF is also described.
The decrease in toxicity and increase in therapeutic benefit resulting from the adjuvant treatment of osteogenic sarcoma with a high dose of methotrexate followed by rescue with citrovorum factor, 5-formyl-5,6,7,8-tetrahydrofolic acid, (5-CHO-THF) has been established by Jaffe et al., New Engl. J. Med., 291, 994 (1974). In this modality, 5-CHO-THF apparently protects normal sensitive tissue without canceling the inhibitory activity of methotrexate against neoplastic tissue. In addition, this form of therapy has been reported as being potentially effective against other malignancies, including refractory acute leukemia, bronchogenic carcinoma and head and neck cancer. Although the ultimate value in terms of cures of this form of therapy has not been fully documented, the development of the high-dose methotrexate regimen requires large amounts of both methotrexate and 5-CHO-THF. Recently, there has been reported by J.R. Piper and J.A. Montgomery, J. Heterocycl. Chem. 11, 279 (1974), an improved method for the large-scale synthesis of methotrexate of high purity, and we now report improved procedures for the large-scale preparation and purification of 5-CHO-THF.
The synthesis and identification of 5-CHO-THF was carried out about 25 years ago, as described, for example, by Pohland et al., J. Am. Chem. Soc., 73, 3247 (1951). In general, the adopted procedure involved the formylation of folic acid with formic acid, catalytic hydrogenation of the pyrazine ring of the resulting formic acid solution of 10-CHO-FA, and treatment of the product of the reduction with base at elevated temperatures to give crude 5-CHO-THF. In one procedure, bioassay of the crude product indicated that about a 22% yield of 5-CHO-THF was obtained. Purification was effected by column chromatography to give a low yield of 5-CHO-THF isolated as the barium salt pentahydrate. Although no yields were reported, a similar procedure was used for the preparartion of the calcium salt of 5-CHO-THF.
In the prior art synthesis described above, it was recognized that 5-CHO-THF was dehydrated under acidic conditions to give (5, 10-CH-THF) + and that the same product was formed from 10-CHO-THF resulting from the hydrogenation of 10-CHO-FA in formic acid. Treatment of (5,10-CH-THF) + with base at room temperature opened the imidazolinium ring to give mainly 10-CHO-THF (kinetic control), which underwent oxidation readily in the presence of oxygen and light to give decomposition products, as described by May et al., J. Am. Chem. Soc., 73, 3067 (1951). In contrast, treatment of (5,10-CH-THF) + with base at higher temperatures resulted in the formation of 5-CHO-THF (thermodynamic control) and decomposition products.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the procedures according to the present invention, the first approach which was carried out including treatment of folic acid with 98% HCO 2 H under N 2 at 60° to give give 10CHO-FA, which was purified by recrystallization from H 2 O. All temperatures as stated herein are in degrees Centigrade. As was noted in the Pohland et al reference cited above, considerable difficulty was encountered in the hydrogenation of 10CHO-FA in HCO 2 H, with this reduction requiring more than 40 hr for the uptake of 2 molar equivalents of H 2 in the presence of platinum at room temperature and atmospheric pressure. Because of these results, conditions were sought for the reduction of 10-CHO-FA tp give 10-CHO-THF, which might undergo in situ rearrangement to give 5-CHO-THF. In the hydrogenation of 10-CHO-FA in pyridine in the presence of Pd, 2 molar equivalents of H 2 appeared to be absorbed within 5 hr; however, the recovery of 10-CHO-FA from this reaction indiated that hydrogenation of the solvent rather than the pyrazine ring of 10CHO-FA had occured. Based on the successful chemical reduction of folic acid to THF with Na 2 S 2 O 4 , the reduction of 10-CHO-FA with this reagent was attempted. However, treatment of solutions of 10-CHO-FA in aqueous pyridine and in water at pH 6, 7, and 8.5 with Na 2 S 2 O 4 at 75° resulted in the formation of complex mixtures (TLC), which were not examined further. In addition, treatment of 10-CHO-FA either at room temperature with excess aqueous NaBH 4 (alkaline medium) or with refluxing aqueous NaBH 3 CN at pH 6.7 resulted in extensive decomposition of the sample with little or no conversion to 5-CHO-THF. Although treatment of 10-CHO-FA with an equal weight of NaBH 4 while maintaining the pH of the medium near 8 with HOAc followed by refluxing the reaction mixture after adjustment to pH 6.7, as described hereinbelow, gave a mixture containning 5-CHO-THF, the mixture contained a large amount of unreduced 10-CHO-FA. These difficulties were circumvented by the catalytic hydrogenation of 10-CHO-FA in CF 3 CO 2 H containing prereduced PtO 2 , which was more than 20 times faster than the hydrogenation of 10CHO-FA in HCO 2 H.
Next, the formylation and hydrogenation of folic acid without isolation of 10-CHO-FA was carried out. The solution of 10CHO-FA in HCO-FA in HCO 2 H resulting from the formylation of folic acid was diluted with an equal volume of CF 3 CO 2 H and hydrogenated in the presence of prereduced PtO 2 (20% by weight of folic acid). The absorption of H 2 was slower than expected, and the reaction was repeated by removing the formic acid after formylation and using a smaller amount of catalyst, 5% by weight of folic acid. Under these conditions, the catalyst appeared to be poisoned after the uptake of 1 molar equivalent of H 2 , but the reduction returned to the original rate after the addition of either freshly reduced PtO 2 (total 7.5% by weight of folic acid) or additional solvent. Based on these results, large-scale preparations were carried out by the formylation of folic acid with HCO 2 H, recovering the HCO 2 H by distillation in vacuo, and dehydrogenation of the resulting dried residue in CF 3 CO 2 H containing prereduced PtO 2 (5% by weight of folic acid) at room temperature and atmospheric pressure. Although it was found that CF 3 CO 2 H was reduced by Pt, the reaction was slower than the reduction of 10-CHO-FA. In addition, none of the reduction products from CF 3 CO 2 H appeared to interfere either with the hydrogenation of 10-CHO-FA or the isolation of its reduction product. Both the solvent and catalyst could be recovered and reused at least five times.
Although the hydrogenation of 10-CHO-FA in CF 3 CO 2 H probably gave 10-CHO-THF initially, this compound was readily dehydrated by the solvent. The resulting product was an acylated derivative (either formyl or trifluoroacetyl or both) of (5, 10-CH-THF) + , isolated as a foam, which was converted by dissolution in 0.5 N HCl and concentration of the resulting solution to give a precipitate of practically pure (5, 10-CH-THF) + Cl - . The obtainment of this product in an amount equal to the weight of the folic acid starting material indicated almost quantitative conversion in each step of the reaction sequence.
As a variation of the above approach, the large-scale reduction of folic acid to THF was investigated. Previously, the reduction of folic acid with borohydride gave a mixture of unreacted folic acid, DHF, and THF, the latter in yields up to 50%. Preliminary experiments indicated that an amount of sodium borohydride equal to the weight of folic acid was necessary to ensure complete reduction. To circumvent the use of a buffered medium, the reduction was carried out by the portionwise addition of an aqueous solution of NaBH 4 while maintaining the pH of the reaction medium near 8by the addition of dilute HCl. However, some oxidation of the product occurred upon acidification of the reaction mixture to precipitate THF. Additional experiments revealed that the addition of HCl during the reduction was unnecessary as the system became buffered with borate at a pH of less than 10. The reoxidation of the THF during the isolation was prevented by the addition of ascorbic acid during the acidification, which gave THF as a boron complex in 96% yield.
The direct conversion of the free acid of THF to 5-CHO-THF was effected with a refluxing 95:5 mixture of pyridine-HCO 2 H containing ascorbic acid. However, after a basic workup, the isolated CF contained a considerable amount of 10-CHO-DHF (TLC,HPLC), and no further work was carried out on this method.
Treatment of the THF product with either HCO 2 H or 2:1 HCO 2 H--CF 3 CO 2 H at room temperature gave mainly (5,10-CH-THF) + . Similarly, the same product resulted from the condensation of THF with (EtO) 3 CH either in the presence of HCl at room temperature or in the presence of aqueous ascorbic acid at reflux. The yields and purity of the product appeared to be better in the procedures using HCO 2 H, and the adopted procedure involved the dissolution of the precipitated THF directly in 98:2 HCO 2 H--CF 3 CO 2 H, which provided (5,10-CH-THF) + free of boron impurities. This procedure was improved by elimination of the step involving the isolation of THF. Treatment of the aqueous solution (pH 7) of THF resulting from the NaBH 4 reduction of FA with an equal volume of HCO 2 H resulted in the isolation of a good yield of (5,10-CH-THF).sup. + CL - .
On TLC many of these samples of (5,10-CH-THF) 30 Cl - exhibited trace amounts of colored fluorescent impurities, which were removed by column chromatography. This imidazolinium chloride appeared to be stable in the solid state and in acidified aqueous solution, but, as noted above, was unstable in the presence of aqueous base. Additional information on the transformation of (5,10 -CH-THF) + Cl - in solutions was provided by the uv spectrum of the eluted peaks obtained on the chromatograms produced by high-pressure liquid reverse-phase chromatography.
When (5,10-CH-THF) + Cl - was dissolved in pH 5 buffer, a mixture of 10-CHO-DHF, (5,10-CH-THF) + , and 5-CHO-THF was formed. Presumably, (5,10-CH-THF) + was converted to 5,10-(HOCH)-THF, which underwent different modes of ring opening to give a small amount of 5-CHO-THF and a large amount of 10-CHO-THF followed by air oxidation of the latter to give 10-CHO-DHF. No 10-CHO-DHF was formed when (5,10-CH-THF) + was dissolved in pH 5 buffer containing ascorbic acid, the resulting solution exhibiting peaks only for (5,10-CH-THF) + and 5-CHO-THF. In contrast, the chromatogram of a solution of (5,10-CH-THF) + at pH 7 in the presence of ascorbic acid showed only a small amount of 10-CHO-DHF and two new peaks, which were tentatively assigned to 10-CHO-THF and 5,10-(HOCH)-THF. A later chromatogram of this solution showed that both of the peaks assigned to 10-CHO-THF and 5,10-(HOCH)-THF decreased with time while the 10-CHO-DHF peak increased even in the presence of ascorbic acid. The possibility was not eliminated from consideration that the peak assigned to 5,10-(HOCH)-THF was a tautomeric form of 10-CHO-DHF formed initially in the oxidation of 10-CHO-THF.
A solution of (5,10-CH-THF) + -Cl - at pH 13 containing ascorbic acid showed only the peak assigned to 10-CHO-THF. Although the uv spectrum of this peak was similar to that of 10-CHO-DHF, this resulted from 10-CHO-THF being converted rapidly to 10-CHO-DHF in the uv cell by uv radiation. This transformation was followed by measuring the increase in absorbance at a wavelength (330 nm) where 10-CHO-DHF gave a maximum after the peak was eluted from the column. Surprisingly, treatment of (5,10-CH-THF) + Cl - with base at pH 11 with no protection from O 2 gave a high yield of 10-CHO-THF, which was isolated as its calcium salt. The structure of the latter was confirmed by its reconversion to (5,10-CH-THF) + Cl - in an acidic medium (uv). Further treatment of 10-CHO-THF in a basic medium, however, resulted in the formation of a mixture of 10-CHO-DHF, 10-CHO-FA, and decomposition products. The obtainment of a purified sample of 10-CHO-DHF by elution of this mixture from a Florisil column with 0.1 M mercaptoethanol was unsuccessful because most of the sample decomposed on the column. Not only was the weight of the recovered material low (15%), but HPLC showed that the 10-CHO-DHF obtained was contaminated with p-aminobenzoylglutamic acid, pterins, and unidentified substances.
Previously, the (5,10-CH-THF) + prepared in situ was converted to 5-CHO-THF in a hot, neutral or alkaline medium with a reaction time of about 1 hour. The solid (5,10-CH-THF) + Cl - prepared above was used in small-scale experiments to determine the effect of base concentration, temperature, and time of reaction on the purity of the 5-CHO-THF obtained. The progress of the reaction was followed by the determination of the uv spectrum of aliquot portions in 0.1 N NaOH and comparison of the λ max 282/ λ min 242 ratio with that observed in the isolated sample of 5-CHO-THF. The uv data indicated that the ratio increased faster at the higher pH values, but also indicated that the ratio reached a maximum and then decreased. In addition, carrying out the reaction in a pressure apparatus at higher temperatues increased the rate of formation of citrovorum factor, but offered no advantage in regard to the purity of the product.
In one reaction in which the initial pH was 8.3 and the final pH 5.9, the same ratio was observed for the last aliquot portion and the isolated product suggesting that the reaction mixture was at equilibrium. In this reaction, a 75% increase in absorbancy at 282 nm occurred within 2.5 hours followed by a smaller increase over the remaining time of the experiment. A log A vs. time plot suggested that the conversion involved two sequential first-order reactions: possibly the transformation of (5,10-CH-THF) + via 5,10-(HOCH)-THF to 5-CHO-THF and 10-CHO-THF followed by the reversible transformation of 10-CHO-THF via 5,10-(HOCH)-THF to 5-CHO-THF, a reaction that would be expected to predominate in the latter part of the conversion.
A highly significant result of this study was the discovery that the rate of opening of the imidazolinium ring of (5,10-CH-THF) + was reasonable and that the purity of the 5-CHO-THF formed was greatest when the reaction was performed under neutral or slightly acidic conditions, at a pH of about 6.2 to 7.0. The latter result was confirmed in reactions with (5,10-CH-THF) + at pH 11.4, 9, and 6.2 to give 5-CHO-THF of increasingly greater purity. However, experiments carried out in dilute solutions of 5-CHO-THF at 100° for 7 hours over the pH range 6.5-5.5 showed that increasing amounts of 10-CHO-DHF, 10-CHO-FA, and p-aminobenzoylglutamic acid (PABGA) were formed as the pH was decreased. For the large-scale synthesis of 5-CHO-THF from (5,10-CH-THF) + Cl - in concentrated solutions, the pH of the reaction medium was maintained near 6.7 for about 11 hours, which gave a product with a uv ratio of 3.4-3.9. These samples of 5-CHO-THF contained 10-CHO-DHF and PABGA as the major impurities and 10-CHO-FA and pterins as minor impurities. On TLC (5,10-CH-THF) + , 10-CHO-DHF, and 10-CHO-FA were detectable at less than 5% of the concentration of 5-CHO-THF. The major portion of the 10-CHO-DHF impurity in 5-CHO-THF samples was formed from unconverted (5,10-CH-THF) + and 10-CHO-THF during the basic workup of the reaction.
The calcium salt of 5-CHO-THF appeared to have little or no solubility in anhydrous organic solvents; in fact, the salt was reprecipitated from an aqueous solution on the addition of DMAC. Also, recrystallization of the salt from a saturated solution of CaCl 2 and fractional precipitation of the salt from water-ethanol mixtures was unsatisfactory for the preparation of purified samples. In addition, the preparation of a purified sample of 5-CHO-THF by column chromatography was unsuccessful with the following packings: cation spherical resin developed with 0.1 M CaCl 2 --Ca(OH) 2 (pH 10); cation exchange cellulose developed with 0.1 M CaCl 2 --HCl (pH 5.5); Avicel cellulose developed with 0.1 M CaCl 2 (pH 8); silica gel H developed with 7:3 H 2 O-acetone under water pressure; polyethylene powder developed with 3:1 H 2 O-acetone; and Sephadex G-75 developed with H 2 O (pH 8). Practically pure 5-CHO-THF was obtained from crude samples by column chromatography on Sephadex G-10 developed with aqueous Ca(OH) 2 (pH 8), as further described hereinafter. A better method, however, was the column chromatography of crude samples on Florisil developed with aqueous mercaptoethanol, which gave 5-CHO-THF in 28-35% yield (from FA). These samples were shown by HPLC to contain only trace amounts of uv-absorbing impurities.
As a further aspect of the present invention, a nonchromatographic procedure was developed for the removal of most of the impurities from crude 5-CHO-THF samples. A solution of the sample in water containing magnesium chloride was adjusted to pH 12 with calcium hydroxide to produce a precipitate of the inorganic oxides, most of the impurities, and some 5-CHO-THF. From the filtrate 5-CHO-THF of good quality was recovered. This method is potentially the most convenient procedure for the purification of 5-CHO-THF.
The various reactions which take place in accordance with the present invention are indicated in the following diagram. ##STR1##
EXAMPLE 1
10-Formylfolic Acid (10-CHO-FA)
A mixture of FA· 2H 2 O (30.0 g. 62.8 mmol) and 98% HCO 2 H (400 ml) was stirred under N 2 in a 60° oil bath for 2 hours. The resulting solution was evaporated to dryness under reduced pressure, and the residue was dried in vacuo over P 2 O 5 and NaOH pellets for 18 hours to give a dry, glassy material: yield, 37.2 g. λ max , nm: 0.1 N HCl--252, 322; pH 7--260, 349; 0.1 N NaOH--257, 365. Pmr (DMSO-d 6 , 5.5% g/ml)--δ8.14 (CHO moiety, position unidentified), 8.63 (7-CH), 8.79 (10-CHO). TLC [Avicel, 0.1 M phosphate buffer (pH 7)]--Rf˜0.85 (fluorescent).
In a 1.0-g run the isolated residue was recrystallized from hot H 2 O (110 ml) to give the monohydrate: yield, 0.57 g (56%). This sample underwent decomposition from about 200°. λ max , nm (ε×10 -3 ): 0.1 N HCl--252 (26.5), 322 (8.69); pH 7--249 sh (24.3), 263 br (25.6), 348 (6.15), 357 sh (5.81); 0.1 N NaOH-257 (39.0), 367 (7.62). ν max , cm -1 : 1680 br. Pmr (DMSO-d 6 , 4.3% g/ml)--δ 8.63 (7-CH), 8.79 (10-CHO).
Anal. Calcd for C 20 H 19 N 7 O 7 ·H 2 O: C, 49.28; H, 4.34; N, 20.12. Found: C, 49.12; H, 4.27; N, 19.97.
EXAMPLE 2
Calcium 10-Formyl-7,8-dihydrofolate
A suspension of (5,10-CH-THF) + Cl - (10.0 g) in H 2 O (315 ml) was stirred and treated with 1 N NaOH (˜85 ml) to give a clear yellow solution (pH 11, meter). After stirring at room temperature with free access to air for 2 hours, the solution was adjusted to pH 7.5 with dilute HCl followed by the addition of a clarified solution of CaCl 2 (2.5 g/5 ml), and EtOH (150 ml). The yellow precipitate (0.6g) that deposited was removed by filtration, and the filtrate was diluted with an additional amount of EtOH (800 ml). The resulting pale yellow precipitate was collected by filtration and dried in vacuo over P 2 O 5 : yield, 9.74 g. The uv spectrum indicated that this solid was mainly calcium 10-formyl-5,6,7,8-tetrahydrofolate. λ max , nm (ε×10 -3 ): pH 7 (1% mercaptoethanol)--257 (18.8), 3.05 sh (6.12), 340 sh (2.85). After 24 hours this solution gave the following spectrum: 262 (17.5), 305 sh (7.56), 340 sh (3.60).
Anal. Calcd for C 20 H 21 N 7 O 7 · Ca·0.75 C 2 H 6 O·2H 2 O: C, 44.36; H, 5.11; N, 16.84; Ca, 6.89; Ash (CaO), 9.65. Found: C, 44.69; H, 4.91; N, 17.06; Ca, 6.82; Ash (CaO), 10.17.
A portion of the above solid (5.0 g) was dissolved in H 2 O (500 ml), and the solution (pH 7.4) was stirred in the presence of air at room temperature for 18 hours. During this period, a yellow solid deposited as the pH of the solution dropped to 6.7. The solid was collected by filtration and dried in vacuo over P 2 O 5 : yield, 0.76 g. The 1 H NMR spectrum, elemental analysis, and HPLC assay of this sample showed that it was a 2:1 mixture of the calcium salts of 10-formyl-7,8-dihydrofolate and 10-formylfolic acid. λ max , nm (ε×10 -3 ): pH 7--233 (30.8), 260 sh (22.8), 266 sh (22.3), 335 (6.68). TLC [Avicel, 0.1 M phosphate buffer (pH 7)]--R f 0.70 (10-CHO-DHF), 0.86 (10CHO-FA) (both fluorescent).
Anal. Calcd for (C 20 H 19 N 7 O 7 ) 2 (C 20 H 17 N 7 O 7 )·Ca·2H 2 O: C, 44.09; H, 4.13; N, 18.00; Ca, 7.36; Ash (CaO), 10.30. Found: C, 44.18; H, 4.10; N, 17.99; Ca, 7.33; Ash (CaO), 9.93.
Dilution of the filtrate from the above solid with EtOH gave a mixture of the salts of 10-formyl-7,8-dihydro- and 10-formylfolic acids (3.21 g) that was contaminated with other impurities (p-aminobenzoylglutamic acid, pterins).
EXAMPLE 3
5,6,7,8-Tetrahydrofolic Acid
To a suspension of folic acid dihydrate (47.8 g, 100 mmol) in deaerated H 2 O (1,000 ml), which was cooled in an ice bath, was added slowly with stirring 50% NaOH (10.5 ml). The resulting dark yellow solution (pH 8.0, meter) was treated over a 10-min period with a solution of NaBH 4 (58 g) in H 2 O (150 ml). The solution was stirred for an additional 30 min, the pH increasing during this period from 8.4 to 8.8. Excess NaBH 4 was decomposed by the addition of 6 N HCl (caution, vigorous effervescence) until the pH of the solution was 6.8. Solid ascorbic acid (5 g) was added and stirring continued until complete dissolution occurred. The resulting solution was adjusted to pH 3.7 with 6 N HCl (total volume, 165 ml). The cream-colored precipitate was collected by filtration under N 2 , washed with ice cold HCl (pH 3.5, 200 ml) containing ascorbic acid (2 g) and dried to constant weight in vacuo over P 2 O 5 at room temperature: yield, 60.0 g (96%). Solutions for the uv spectra determinations were obtained by dissolution of tetrahydrofolic acid (5.5 mg) by the successive addition of mercaptoethanol (2.5 ml) and water (22.5 ml) and dilution of the resulting stock solution with the appropriate priate solvent (5→ 50 ml). λ max , nm (ε × 10 -3 ): 0.1 N HCl--270 (23.5 ), 292 (20.8); pH 7--297 (25.7); 0.1 N NaOH--297 (25.9). TLC [DEAE cellulose: 0.005 M KH 2 PO 4 + 0.5 M NaCl + 0.2 M mercaptoethanol (pH 7)] --R f ˜0.44 (elongated).
This sample analyzed for the following composition;
Anal. Calcd for C 19 H 7 O 6 ·1·66HCl·1·68H 3 BO 3 ·0·74H 2 O: C, 36.66; H, 5.04; B, 2.92; Cl, 9.45; N, 15.75. Found: C, 36.69; H, 5.20; B, 2.89; Cl, 9.45; N, 15.66.
EXAMPLE 4
Calcium Salt of Citrovorum Factor
The combined crops of (5,10-CH-THF) + Cl - (1212 g), prepared as described below, were added with stirring under a N 2 atmosphere to boiling H 2 O (30 l.) over a period of 20 minutes. During the addition and thereafter for 1 hour, hot, oxygen-free 3.7 NaOH (˜21) was added at a rate to maintain an acidic reaction medium. At this point, complete dissolution of the solid was obtained with oxygen-free 1 N NaOH. The resulting solution was refluxed for 11 hours while maintaining the pH between 6.5-6.9 (meter) with 1 N NaOH (total, ˜450 ml). The progress of the reaction was followed by determining the HPLC chromatograms of aliquot portions. After standing for an additional 8 hours without heat, the solution (56°, pH 7.7) was treated with a clarified solution (1200 ml) of CaCl 2 (600 g), which lowered the pH to 7.2. The solution was diluted with EtOH (3.2.1) and transferred through tygon tubing with a peristaltic pump to a flask cooled in an ice-salt mixture. When the temperature of the mixture was less than 10°, the bright yellow solid that deposited was removed by filtration. On exposure to air, this solid darkened to a brown color and became gummy. TLC of the semidried residue (˜400 g) showed that it contained 5-CHO-THF contaminated with numerous impurities. Further work on the characterization of this residue is described in the section of the nonchromaographic purification of 5-CHO-THF.
The clear yellow filtrate from above was pumped into a large container and diluted with EtOH (total, 102.1). The resulting slurry of cream-colored precipitate of 5-CHO-THF·Ca was cooled (<10°) in an ice bath for 18 hours, the solid was collected by filtration, washed with EtOH (7 l.) and dried in vacuo over P 2 O 5 : yield, 897 g (˜45% from FA). λ max , nm (ε× 10 -3 ): 0.1 N NaOH-282 (28.8) [λ max 282 /λ min 242 (0.1 N NaOH), 3.6]. TLC [Avicel, 0.1 M phosphate buffer (pH 7)--R f 0.76 (10-CHO-DHF),
Anal. Calcd for C 20 H 21 N 7 O 7 ·Ca·0.5C 2 H 6 O·1.8H 2 O: C, 44.49; H, 4.91 ; N, 17.29; Ca, 7.07; Ash (CaO), 9.89. Found: C, 44.49; H, 4.97; N, 17.29; Ca, 7.18; Ash (CaO), 9.65.
HPLC assay of this sample indicated the presence of 5-CHO-THF·Ca (78%) and, excluding ethanol and water, the following impurities; PABGA·Ca (3.1%), 10-CHO-DHF (4.6%), 10-CHO-FA (<0.5%) pterins (1.0%) and unidentified and undetected material (3.0%).
EXAMPLE 5
5,10-Methenyl-5,6,7,8-tetrahydrofolic Acid (5,10-CH-THF) + (A)
A suspension of PtO 2 (1.50 g) in CF 3 CO 2 H (600 Ml) was hydrogenated at 24° and atmospheric pressure until the theoretical volume (322 ml) of H 2 was absorbed (< 5 min). To this mixture was added a solution of crude 10-CHO-FA (37.1 g, from 30 g FA) in CF 3 COH 2 H (900 ml), and the whole was hydrogenated with rapid magnetic stirring at 24.5° and atmospheric pressure. Within 2.5 hours, the theoretical amount of H 2 was absorbed (3,095 ml). The resulting mixture was filtered (Celite) under N 2 pressure, and the filtrate was evaporated at less than 40° under reduced pressure to give a dry, porous foam. After drying this sample for 18 hours over P 2 O 5 , the foam was dissolved in 0.5 M HCl (200 ml) that was 0.1 M in 2-mercaptoethanol. The dark solution was warmed to 40° (H 2 O bath), treated with charcoal (0.5 g), and filtered (Celite). The filter pad was washed with the 0.5 M HCl-0.1 M mercaptoethanol solvent (100 ml) and the clear yellow filtrate was concentrated at 40° to 2/3 volume under aspirator vacuum. The resulting mixture was cooled: the yellow solid of the chloride salt was collected by filtration, washed with the 0.5 M HCl-0.01 M mercaptoethanol solvent (25 ml), and dried in vacuo over P 2 O 5 and NaOH pellets for 18 hours; yield, 29.9 g. λ max , nm: 1 N HCl--286, 347 (A max 347 ; A min 302 = 2.60; lit. A max 348 /A min 305 = 2.46). ν max , cm -1 ; 1730, 1655 sh, 1630, 1620 sh. Pmr (Cf 3 CO 2 D, 5.3 % g/ml), δ 9.57 (methenyl CH). TLC [Avicel, 0.1 M phosphate buffer (pH 7)] showed an elongated bluish-white fluorescent spot at R f 0.47 and a yellow fluorescent impurity spot near the origin. Concentration of the filtrate to about 20 ml from the first crop gave a dark colored solid: yield 0.9 g. TLC indicated that this sample contained more of the yellow fluorescent impurity. In this hydrogenation both the catalyst and solvent could be recovered and reused at least 5 times.
The yellow fluorescent impurity in crude (5,10-CH-THF) + Cl.sup. - from another run was removed by column chromatography. This sample (0.50 g ) was eluted at a rate of 6 ml/10 min from an Avicel (75 g) column with HCl (pH 2.3) that was 0.01 M in 2-mercaptoethanol. Fractions 20-25, which contained crystalline (5,10-CH-THF) + CL - , were combined and concentrated in vacuo below room temperature to a thick slurry. The yellow solid was collected by filtration under N 2 , washed with EtOH and Et 2 O, and dried in vacuo over P 2 O 5 for 18 hours; yield, 0.24 g (48% recovery). λ max , nm (ε× 10 -3 ); N NCl--286 (12.4), 347 (25.8) [A max 347 /A min 303 = 2.57]. λ max , cm -1 1730, 1660 sh, 1630 br. Pmr (CF 3 CO 2 D, 5.3% g/ml), 67 9.56 (Methenyl CH). TLC [DEAE cellulose; 0.005 M phosphate buffer, 0.5 M NaCl, 0.2 M mercaptoethanol (pH 7)] showed one major spot and a trace amount of a lower absorbing impurity spot.
Anal. Calcd for C 20 H 22 CLN 7 O 6 · 0.1HCl·H 2 O: C, 46.78; H, 4.73; Cl, 7.59; N, 19.09. Found C, 46.87; H, 4.79; Cl, 7.50; N, 18.99.
Fractions 26-42 from the above column were treated in the same manner: yield 0.14 g (28% recovery). λ max , nm: 1 N HCl-286, 347 [A max 347 /A min 303 = 2.62]. TLC of this sample was similar to the first crop. The total amount recovered was 0.38 g (76%).
In another run a sample of crude (5,10-CH-THF) + Cl - (100 mg) was eluted at a rate of 4 drops/min from an Avicel (15 g) column (1× 55 cm) with 0.1 M HCO 2 H-0.01 M mercaptoethanol. Twelve fractions (5 ml each ) were collected in which fractions 5-7 deposited crystalline product. These fractions were combined and cooled; the solid was collected by filtration, washed with 0.1 M HCO 2 H-0.01 M mercaptoethanol, and dried in vacuo over P 2 O 5 ; yield, 12 mg (12% recovery). This material was homogeneous on TLC (DEAE cellulose). The mother liquor from this sample and fractions 4 and 8-12 were combined and evaporated to dryness. The resulting residue (70 mg) was recrystallized from 0.1 M HCO 2 O-0.01 M mercaptoethanol; yield, 35 mg (35% recovery). λ max , nm (ε × 10 -3 ); 1 N HCl--286 (12.1), 347 (25.5) ]A max 347 /A min 303 = 2.60]. This material was homogeneous on TLC; however, elemental analyses indicated that this material was a mixture of the chloride (34%) and the corresponding meso-ionic compound (66%).
Anal. Calcd for [34% [(C 20 H 22 N 7 O 6 ) + Cl - ]·66% (C 20 H 21 N 7 O 6 )]·3H 2 O: C, 46.03; H, 5.28; Cl, 2.31; N, 18.79. Found: C, 46.00; H, 5.20; Cl, 2.37; N, 18.57.
(B) To a suspension of FA·2H 2 O (1673 g, 3.500 mol) in H 2 O (35 1.) which was under an atmosphere of N 2 and cooled to 8° in an ice bath, was added slowly with stirring 50% NaOH (370 ml). The resulting clear yellow solution (pH 8, meter) was treated over a one-hour period with a solution of NaBH 4 (1673 g) in H 2 O (5 l.). During the addition, the temperature increased to a maximum of 17°. The solution was stirred for an additional 30 minutes, followed by the decomposition of excess MaBH 4 with concd HCl. The large amount of H 2 generated was vented to a hood. During the first half of the decomposition step, efficient cooling was required to maintain the temperature of the solution below 24°. The decomposition of NaBH 4 was essentially complete after the addition of 2000 ml of concd HCl, which required a period of 3 hours. The resulting solution (pH 8.3) was adjusted to pH 6.6 with 500 ml of concd HCl over a period of 30 minutes. At this point, a solution of ascorbic acid (175 g) in H 2 O (800 ml) was added to protect THF against air oxidation. The pH of the solution was then adjusted to 3.5 with an additional 1800 ml of concentrated HCl over a period of one hour. The resulting cream-colored suspension of THF was pumped into a Buchner funnel (11-l. capacity) fitted with a glass fiber paper (Whatman GF/D) and under an atmosphere of N 2 . This filtration (aspirator pressure) was carried out in two batches because of the large amount of solid. Near the end of the filtration, a small portion (˜ 50 g) of the THF slurry was exposed to air and was discarded. Each batch of the wet precipitate was dissolved in a mixture of 98:2 HCO 2 H (97%)-CF 3 CO 2 H and transferred under aspirated vacuum to a 24-l. flask. A total volume of 12,750 ml of the acid mixture was used. After standing at room temperature for 14 hours, the dark red solution was evaporated to dryness in vacuo at a maximum H 2 O-bath temperature of 60°. The superficially dried residue was suspended in 0.5 N HCl (35 l.) containing 2-mercaptoethanol (1 ml/l. of acid), warmed to 45°, and the whole was concentrated under aspirator pressure to remove formic and trifluoroacetic acids (˜3 l.). After standing at room temperature for 18 hours, the (5,10-CH-THF) + Cl - was collected by filtration on a glass fiber paper, washed with 0.01 N HCl (6 l.), and dried in vacuo over P 2 O 5 : yield, 1119 (63%). A boron analysis indicated the absence of boron salts.
Anal. Calcd for (C 20 H 22 N 7 O 6 ) + Cl - ·H 2 O: C, 47.11; H, 4.74; Cl, 6.75; N, 19.23. Found; C, 47.24; H, 4.65; Cl, 7.16; N, 19.28.
Concentration of the filtrate to about one-third the original volume deposited a second crop, which was less pure (5,10-CH-THF) + Cl - : yield, 95 g (˜ 5%). The total yield was 1214 g (˜68%).
Modification of the procedure described above gave a higher yield of (5,10-CH-THF) + Cl - . FA·2H 2 O (10.0 g, 20.9 mmol) was treated with NaBH 4 , the excess NaBH 4 was decomposed, and the resulting solution (pH 7) was diluted with 95% HCO 2 H (270 ml). During the addition of HCO 2 H, a precipitate of 5,6,7,8-tetrahydrofolic acid was formed, which redissolved rapidly as the volume of HCO 2 H increased (final pH, 1.1). After standing for 18 hours at room temperature, an inorganic precipitate (5.6 g) was removed by filtration. The filtrate was treated with concentrated HCl (3.5 ml) and evaporated to dryness under reduced pressure at 40°. The resulting solid was washed by stirring with cold 1% ascorbic acid (100 ml), collected by filtration, washed with additional 1% ascorbic acid solution, and dried in vacuo over P 2 O 5 : yield, 10.0 g. A boron analysis indicated that this sample contained boron.
Anal. Calcd for C 20 H 22 ClN 7 O 6 ·0.3H 3 BO 3 ·2H 2 O: C, 43.96; H, 4.96; B, 0.59; Cl, 6.49; N, 17.94. Found: C, 43.78; H, 4.89; B, 0.61; Cl, 6.59; N, 17.70.
The above solid was stirred for one hour in cold 0.5 contained HCl (100 ml) containing mercaptoethanol (0.1 ml), recollected by filtration under N 2 pressure, washed in the funnel with additional 0.01 N HCl (100 ml), and dried in vacuo over P 2 O 5 : yield, 8.4 g (79%). A boron analysis indicated that this sample containing a trace amount of a boron impurity (found, 0.06%).
Anal. Calc for C 20 H 22 ClN 7 O 6 ·H 2 O: C, 47.11; H, 4.74; Cl, 6.95; N, 19.23. Found: C, 47.34; H, 4.73; Cl, 6.84; N, 19.29.
(C) A solution of THF·1.66HCl·0.74H 2 O·1.68H 3 BO 3 (2.4 g, 3.9 mmol) in a 1:2 mixture of H 2 O--(EtO) 3 CH (60 ml) containing ascorbic acid (0.25 g) was refluxed for five hours and allowed to stand at room temperature for 18 hours. The resulting mixture was diluted with (EtO) 3 CH, and the solid was collected by filtration, washed with Et 2 O, and dried in vacuo over P 2 O 5 to give crude (5,10-CH-THF) + Cl - : yield, 1.5g. TLC (Avicel, 0.1 M phosphate, pH 7) showed that the product was contaminated with fluorescent impurities and ascorbic acid.
EXAMPLE 6
Purification of 5-CHO-THF (Citrovorum Factor) (A) Sephadex G-10 Column Chromatograph
A glass column (5 × 118 cm) was poured in one portion with Sephadex G-10 (825 g) in H 2 O and packed to a height of 108 cm with H 2 O adjusted to pH 8 (meter) with CaO. A solution of impure 5-CHO-THF·Ca (9.0 g) in aqueous Ca(OH) 2 (pH 8) (40 ml) was applied to the column over a period of four hours, and the resulting column was developed with the same solvent at a rate of about 16 ml/hour (unless otherwise noted). After about 48 hours, a mixture of 10-CHO-FA and 10-CHO-DHF, which trailed back into the band containing 5-CHO-THF, was eluted. The front of the band containing 5-CHO-THF was visibly yellow. Fractions were taken every 30 minutes, and the presence of 5-CHO-THF in a fraction was determined by TLC on Avicel plates (0.1 M NaH 2 PO 4 , pH 7). The combined fractions were adjusted to about ph 7.5 with aqueous Ca(OH).sub. 2 and diluted with EtOH to the point of cloudiness. After cooling in an ice bath (unless otherwise noted), the first crop was collected by filtration under N 2 . A second crop was obtained from the filtrate by the addition of 5 volumes of EtOH. The first experiment involved three column runs, the results of which are summarized in Table 1. On alternate weeks, a second sample of 5-CHO-THF was chromatographed on the same column, the results of which are also shown in Table 1.
The results in Table 1 indicated that p-aminobenzoylglutamic acid in eluted toward the end of the band containing 5-CHO-THF. Also, this impurity is concentrated in the (B) samples, which were obtained by intentionally diluting the filtrate with a large volume of EtOH to recover as much weight as possible. In addition, the results indicated that elution of most of 10-CHO-FA and 10-CHO-DHF occurred near the front of the band containing 5-CHO-THF. A greater concentration of 10-CHO-DHF is found in the (A) samples, indicating that the solubility of the Ca salt of 10-CHO-DHF is less than the Ca salt of 5-CHO-THF.
One sample (0.82 g) in Table 1 (run I, column 3) was retained. The last 3 samples from both run I, column 3, and run II, column 2, were conbined, and the composite sample (6.3 g) was dissolved in H 2 O (125 ml). This solution was adjusted to pH 7.5 (meter) with aqueous Ca(OH) 2 and diluted with EtOH (˜15 ml) to give a slightly cloudy solution containing a small amount of trash. During the filtration (under N 2 ) of this mixture under aspirator pressure a yellowish precipitate began to deposit from the unfiltered portion. the solid was collected by filtration and dried in vacuo over P 2 O 5 : yield, 0.70 g (11% recovery), TLC (Avicel, 0.1 M NaH 2 PO 4 , pH 7) showed that this sample was mainly 5-CHO-THF contaminated with 10-CHO-DHF, (5,10-CH-THF) + , and a yellow fluorescent impurity near the origin. HPLC indicated the presence of PABGA (<1%), 10-CHO-DHF (<2.9%), (5,10-CH-THF) + (<1%), and 5-CHO-THF (95.1% by difference). λ max 282 1λ min 242 = 4.50.
Table 1.sup.a__________________________________________________________________________ Percent.sup.d Number of fractions 10-CHO-FA (30 min each) Wt.sup.b andExperiment combined (vol., ml) Recovered (g) A.sub.max.sup.262 /A.sub.min.sup.242.spsp.c PABGA (5,10-CH-THF).sup.+ 10-CHO-DHF 5-CHO-THF__________________________________________________________________________Crude 5-CHO-THF -- -- 3.43 <3 <1 <10 ˜86Run I, Col. 1 A, 2.04.sup.e 3.04 1.3 2.7 <25.6 ˜72Crude 5-CHO-THF 8(120) B, 1.51 3.94 <1 <1 <8.5 ˜90(9 g) in 40 ml ofsolvent A, 1.79 3.99 2 trace <6.4 ˜92 16 (240) B, 1.98 4.59 2 trace <2.5 ˜95 total 7.32 (81%)Run I, Col. 2 A, 1.09.sup.f 3.46 trace 2.3 <10.4 ˜87 11 (105)5-CHO-THF (6.4 g) B, 1.24 4.31 trace <1.0 <4.0 ˜95from Col. 1 in 30 mlof solvent 9 (86) A, 0.56 4.26 trace <1.0 <5.4 ˜94 B, 0.95 4.52 2.4 -- <2.3 ˜95 15 (143) A, 0.90 4.40 trace <1.0 <2.2 ˜97 B, 0.75 4.61 1 -- <1 ˜98 total 5.48 (86%)Run I, Col. 3 10 (78) A, 0.08.sup.g 4.22 trace <1 <6.5 ˜925-CHO-THF (4.2 g) B, 0.82 4.59 trace -- <3.8 ˜96from Col. 2 in 20 mlof solvent 18 (140) A, 0.08.sup.g 4.54 trace -- <2.5 ˜97 B, 2.04 4.58 1 -- <1.3 ˜98 4 (32) A, --.sup.g -- -- -- -- -- B, 0.21 4.73 -- -- <1 ˜99 3 (24) A, --.sup.g -- -- -- -- -- B, 0.18 4.69 -- -- <1 ˜99 total 3.40 (81%)Run II, Col. 1 12 (94) A, 1.45.sup.h 3.43 <1 1.7 <17.4 ˜80Crude 5-CHO-THF B, 2.18 4.14 <1 < 1 <7 ˜91(9 g) in 40 ml ofsolvent 12 (94) A, 1.13 4.16 1.1 -- <5.4 ˜93 B, 1.09 4.50 8.0 -- <1.6 ˜90 10 (78) A, 0.41 4.66 <1 -- <3 ˜96 B, 0.67 4.54 2.2 -- <1 ˜97 total 6.93 (77%)Run II, Col. 2 7 (53) A, 0.01.sup.g -- trace 3.4 <22 ˜755-CHO-THF (5.4 g) B, 0.53 4.04 trace 1.1 <9.4 ˜89in 25 ml of solvent 14 (105) A, 0.17.sup.g 4.35 trace <1 <5.6 ˜93 B, 1.65 4.61 <1 -- <3.1 ˜96 26 (195) A, 0.32.sup.g 4.44 <1 <1 <2.5 ˜95 B, 1.99 4.52 4.3 -- <1.3 ˜94 total 4.67 (86%)__________________________________________________________________________ .sup.a The Sephadex G-10 column was washed with aqueous Ca(OH).sub.2 (5,000 ml) between each run. .sup.b A refers to the first crop, B to the second crop. .sup. c Determined in 0.1 NaOH, Lederle's 5-CHO-THF, ratio 4.86. .sup.d Amount of impurities estimated by HPCL; 5-CHO-THF determined by difference and does not take into account the percentage of solvates and calcium. Also, small peaks of unidentified substances are observed. .sup.e Reprecipitated from H.sub.2 O with EtOH to give 1.1 g (ratio = 3.36), which was included in sample used for column 2. .sup.f Excluded from column 3. .sup.g The cooled mixture was allowed to rewarm to room temperature, whic redissolved most of the precipitate. .sup.h Excluded from column 2, run II.
The filtrate was diluted with additional EtOH (total, 250 ml), and the white precipitate was collected by filtration under N 2 : yield, 4.8 g (76% recovery). TLC showed that the sample contained trace amounts of 10-CHO-DHF and a yellow fluorescent impurity near the origin. HPLC indicated the presence of PABGA (<1%), 10-CHO-DHF (<1%), and 5-CHO-THF (˜98% by difference). λ max , nm (ε×10 -3 ): pH 7--286 (30.4); 0.1 N NaOH--282 (29.7). λ max 282 /λ min 242 =4.67.
Anal. Calcd for C 20 H 21 N 7 O 7 ·2H 2 O·Ca: C, 43.87; H, 4.60; N, 17.91; Ca, 7.32; Ash (CaO), 10.24. Found: C, 43.91; H, 4.63; N, 17.80; Ca, 7.10; Ash (CaO), 10.64.
The filtrate from the above sample was diluted with additional EtOH (total, 625 ml), and the white solid was collected by filtration under N 2 : yield, 0.32 g (5% recovery). TLC showed only 5-CHO-THF. HPLC indicated the presence of PABGA (4.3%) and 5-CHO-THF (95.7% by difference). λ max 282 /λ min 242 =4.65.
The total amount recovered was 5.8 g (92%).
Purified samples of the calcium salt of 5-CHO-THF gave a λ max 282 /λ min 242 value between 4.6-5.4, probably because a slight change in the minimum resulted in a large change in the ratio.
(B) Florisil Chromatography. Florisil (350 g, 100-200 mesh) was suspended in H 2 O (3 times), and the fines were removed by decantation. The defined slurry of florisil was poured into a glass column (3.8×67 cm) and washed with H 2 O until the effluent was clear and then with 0.2% aqueous mercaptoethanol (4000 ml). After a solution of impure 5-CHO-THF (3.0 g) in 0.2% aqueous mercaptoethanol (10 ml) was applied, the column was developed with 0.2% aqueous mercaptoethanol at a rate of 0.3 ml/min. The progress of the development was followed by a uv monitor. After 17.5 hours a uv-absorbing material, probably p-aminobenzoylglutamic acid, was eluted from the column over the next 8 hours. At this time (25.5 hours), 5-CHO-THF began to elute and four fractions were collected (see Table 2). Each fraction was concentrated to about 1/5 volume in vacuo (oil pump) at ˜45° when an off-white flocculent solid began to precipitate. Each of the resulting mixtures was adjusted to pH 12 (meter) with 1 N NaOH and filtered through a thin Celite pad to remove the somewhat gelatinous insoluble material (MgO). The clear filtrates were adjusted to pH 7 (meter) with dilute HCl, treated with 25% aqueous CaCl 2 solution (clarified by filtration), readjusted to pH 7.5 (meter), and diluted slowly with 5 volumes of cold EtOH. The white precipitates were collected by filtration and dried in vacuo over P 2 O 5 .
Table 2__________________________________________________________________________Flow rate Collection Volume, Volume 25%.sup.a SampleFractionml/min time, hr ml CaCl.sub.2, ml wt, g λ.sup.282 .sub.max /λ.sup.24 2 .sub.min__________________________________________________________________________1 0.6 6.5 ˜234 2 0.36 4.382 0.6 10 ˜360 3 1.2 4.623 3.0 8 ˜1,400 2 0.50 3.864 0.6 16 ˜576 .sup.b5.0 5 ˜1,500 4 0.18 2.84 total 2.24 (75% recovery)__________________________________________________________________________ .sup.a After concentration of the fraction in vacuo. .sup.b Eluates combined.
In earlier work on florisil chromatography of crude 5-CHO-THF samples at a faster flow rate, the blue fluorescent spots above and below 5-CHO-THF (TLC) were eluted before and during the elution of 5-CHO-THF rather than after 5-CHO-THF as described above. Although florisil might have better absorbent characteristics for 10-CHO-FA and 10-CHO-DHF at the slower rate, other work suggested that under these conditions the basic nature of the mobile phase (pH˜ 8.5) resulted in the decomposition of these impurities.
The sample from fraction 1 appeared to contain a water-insoluble material and was reprecipitated from an aqueous solution with EtOH: yield, 0.29 g (6.5% from FA); λ max 282 /λ min 242 =4.37. HPLC indicated that this sample contained only trace amounts of uv-absorbing impurities.
Anal. Calcd for C 20 H 21 N 7 O 7 ·.3.8H 2 O·Ca: C, 41.42; H, 4.97; N, 16.91; Ca, 6.91; Ash (CaO), 9.67. Found: C, 41.36; H, 4.91; N, 16.74; Ca, 7.04; Ash (CaO), 9.78.
The sample from fraction 2 (1.2 g, 27% from FA) contained only trace amounts of uv-absorbing impurities (HPLC) and was analyzed without further purification.
Anal. Calcd for C 20 H 21 N 7 O 7 ·.3.5H 2 O·Ca: C, 41.81; H, 4.91; N, 17.07; Ca, 6.98; Ash (CaO), 9.77. Found: C, 41.85; H, 4.85; N, 16.90; Ca, 6.93; Ash (CaO), 10.17.
The total yield of practically pure 5-CHO-THF was 1.49 g (33.5% from FA).
Fraction 3 gave a sample that was shown by HPLC to contain the following uv-absorbing components: p-aminobenzoylglutamic acid (<1%), 10-CHO-DHF (<5.5%), 10-CHO-FA (˜1%), and 5-CHO-THF (˜92.5% by difference).
The sample from fraction 4 showed (HPLC) the following components: p-aminobenzoylglutamic acid (<2%), 10-CHO-DHF (<20%), 10-CHO-FA (˜1%), and 5-CHO-THF (˜77% by difference).
In a large-scale synthesis, folic acid (600 g) was converted to the impure calcium salt of 5-CHO-THF via the catalytic hydrogenation of 10-CHO-FA over Pt in CF 3 CO 2 H. Four glass columns (8 × 120 cm) containing Florisil (2.6 kg) were prepared as described above. The 5-CHO-THF sample (465 g) was divided into 16 portions, and each portion (24-30 g) was eluted (rate, 3-5 ml/min) from one of the columns, each column being used four times. The development of a column was followed by determining the HPLC chromatogram of the eluate. During the first run, the 5-CHO-THF band appeared after a volume of 5 l. was collected. In later runs on the same column, a volume of 7.5 l. was collected before 5-CHO-THF started to eluate. Each 5-CHO-THF fraction (˜4.5 l.) was treated as described above. The combined samples were extracted with O 2 -free H 2 O and filtered to remove an insoluble material. The filtrate was lyophilized to give the product: yield, 213 g (28% from FA). The HPLC chromatogram showed only trace amounts of p-aminobenzoylglutamic acid and 10-CHO-DHF. λ max , nm (ε× 10 -3 ); pH 7-287 (31.5); 0.1 N NaOH--282 (30.8). λ max 282 /λ min 242 = 4.8.
(C) Nonchromatographic Purification of Citrovorum Factor. (1) The hygroscopic, brown, gummy residue (˜400 g) containing glass-fiber filter pads obtained in the conversion of (5,10-CH-THF) + Cl - to 5-CHO-THF·Ca was stirred under N 2 in deaerated H 2 O (4 l.), and the pH of the medium was adjusted to 7.5 with solid Ca(OH) 2 (˜1 g). The glass fibers were removed by filtration, and the residue was washed with portions of deaerated H 2 O (2 l.) until the washings were colorless. The clear filtrate was cooled in an ice bath and diluted with 0.1 volume of EtOH (600 ml). The precipitated dark, hygroscopic, yellow-brown solid was collected by filtration, washed with EtOH, and dried in vacuo over P 2 O 5 : yield, 199 g. λ max 282 /λ min 242 =3.7
The filtrate was diluted with additional EtOH (total, 3 l.), and the precipitated pale yellow solid was collected by filtration, washed with EtOH and dried in vacuo over P 2 O 5 : yield, 17 g. λ max 282 /λ min 242 =3.90.
The clear, yellow filtrate was diluted with additional EtOH (total, 15 l.); after cooling, the resulting cream-colored precipitate was collected by filtration, washed with EtOH, and dried in vacuo over P 2 O 5 : yield, 75 g. λ max 282 /λ min 242 (0.1 N NaOH)= 4.19. HLPC assay of this sample indicated the presence of 5-CHO-THF·Ca (85%). PABGA· Ca (˜2%), 10-CHO-DHF·Ca (˜2%), 10-CHO-FA·CA (trace), and pterins (˜1%). No doubt this sample also contained EtOH and H 2 O (<10%).
(2) Additional experiments were carried out on portions of the large crop of impure 5-CHO-THF obtained as described under procedure (C-1) above.
A turbid solution of this material (3.00 g) in H 2 O (100 ml) containing about an equimolar amount of MgCl 2 ·6H 2 O (1g) was treated portionwise with solid Ca(OH) 2 . . The pH increased rapidly to ˜10.5, then remained between 10.5-10.8. During this period a yellow-brown granular precipitate separated from the mixture after which the pH increased rapidly to 12 as more Ca(OH) 2 was added. After stirring for an additional 30 minutes, the solid was removed by filtration under N 2 pressure and dried in vacuo over P 2 O 5 : Yield, 1.40 g. The major portion of this residue is probably composed of CaO and MgO; however, the HPLC chromatogram showed the presence of a number of impurities and some 5-CHO-THF.
The clear filtrate was adjusted to pH 7.5 with dilute HCl followed by the dropwise addition of EtOH (˜20 ml) until permanent turbidity was reached. This mixture was cooled to 10°, and the yellow solid was collected by filtration and dried in vacuo over P 2 O 5 : yield, 0.64 g. λ max 282 /λ min 242 =3.71. The HPLC chromatogram showed that this sample contained only small amounts of the usual impurities, but increased amounts of FA and an unidentified material with a longer retention time. Apparently FA and the unidentified material were generated during the base treatment of this sample in the presence of MgCl 2 . A magnesium analysis indicated the presence of a trace amount of magnesium (0.003%).
Anal. Calcd for C 20 H 21 N 7 O 7 · Ca·0.5C 2 H 6 O·1.2H 2 O: C, 45.35; H, 4.78; N, 17.63; Ca, 7.21; Ash (CaO), 10.08. Found: C, 45.11; H, 5.01; N, 17.38; Ca, 7.20; Ash (CaO), 10.07.
The filtrate was diluted with three volumes of EtOH (300 ml), and the resulting mixture was cooled in an ice bath. The white solid was collected by filtration, washed with EtOH, and dried in vacuo over P 2 O 5 : yield, 1.33 g. λ max 282 /λ min 242 =4.78. HPLC assay and elemental analysis indicated the presence of 5-CHO-THF· Ca (86%), PABGA· Ca (1%), 10-CHO-DHF (<1%), 10-CHO-FA (<1%), pterins (<1%), EtOH (4.2%), H 2 O (3.3%), and unidentified material (˜2.5%).
Anal. Calcd for C 20 H 21 N 7 O 7 ·Ca·0.5C 2 H 6 O· H 2 O: C, 45.65; H, 4.74; N, 17.75; Ca, 7.25; Ash (CaO), 10.14. Found: C, 45.59; H, 17.69; Ca, 7.51; Ash (CaO), 10.51.
When the above experiment was repeated using twice the weight of MgCl 2 , a smaller amount (0.77 g) of purified 5-CHO-THF was recovered.
It is thought that the invention and many of its attendant advantages will be understood from the foregoing description, and it will be apparent that various changes may be made in the methods as described herein without departing from the spirit and scope of the invention or sacrificing its material advantages, the forms hereinbefore described being merely the preferred embodiments thereof.
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Improved methods for the preparation and purification of citrovorum factor are disclosed. The method includes improved procedures for hydrogenation of 10-formylfolic acid as well as for the reduction of folic acid. Also disclosed are improved procedures for opening of the imidazoline ring, and a non-chromatographic method for the purification of crude samples of citrovorum factor.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of patent application Ser. No. 13/644,322, filed Oct. 4, 2012, which is now U.S. Pat. No. 8,863,464 and incorporated herein.
FIELD OF THE INVENTION
[0002] The present invention relates to an interlocking masonry unit. One embodiment of the invention comprises an interlocking masonry unit for use in mortared or similar wall construction which reduces the need for constant measurements and alignment, resulting in a wall with increased strength.
BACKGROUND OF THE INVENTION
[0003] The creation of buildings by utilizing walls made of concrete or similar stonework is a popular method of construction. Many traditional masonry walls are created using masonry units commonly referred to as cinder blocks. A cinder block is a masonry unit in the shape of a rectangular prism with two vertical chambers. A wall is constructed by creating successive rows of cinder blocks. Often each row of cinder blocks is offset by half a block from the previous row to increase stability. Some form of mortar or similar bonding material is placed between each row of blocks to bond the blocks into a solid structure.
[0004] One of the primary difficulties of creating cinder block walls is that constant measurements and adjustments must be made as the construction process is undertaken. Bonding material must be laboriously applied between each new block and all adjacent blocks. The craftsman must constantly adjust the wall as each block is placed to ensure that each row is level and straight. Failure to make constant adjustments often results in a wall that is uneven, non-level, angular, or otherwise unstable and not ascetically pleasing. This process is both time consuming for the craftsman and subject to significant human error. The resulting wall is also only as strong as the weakest bonded joint between two adjacent blocks.
[0005] Accordingly, there is a need for an interlocking masonry unit. The interlocking masonry unit should connect with adjacent masonry units in a standard way that reduces the need for precision and skill. The interlocking masonry unit should also be designed to accept bonding material that is poured into the wall after each course of the wall is completed in order to reduce overall construction time. The interlocking masonry unit should also be designed to allow the bonding material to pour inside of and between the masonry units in both the horizontal and vertical dimensions to create a strong wall that is bonded together internally in all directions forming a matrix. Furthermore, other desirable features and characteristics of the present invention will become apparent when this background of the invention is read in conjunction with the subsequent detailed description of the invention, appended claims, and the accompanying drawings.
SUMMARY OF INVENTION
[0006] An object of the present invention is to provide an interlocking masonry unit that can overcome the aforementioned deficiencies. One embodiment of the invention comprises an interlocking masonry unit that can be placed in connection with an adjacent masonry unit in a standard manner that reduces the need for constant measurement and adjustment for alignment purposes. Bonding material can be poured as the wall is created so that the need for adjustment is clear to the craftsman before the units become permanently bonded together. The interlocking masonry unit can include both horizontal and vertical cavities to accept bonding material in order to create a matrix of bonding material to increase the overall strength of the wall.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The drawings contained herein illustrate embodiments of the invention. The invention is not limited to the particular embodiments shown in the drawings. The embodiments shown are examples, and the invention is capable of many variations of said embodiment in the drawings;
[0008] FIG. 1 illustrates a perspective view of the concave upper surface and a side surface of an interlocking masonry unit according to an embodiment of the present invention;
[0009] FIG. 2 illustrates a perspective view of the concave lower surface of the interlocking masonry unit of FIG. 1 ;
[0010] FIG. 3 illustrates an end plan view of two vertically adjacent interlocking masonry units according to an embodiment of the present invention. The masonry unit may be offset by one half block as desired to increase the strength and stability of a stack or wall;
[0011] FIG. 3A illustrates an end plan view of two vertically adjacent interlocking masonry units according to another embodiment of the present invention;
[0012] FIG. 3B illustrates another end plan view of the masonry units of FIG. 3A ;
[0013] FIG. 4 illustrates a top plan view of a complete and a partial horizontally adjacent interlocking masonry unit according to an embodiment of the present invention; and
[0014] FIG. 4A illustrates a partial bottom plan view of the interlocking masonry unit of FIG. 4 ;
[0015] FIG. 5 illustrates perspective view of a wall comprising multiple masonry units according to an embodiment of the invention. FIG. 5 also shows the use and placement of rebar reinforcement in the wall system for added strength.
[0016] FIG. 6 illustrates a partial cross sectional view of a support member according to an embodiment of the invention;
[0017] FIG. 7 illustrates a partial cross sectional view of an interlocking masonry unit according to an embodiment of the invention; and
[0018] FIG. 8 illustrates a front elevation of a wall comprised of a plurality of interlocking masonry units according to an embodiment of the invention.
DETAILED DESCRIPTION OF INVENTION
[0019] An interlocking masonry unit according to a preferred embodiment of the invention is illustrated in FIGS. 1 and 2 , and is shown generally at reference numeral 100 . FIG. 1 illustrates a perspective view of the concave upper surface and a side surface of the masonry unit 100 . The masonry unit 100 comprises a generally rectangular prism shape with a concave upper surface 10 as shown in FIG. 1 . a concave lower surface 20 as shown in FIG. 2 , two side surfaces 11 as shown in FIG. 1 , and two end surfaces 30 as shown in FIG. 3 . The masonry unit 100 can be made of traditional masonry material, such as concrete. Alternatively, the masonry unit 100 can be made of foam. One skilled in the art will recognize that any three dimensional object with a rectangular prism shape generally comprises six surfaces. The surface names, as used throughout the application, are chosen for purposes of designation rather than functionality and should not be considered limiting. The purpose of the concave shape of the upper surface 10 and lower surface 20 is discussed below in reference to FIG. 3 .
[0020] The masonry unit 100 comprises one or more central vertical cavities 12 , as shown in FIGS. 1 and 2 . The central vertical cavities 12 should extend between the lower surface 20 and the upper surface 10 of the present invention and should be capable of accepting bonding material. In the preferred embodiment, two central vertical cavities 12 are employed, and each of the central vertical cavities 12 comprise the same shape mirrored about an axis passing through the center of the unit and perpendicular to the side surfaces 11 . In the preferred embodiment, the central vertical cavities 12 comprise a rounded triangular shape, however, many central vertical cavity 12 shapes could be substituted. When two or more interlocking masonry units 100 , 100 ′ are placed in a vertically adjacent position relative to one another, also referred to hereinafter as a stack as shown in FIG. 3 ., the central vertical cavities 12 of each masonry unit should be generally aligned with the central vertical cavities 12 of the other units. So long as the central vertical cavities 12 of each unit are generally the same shape and are generally aligned, any bonding material poured into a central vertical cavity 12 of the uppermost unit 100 will also pour through the corresponding central vertical cavity 12 of each unit below in the stack due to the force of gravity. This allows a craftsman to quickly create a wall by stacking the masonry units, one on top of one another, and then pouring bonding material through each vertical cavity as the wall is completed and judged to be in the proper shape and alignment. In the preferred embodiment, the central vertical cavities 12 are surrounded by a sloped edge 12 A as shown in FIGS. 1 and 2 , preferably at or near a forty five degree angle from the horizontal plane, to act as a funnel creating a larger void between the upper and lower masonry units, thus assisting the bonding material in its movement into the lower portions of the stack.
[0021] As shown in FIG. 2 , the masonry unit 100 comprises a plurality of support members 21 projecting vertically out from the lower surface 20 of the masonry unit. Preferably, eight support members 21 are employed, however, a greater or fewer number of support members 21 can be employed. As shown in FIG. 1 , the masonry unit comprises a plurality of receiving port depressions 13 each projecting vertically into the upper surface 10 of the masonry unit 100 . Preferably, eight receiving port depressions 13 are employed. Each receiving port depression 13 can be shaped and positioned to be capable of receiving a corresponding support member 21 from another masonry unit. As such, multiple masonry units can be stacked one on top of another. When creating the stack, the support members 21 of the upper masonry unit are received by the receiving port depressions 13 on the upper surface 10 of the masonry unit immediately below it. In this manner, each masonry unit is effectively interlocked into position relative to the masonry units below. Absent manufacturing defects or variable terrain, the resulting stack is straight and level without requiring the user to undertake efforts to adjust or otherwise level the stack. As variable terrain and manufacturing irregularities are possible, the user can rapidly create a stack and quickly observe and correct any alignment concerns prior to pouring bonding material through the vertical cavities. Preferably, each receiving port depression 13 is larger than the support members 21 to allow the user to make minor adjustments to the wall as it is completed.
[0022] In a preferred embodiment, each end surface 30 as shown in FIG. 3 further comprises two end projections 14 . As shown in FIG. 4 . the end projections 14 can be shaped and positioned so that when two interlocking masonry units are placed in a horizontally adjacent configuration, an intermediate vertical cavity 40 , as shown in FIG. 4 , extending between the masonry units is created. When the masonry units are stacked in rows, the intermediate vertical cavity 40 can accept bonding material. So long as the masonry units are not offset, the bonding material can be capable of poured through an intermediate vertical cavity 40 , as shown in FIG. 5 , that is placed in a higher position in the stack to intermediate vertical cavities 40 that are placed lower in the stack due to the force of gravity. However, even in an offset configuration, as can be seen in FIG. 5 , the bonding material can be poured into each intermediate vertical cavity 40 from the central cavity 12 above it, due to the shape and positioning of the central cavities 12 . Each of the end projections 14 include a sloped edge 14 A, as shown in FIG. 1 , preferably at or near a forty five degree angle from the horizontal plane, to act as a funnel and assist the bonding material in its movement into the lower portions of the stack. The end projections 14 should be omitted on the end surface 30 of any masonry unit that is to be used at the corner of a wall. It should also be noted that, in the preferred embodiment, portions of each block end come in contact with an adjacent block. This allows for proper alignment and spacing which maximizes amount of bonding material to attach between each unit to strengthen the bond. It should also be noted that, preferably, the shape of the intermediate vertical cavity 40 is irregular. This configuration increases the surface area available for the bonding material to attach to for a stronger bond. This configuration also ensures that the end projections 14 each attach around the cured bonding material contained in the vertical cavity 40 , which further reduces the possibility of a breach in the wall, even if the bonding material should become separated from the associated masonry unit.
[0023] As shown in FIGS. 1 and 4 , the masonry unit 100 can include one or more vertical depressions 15 in one or both of the side surfaces 11 . Preferably, each vertical depression 15 has a width greater than one-half inch and less than two inches. Preferably, each vertical depression 15 projects into the masonry unit 100 between one-half inch and two and a half inches, and each vertical depression 15 also preferably extends down the entire side surface 11 of the masonry unit. When crafted to these preferred dimensions, each vertical depression 15 is capable of accepting a wall stud. The vertical depressions can further comprise a plurality of stud support notches 17 , as shown in FIGS. 1 and 2 . Each of the stud support notches 17 can be capable of accepting a peg to hold a wall stud in place. When a wall is finalized, a wall stud can be inserted into the vertical depression 15 and secured in position by means of plurality of pegs or similar items hammered or screwed into the stud support notches 17 . In an alternate embodiment, no support notches 17 are provided and the wall studs can be secured by a toggle bolt or other securing means. This allows the user to create a wooden wall, capable of accepting drywall or similar finishing material without the structure that is typically associated with a standard wall. Referring to FIG. 4 , the end projections 14 may also be shaped and positioned to create a vertical depression 15 in the side surface 11 between two horizontally adjacent interlocking masonry units 100 , 100 ′ that are capable of accepting a wall stud. This ensures that in the case of stacked rows where one or more rows are offset by half a masonry unit from one another, the vertical depression 15 in the side surface 11 of a masonry unit lines up with the vertical depression 15 created between two horizontally adjacent masonry units on a different row. This allows a wall stud to be accepted into all of the rows at once. Preferably, the vertical depressions 15 are positioned to create a distance of eight inches between the center of each wall stud and the center of the horizontally adjacent wall studs, once said wall studs are accepted. This allows the user to easily attach standard building materials to the wall studs.
[0024] FIG. 3 illustrates an end plan view of two vertically adjacent interlocking masonry units 100 , 100 ′. In the preferred embodiment, the concave upper surface 10 of the lower masonry unit and the concave lower surface 20 of the upper masonry are shaped to create a horizontal cavity 31 which extends between the two masonry units. The horizontal cavity 31 is capable of accepting bonding material poured from upper rows through the vertical cavities and channeling the bonding material horizontally between two rows in the wall. The channel created by the horizontal cavity 31 and the vertical cavities 12 create a matrix of cured bonding material which increases the overall strength of the wall in relation to standard cinderblock walls. The channel created by the horizontal cavity 31 also allows bonding material to pour into the intermediate vertical cavities 40 in cases where the rows of the wall are offset. An end surface 30 of any masonry unit that is to be used at the corner of a wall can include an additional projection on the upper surface 10 and the lower surface 20 capable of closing the horizontal cavity 31 and vertical cavity 40 preventing any bonding material from escaping from the channel created by the horizontal cavities 31 of the masonry units 100 , 100 ′ in the wall.
[0025] In a preferred embodiment, the upper surface 10 further comprises a plurality of upper projections 32 as shown in FIG. 3 . The upper projections 32 can accept one or more reinforcing elements 16 , as shown in FIG. 1 and FIG. 5 , such as concrete reinforcing bar, also known as rebar, and/or similar items. The vertical channels created by the central vertical cavities 12 are also capable of accepting one or more reinforcing elements 16 . The presence of the reinforcing elements 16 increases the overall structural integrity of the resultant wall after the bonding material is poured inside and allowed to cure. The matrix of vertical and horizontal channels associated with a wall constructed with the interlocking masonry units, as described herein, along with associated reinforcing elements 16 , creates a structural integrity that is significantly increased over a standard cinder block wall.
[0026] In a preferred embodiment, the masonry unit 100 has sharp edges 14 , 35 at the outer perimeter at the top and bottom and on both ends of the masonry unit 100 , as shown in FIGS. 1 and 2 . The sharp edges 14 , 35 form one-half of a mortar seam. The edges 14 , 35 slope inward, toward the center of the masonry unit 100 to form a “V” or pinch point 37 , 45 , as shown in FIGS. 3B , 4 and 8 , between masonry units 100 , 100 ″, when the units are stacked end to end and/or one on top of the other. The pinch points 37 , 45 preferably should be approximately one-sixteenth to one eighth inch in width. The pinch points 37 , 45 are shaped similar to a funnel to guide the bonding material from a wide area or space to the narrow space where the grit, sand and gravel of the bonding material fill in, forcing out air from the masonry units and sealing the space, bonding the units together. In addition, the masonry unit 100 can have sloped, concave outer edges 34 , as shown in FIG. 3 .
[0027] In a preferred embodiment, each end projection 14 further comprises a bumper projection 33 . As can be seen in FIG. 4 , each bumper projection 33 is shaped and positioned to come in contact with a bumper projection 33 of an equivalent horizontally adjacent interlocking masonry unit when the masonry units are being placed by the user. In this manner, the user may place each masonry unit, verify the bumper projections 33 of each masonry unit are properly touching, and thereby verify that the row of masonry units being created is level and aligned. The bumper projections 33 hold the blocks of the masonry units apart a pre-determined distance, as shown at reference numeral 45 in FIG. 4 . Preferably, the bumper projections 33 create a space 45 of approximately one-sixteenth to one-eighth inch wide. This space 45 lets the air out when the masonry units are being filled with bonding material. The grit, rock and sand that is part of the bonding material fills the internal block voids are stopped from exiting at this point
[0028] FIG. 5 illustrates a perspective view of a wall comprising multiple masonry units according to a preferred embodiment of the invention. A method of assembling a wall comprising interlocking masonry units as depicted in FIG. 5 is now more fully described. A row of interlocking masonry units can be created by placing a plurality of interlocking masonry units on a prepared surface in a manner that causes the end surface 33 of each masonry unit to come in contact with an end surface 33 of one or more adjacent masonry units. Subsequent rows of interlocking masonry units can be positioned on top of the previously created row of interlocking masonry units by placing the support members 21 of the masonry units in the subsequent row into the receiving port depressions 13 of the previously placed row. This process can be repeated until a wall or structure of the desired height is created. Reinforcing elements 16 can be placed into the horizontal cavities 31 between each row. Depending on the embodiment, the user may shift each subsequent row by half of the length of a masonry unit in the horizontal axis from the previously placed row to increase the stability of the resultant wall. The reinforcing elements 16 can be placed in the horizontal cavities 31 prior to placing any associated corner units. Reinforcing elements 16 should also be placed into the central vertical cavities 12 and 40 of each masonry unit for greater structural integrity. Bonding material can be poured into the vertical cavities and allowed to spread and seep into the horizontal cavities to create a matrix of bonding material throughout the cavities of the wall. A mechanical means may be employed to vibrate and to assist the bonding material in its spread throughout the matrix of cavities in the structure. The bonding material should then be allowed to cure in the wall. In an alternate embodiment, bonding material can be poured into the cavities after each row is positioned.
[0029] The support members 21 can serve a number of purposes. The support members 21 can align the upper block 200 and the lower block 300 with each other. Also, the support members 21 lift or hold the block 200 above the lower block 300 , as shown in FIG. 8 . Preferably, the support members 21 are about 1/16 to ⅛ inch longer than the members 21 would be when positioned in the port depressions to align the upper block 200 and lower block 300 the outer horizontal sides or edges to sit flat or flush against each other. The support members 21 keep the block 200 raised off the outer edges of the block 300 below it creating an air gap 37 , shown in FIG. 8 , between the upper block 200 and the lower block 300 , as shown in FIG. 8 . The outer edge of the upper block and lower block has a molded in mortar seam, as shown in FIG. 3 , on each horizontal edge 34 of the block next to or adjourning the horizontal edge of the block where the molded in mortar seams run horizontally at the back top edge. Starting from the top front edge of the mortar joints or seam, this is where the gap 37 is formed and mortar fills the gap between the blocks to seal and bond the blocks together. The surfaces of the back top edge begin to slope or taper off inward to the concave surface. This sloping edge runs the horizontal length of the block, and the inward sloping mortar joint goes around the outer edge of the vertical cavities 15 , as shown in FIG. 1 .
[0030] This inward sloping taper of the back of the mortar joint or seam can be on both edges of the block, top and bottom. When the top block support members 21 are positioned in the bottom block port depressions, the horizontal edges between the two blocks are separated by a space or an air gap by approximately 1/16 to ⅛ of an inch. This space has the purpose of exhausting of the air as the block is filled with bonding material. The support members 21 hold the blocks apart about 1/16 to ⅛ of an inch support and align the block. The support members 21 holding the blocks apart leave a gap or space between the blocks. When bonding material flows into the vertical cavities 12 , 40 , bonding materials also flows into the horizontal concave cavities 31 and the blocks become filled with bonding material in vertical cavities 12 , 40 and the horizontal concave cavities 31 . Bonding material forces air out through this space or air gap between the blocks, filling the space between the blocks with bonding material. The bonding material continues to seep into the space, sealing the space, filling out the mortar seam, surrounding the support members filling the horizontal concave space or voids and the vertical spaces allowed to cure the blocks will not separate without destroying the assembly.
[0031] As shown in FIG. 4 , an air gap 45 is created vertically between the two blocks end when the blocks are placed in close proximity to one another. The air gap 45 is approximately 1/16 to ⅛ of an inch wide.
[0032] The front top edge of the one half mortar seam begins to slope or taper off to the interior. The top edge of the one half mortar seam is a vertical pointed area. When the two blocks with the same pointed area come together they form a pinched point 45 as shown in FIG. 4 (also see reference numeral 37 in FIGS. 3B and 8 ).
[0033] When the ends of two blocks come together and are aligned, and the bumpers or spaces touch properly, the vertical cavity 40 is formed. When the bonding material fills the cavity, it pushes air out through the air gap 45 , as shown in FIG. 4 , since the opening forming the air gap tapers down to 1 / 16 to 1 / 8 of an inch between the two half mortar seams. Bonding material cannot go through the gap 45 . The bonding material bonds and seals the air gap 45 creating a finished mortar seam or joint. As shown in FIG. 4 , the block ends are kept apart by the bumper 33 or spaces located on each end. The purpose of the bumpers 33 or spaces is to keep the blocks the proper space or distance apart so that no other part of the block touches the other. The bumper or spacers touch at a predetermined point at its outer edge. This keeps the blocks properly spaced apart and aligned with the other block so that there is an air gap 45 , shown in FIG. 4 , at the vertical ends of the block.
[0034] The vertical channels 12 , 40 , shown in FIG. 4 , increase the flow of bonding material between both blocks when the blocks are offset. An extra wide void 31 , shown in FIG. 3 , is created in the concave horizontal design of the block. The concave is extra wide and deep to increase the bonding flow and more adhesive surfaces. The void is concave on the upper blocks, lower or bottom surface, and concave on the lower blocks upper surface. The concave surfaces can accomplish several things. The concave surfaces open up or increase the open space or void between the upper and lower blocks, increase the amount of surface area the bonding material can attach to and increases the ease whereby the bonding material can flow between blocks to fill open spaces or voids, and increase or enhance the flow of bonding material over or through the vertical cavities 12 .
[0035] The vertical cavities 12 , 40 can have angled or sloped top edges 51 , as shown in FIG. 3A . The angle or slope on the top edge of the vertical cavities 12 , 40 are cut away at an angle of about thirty to forty-five degrees to enhance or increase the flow of the bonding material through the vertical cavities 12 , 40 and concave spaces and/or voids. The top sloping edges 51 and bottom sloping edges 50 of the vertical cavities 12 , 40 , of the block add to the overall surface area for bonding material to attach to for added adhesion or bonding surface for added strength of the structure. In addition, the sloping edge forms a locking plug in the vertical cavities so if the bonding materials become detached from the vertical cavities the overlap or lock formed by the cured bonding material lapping over the edge or sloping outward from the vertical cavities 12 , shown in FIGS. 1 and 2 , lock the plug into the vertical cavities by virtue of the lip or the slope. Therefore, when the wall structure is built the bonding materials form a matrix or lattice in the interior of the block. If a horizontal or vertical force is applied to the wall, the wall resists movement because of the matrix or lattice in the interior cured bonding material and the rebar structure.
[0036] The bonding material surrounds all support members 21 to hold them in place. The upper and lower concave areas of the two blocks are bonded together by the bonding materials that fill the connected spaces. The upper and lower blocks are bonded together through the bonding materials in the vertical cavities. The studs in the vertical cavity 15 , shown in FIG. 1 , help support the wall. The studs can be locked in each block by pegs or similar devices to keep it from moving vertically or horizontally. The lips or slopes (angles) 12 A, 14 A keep the block from pulling apart vertically.
[0037] The introduction of the rebar between the upper and the lower block with their ends tied together adds strength to the matrix of the cured bonding material that runs within the interior of the structure. The bonding material matrix within the block and the vertical rebar in the vertical structure in combination with the two rebar that run across the blocks top center rebar supports 16 , 32 , shown in FIGS. 1 and 3 , add to the durability, strength, and integrity of the structure holding the blocks together both horizontally and vertically.
[0038] The point of the vertical triangular cavity 12 points inward between support members 21 , as shown in FIG. 2 , to extend far enough into the center of the block to be over the opening of the cavity 40 . The blocks are offset by one half block for cavity 40 to be fully filled with bonding material, since the opening between cavity 12 and cavity 40 vertically is narrow.
[0039] So that there are the minimum number of unbonded surfaces within a structure, an air gap 52 can be made around the support member 21 , as shown in FIG. 6 . As shown in FIG. 6 , the support member 21 can be seated loosely, for slight movement in the port depression 13 . The upper part of the support member at the concave surface 54 has a large air gap around the support member 21 . This air gap allows bonding material to flow down into the port depression along the sides of the support member 21 inside the port depression bonding everything together in the concave surface.
[0040] In order for bonding material to flow more easily into cavity 40 , which is below the rebar bridge, when the masonry units are offset by one-half masonry unit, the triangular shaped vertical cavities 12 on both ends of the masonry unit have been cut down or cut away, as shown in FIG. 3A at reference numerals 50 and 51 . This feature, in addition to the feature shown in FIG. 2 at reference numeral 12 B increases the volume of flow of bonding material below the rebar bridge to cavity 40 . FIG. 4A provides a reverse view, in which the shaded area which is normally below the rebar bridge is shown on top for the purpose of showing the limited space between the masonry unit for bonding material to flow into cavity 40 when the rebar bridge is above. The white area shown at reference numeral 47 in FIG. 4A shows the limited opening to the cavity 40 below the rebar bridge area limiting bonding material flow to cavity 40 below.
[0041] Filling cavity 40 can be a problem, because of the rebar support bridge. The bridge adds strength to the center of the block and gives the wall integrity. The width of the center of the block and the position of cavities 12 over cavity 40 can make it necessary to use an enhanced triangular shaped vertical cavity with a cutaway section 12 B on the bottom of the block, as shown in FIG. 2 .
[0042] The width between the two support members 21 , shown in FIG. 2 , where the triangular shape vertical cavity points to the center of the block has limited opening. To overcome the narrowed opening to cavity 40 , the triangular shaped cavity is used to extend between support members 21 , as shown in FIG. 2 at reference numerals 12 , 12 B. This creates a larger opening to the vertical cavity 40 below on both sides of the rebar support bridge, shown in FIG. 3 at reference numeral 32 . FIG. 4A shows a reverse view with cavity 40 on top for the purpose of showing the limited opening to cavity 40 below the rebar bridge. The cavity 40 is below the rebar bridge 32 , shown in FIG. 3 , for this purpose. Looking down along both sides of the rebar bridge, only the area 47 (shown in FIG. 4A in white) of cavity 40 can be seen from above the rebar bridge. This shows the narrow opening to cavity 40 below.
[0043] As shown in FIG. 2 , the concave area between the upper and lower block and the position of the triangular vertical cavity 12 and the cutaway area 12 B gives the cavity 40 spanned between the two blocks a wider opening for bonding material to flow through.
[0044] The cutaways 12 B are widening inward protruding point of the triangular vertical cavity 12 , as shown in FIG. 2 , enhances the flow of bonding material to vertical cavity 40 , as shown in FIG. 4A , which is a reverse overlay. The cutaway are 12 B widening and increasing the opening between the cutaway point of the triangular vertical cavity 12 and cutaway 12 B on the bottom of the block, opening up the horizontal concave cavity to vertical cavity 40 below.
[0045] As shown in FIG. 1 , the vertical cavity 15 adds to the overall durability, strength, and integrity of the structure. The two by four or other structure having been locked into the vertical cavities 15 by the peg system resists being pulled out vertically or horizontally, thereby maintaining the structure.
[0046] When cavity 40 is over the blocks rebar support, the problem of bonding material flow is lessened by the fact that vertical cavities 12 on either side of cavity 40 has a wide opening to the vertical cavities below the block and can be easily filled. When the rebar support area is offset by one half block vertical cavity 40 opening or passage way between the upper block vertical cavity 12 and the lower block vertical cavity 40 is greatly narrowed.
[0047] To overcome the narrow passage way that the bonding material has to go through, the opening should be opened up greatly. To do this, the vertical triangular opening 12 , shown in FIG. 2 , should be between the support members 21 and pointed inward toward the center of the block. Next, the concave surface on the top of the block and the bottom of the block had to be as deep as possible.
[0048] To accommodate the fast flow of the bonding material for maximum opening of the upper and lower block. Next, the edges of the cavities 12 and 40 had to be opened up or widened to create a larger gap between the lower vertical cavity 12 edge of the top block and the top edge of the vertical cavity of the bottom or lower block. To do this, the edges of the vertical opening 12 A and 14 , shown in FIG. 1 , are trimmed back to a thirty to forty-five degree angle or slope. With the sloping edges of the vertical cavities and a distance between 2½ to 3 inches maximum between the upper and the lower concave surfaces bonding flow is increased.
[0049] The opening between the upper block vertical cavity 12 and the lower block cavity 40 can be opened up or widened further by cutting away part of the center of the block, as shown in FIG. 2 at reference numeral 12 B. The cutaway of the center of the block gives more opening or space between the upper block vertical cavities 12 and the lower vertical cavity 40 , thus the bonding material has a greater opening for bonding material to flow through to fill the cavities.
[0050] When the blocks are offset by one half block, the rebar support area is shifted to be over the vertical cavity 40 , as shown in FIG. 4A . This reduces the opening between vertical cavity 12 and the vertical cavity 40 in the block below.
[0051] The triangular shape vertical cavity 12 enhances the flow of bonding material in the vertical cavities 12 and 40 . The edges on the concave surfaces of the block can be cut deeply, such as at a thirty to forty-five degree angle as shown in FIGS. 1 and 2 at reference numerals 12 A, 14 A. The lip or slope of the edge of the cavities on the top concave surface and the bottom concave surface prevent the cured bonding material from pulling out.
[0052] The triangular shape of the vertical cavities should be pointed inward toward the center of the block to be able to reach in far enough to be over cavity 40 , as shown in FIG. 4A at reference numeral 47 . FIG. 4A provides a reverse image with cavity 40 on top of the rebar area, and area 47 (shown in white in FIG. 4A ) being the opening to the cavity 40 below. FIG. 4A shows cavity 40 on top to illustrate the narrow opening to vertical cavity 12 .
[0053] An extended area of the lip or slope inward to the center of the block area can be cutaway, as shown in FIG. 2 at reference numeral 12 B. This area opens up or widens the distance or space between vertical cavities 40 and the cavity 12 and area 12 B. This cutaway area 12 B gives the bonding material a bigger opening to flow through. Also, the triangular shape gives the vertical cavity 12 a wider opening in the concave cavity, as shown in FIG. 2 . The outer edges of the triangular shape and sloping lip extended between and beyond the mounting area of the support members 21 gives the horizontal cavity a wider opening in the concave cavity for bonding material to flow through to cavity 40 . The interior of the vertical cavities 12 can have rounded corners or points, since sharp angles have a greater tendency to crack or break. The maximum amount of material has been removed from the block without sacrificing the structural integrity of the block. As such, the area for the bonding material to attach to is maximized, thereby making the block lighter and minimizing the amount of material needed in the manufacturing process.
[0054] When two block ends come together, each forms one half of the vertical cavity 40 , as shown in FIG. 4 . The end vertical cavity of a block is one half part of vertical cavity 40 , and has a locking design in that the horizontal opening is narrower, as shown in FIG. 4 at reference numeral 42 , than the back side open vertical area. The cavity 40 includes an area 14 A on the upper and lower lip or edges of the vertical cavities 40 . When the end of the two blocks are placed together, as shown in FIG. 4 , and bonding material fills the area and is allowed to cure, the blocks become inseparable. The cured bonding material cannot pull out vertically, because the bonding material overlaps the slope of area 14 A, as shown in FIG. 1 . Also, the bonding material cannot pullout of the vertical cavity 40 , because it is locked in the vertical cavity 40 by the vertical lip and narrow opening, as shown in FIG. 4 at reference numeral 42 .
[0055] While the present invention has been described above in terms of specific embodiments, it is to be understood that the invention is not limited to the embodiments described above. Various modifications and other embodiments can be made without departing from the scope of the present invention. The foregoing description of various embodiments of the invention and the best mode for practicing the invention are provided for the purpose of illustration only and not for the purpose of limitation—the invention being defined by the following claims and equivalents thereof.
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A multi-purpose interlocking masonry unit includes support members extending from its lower surface and port depressions formed in its upper surface. Each masonry unit can be placed on top of a previously placed masonry unit. The interlocking masonry unit allows for the rapid creation of a wall that is substantially straight and aligned while minimizing the need to perform precise measurements and make alignment adjustments during the creation process. Bonding material can be poured through the resultant wall ports, creating a matrix pattern of bonding material throughout the wall, which results in a stronger more durable construction.
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BACKGROUND OF THE INVENTION
The field of the invention generally relates to voltage regulators, and more particularly, relates to tapped voltage regulators.
As is well known, electronic voltage regulators are used to provide a accurate and steady desired DC output voltage level from a source of higher voltage level that may fluctuate in voltage level over time. Three common types of electronic voltage regulators are the series, shunt, and the switching regulators. In the series regulator a series "pass" element is connected in series with the voltage source. The series pass element is most commonly a transistor which acts as a variable resistance, a variable current source, or a variable voltage source. The output voltage of the series pass element is varied in accordance with a feedback signal. This feedback signal is derived from the desired output voltage, and acts in such a way as to vary the characteristics of the series pass element to keep the desired output voltage at a constant, desired level. With such an arrangement, the desired output voltage remains at a relatively constant level regardless of fluctuations of the source voltage level, or in the impedance of the load. One problem with the series electronic voltage regulator is that its efficiency is relatively low when there is a relatively large differential between the voltage level of the voltage source and the desired output voltage level. For example, if the source voltage level is supplied by a DC battery, the level of which may decrease over time, the initial source voltage level must be relatively high with respect to the desired output voltage level to assure continued proper operation after the source voltage has decreased. However, in the initial operating period, with the relatively high voltage level differential between the source voltage level and the desired output voltage level, power is dissipated in the series pass element at a relatively fast rate thereby reducing the efficiency of the regulator during the initial operating period. This dissipation of power at a relatively fast rate gives rise to the generation within the regulator of heat which must be dissipated.
In the shunt regulator, a shunt "pass" element is connected across, or in parallel with, the voltage source which has a finite output impedance. The shunt pass element is most commonly a Zener diode. The Zener diode acts as a variable resistance which is self-adjusting so as to keep the voltage level across the load equal to the Zener breakdown voltage level by forcing excess source voltage to be dropped across the voltage source output impedance. Therefore, a Zener diode should be chosen which has a Zener voltage equal to the desired output voltage level. Shunt electronic voltage regulators may also have relatively low efficiency during the initial operating period. For example, the efficiency of shunt regulators decreases as the current through the shunt "pass" element increases, as is the case during the initial operating period when the source voltage is substantially greater than the desired output voltage level.
A common switching electronic voltage regulator is a modification of the series electronic voltage regulator, such modification having additional energy storage elements. The difference is that in the switching electronic voltage regulator, the series switching "pass" element, or transistor, is switched between an "on" (low resistance) state, and an "off" (high resistance) state, instead of being set to a variable resistance or a variable current or voltage source somewhere between the aforementioned two extremes. During the "on" state, current flows through the series switching pass element, which has a very small resistance. Because the resistance of the series switching "pass" element is small, very little power is dissipated in the series switching "pass" element. During the "off" state, the resistance of the series switching "pass" element is very high, resulting in a negligible current flowing through the series switching "pass" element. As a result of only negligible current flowing through the series switching "pass" element, very little power is dissipated in it. The desired output voltage level is maintained by a feedback circuit which controls the duty cycle of the series switching "pass" element, or the amount of time the series switching "pass" element is in the "on" state compared to the amount of time it is in the "off" state. The duty cycle is inversely proportional to the difference between the source voltage level and the desired output voltage. That is, as the aforementioned difference increases, the duty cycle decreases; as the aforementioned difference decreases, the duty cycle increases. The pulsed voltage at the output of the series switching "pass element is then filtered to provide the desired output voltage. One problem with the switching voltage regulator is that the peak current through, and in some cases the peak voltage across, the series switching "pass" element is higher than the peak current through, and in some cases the peak voltage across, the series and shunt "pass" elements because the series switching "pass" element must provide the same amount of power in a shorter period of time, i.e., the time during which the series switching "pass" element is "on." Thus, a relatively large and expensive series switching "pass" element is generally required in switching regulators. Further, the corresponding pulses of current created by the switching action have fast rising and falling edges and therefore, high frequency components of current are generated. Such high frequency components may tend to cause high frequency energy to radiate from the switching regulator and cause interference in nearby circuitry.
Another well known method of voltage regulation is provided by a tapped voltage regulator. In such regulator, a plurality of successively increasing voltages is produced at a corresponding plurality of output taps. The desired output voltage is manually selected from one of the plurality of output taps. For example, a plurality of serially connected batteries may be used, each having one of the output taps. With such arrangement, a jumper may be used to physically connect the one of the taps which has a slightly greater voltage than the desired output voltage to the output terminal of the tapped regulator. As the voltage level at the selected tap decreases, the next higher voltage tap is manually connected by the use of the jumper. In this way, there is a small differential between the source voltage and the desired output voltage, as compared with a series voltage regulator, because the selected tap is only slightly higher in voltage than the desired output voltage. However, such arrangement makes a tapped regulator generally unsuitable for use where manual selection of the desired tap voltage is not feasible, such as in systems where the desired tap voltage must be selected more quickly and more accurately than can be done manually, where the cost makes manual selection impractical, or where the desired voltage must be a more exact value than which may be provided by any one of the plurality of taps.
SUMMARY OF THE INVENTION
With this background of the invention in mind, it is therefore an object of this invention to provide an improved voltage regulator.
It is another object of the invention to provide an improved voltage regulator having improved efficiency.
It is a further object of the invention to provide an improved voltage regulator of the type wherein the difference between the level of source voltage to the regulator and the level of the desired output voltage to be produced by the voltage regulator is automatically maintained at a minimum level.
It is still a further object of the invention to provide an improved voltage regulator of the type wherein the amount of generated high frequency energy is reduced.
These and other objects of the invention are attained generally by providing a voltage regulator for producing a predetermined output voltage level. The voltage regulator has a voltage source for providing a plurality of successively increasing voltage levels at a corresponding plurality of output terminals, or taps. A controller is provided for automatically selecting, in response to an electrical control signal, the one of the taps providing a voltage level above the predetermined output voltage level. In a preferred embodiment of the invention, the selected tap is the one of the plurality of taps producing a voltage level closest to, and greater than, the predetermined output voltage level. With such an arrangement, the electronic control signal allows a convenient way to select an output voltage level closest to, and greater in magnitude than, the predetermined voltage level thereby improving the efficiency of the regulator.
In accordance with an additional feature of the invention, a voltage regulator is provided for producing a predetermined output voltage level. The voltage regulator includes a voltage source for providing a plurality of successively increasing voltage levels at a corresponding plurality of output terminals, or taps. A voltage smoothing regulator is provided. The regulator includes a selector for coupling a selected one of the plurality of taps to the smoothing regulator. In a preferred embodiment, the one of the plurality of taps that is providing the voltage level closest to, and greater in magnitude than, a desired output voltage is selected and coupled to the smoothing regulator in response to a control signal. Such smoothing regulator produces, at an output thereof, the predetermined output voltage level in response to the control signal and the selected one of the plurality of voltage levels. With such an arrangement, the smoothing regulator, which may be of the series, shunt, or switching type is fed with a source of voltage having a minimum level to thereby reduce the power loss in any "pass" or power dissipative circuit element included in such smoothing regulator.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing features of this invention, as well as the invention itself, may be more fully understood from the following detailed description of the drawings, in which:
FIG. 1 is a block diagram of a voltage regulator in accordance with the invention.
FIG. 2 is a schematic diagram of a controller used in the regulator of FIG. 1;
FIG. 3 is a schematic diagram of a smoothing regulator used in the voltage regulator of FIG. 1;
FIG. 4 is a graph showing a signal VSELECTED produced by the controller of FIG. 2 plotted against a signal VCONTROL used by the regulator of FIG. 1; and
FIG. 5 is a graph showing a signal VREGULATED produced by the smoothing regulator of FIG. 3 plotted against the signal VCONTROL used by the regulator of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, a voltage regulator 10 is shown to produce a regulated output voltage, VREGULATED, having a predetermined output voltage level. More specifically, voltage regulator 10 includes a voltage source 12, having a plurality of, here 5, batteries 14 1 -14 5 serially connected to produce a plurality of successively increasing voltage levels V 1 -V 5 , at a corresponding plurality of output taps 16 1 -16 5 . A controller 18, the details of which will be described in detail in connection with FIG. 2, is provided. Suffice it to say here, however, that controller 18 includes: a plurality of, here 4, comparators 20 1 -20 4 ; a plurality of, here 4, diodes D 1 -D 4 ; and a plurality of, here 4, switches 22 1 -22 4 arranged, as shown, to automatically couple, in response to control voltage VCONTROL, a selected one of the taps 16 1 -16 5 (and hence a selected one of the voltage levels V 1 -V 5 ) to the input of smoothing regulator 24. More particularly, the one of the taps 16 1 - 16 5 selected produces a voltage level closest to, and greater than the predetermined output voltage level to be produced by the voltage regulator 10. In this way the efficiency of a smoothing regulator 24, included in the voltage regulator 10, is maximized. As will be described in detail in connection with FIG. 3, smoothing regulator 24, in response to VCONTROL, generates the desired output voltage VREGULATED.
Voltage source 12 includes DC batteries 14 1 -14 5 connected in series (with the negative potential of battery 14 1 connected to ground potential) to generate voltages V 1 -V 5 , with V 1 being of the lowest voltage potential and V 5 being of the highest voltage potential. The voltage potentials of V 1 -V 5 here range from 90 to 130 volts in 10 volt increments, although one skilled in the art will see the range, increment values and number of voltages can be changed while keeping within the scope of the invention. Voltage V 1 -V 4 are coupled to negative (-) input terminals A 1 -A 4 , respectively, of a corresponding one of the comparators 20 1 -20 4 , respectively, as shown. Coupled to positive (+) input terminals B 1 -B 4 , of the comparators 20 1 -20 4 is a signal, VCONTROL, on line 15. Comparators 20 1 -20 4 compare the voltage level of signal VCONTROL with the voltage levels V 1 - V 4 . The outputs of comparators 20 1 -20 4 are coupled to terminals S 1 -S 4 , respectively, of the switches 22 1 -22 4 , respectively, as shown. When the voltage level of VCONTROL is greater than a number of the voltages V 1 -V 4 , a corresponding number of respective switches 22 1 -22 4 are closed. For example, if the level of VCONTROL is greater than V 1 , V 2 and V 3 , then switches 22 1 -22 3 are closed. The inputs C 1 -C 4 of switches 22 1 -22 4 , respectively, are coupled to voltages V 2 -V 5 , respectively, as shown. The outputs O 1 -O 4 of switches 22 1 -22 4 are all coupled to the input I 1 of smoothing regulator 24, via line 30, as shown. Diodes D 1 -D 4 act to prevent a short circuit from occurring between any combination of two or more voltages potentials V 1 -V 5 . For example, if the level of signal VCONTROL is greater than V 2 , then switches 22 1 -22 2 are closed. If diodes D 1 -D 2 were not in place, voltage V 3 would be short circuited to V 1 and V 2 . With diodes D 1 -D 2 in place, when switches 22 1 -22 2 are closed, diodes D 1 -D 2 become reversed biased, thereby preventing a short circuit between V 3 , V 2 and V 1 .
Smoothing regulator 24 will be described in detail in connection with FIG. 3. Suffice it to say here, however, that it is responsive to the signal VCONTROL in such a way that its output voltage, VREGULATED, on line 32 is always a nominal voltage, here two volts, below the level of the voltage of signal, VCONTROL. That is, the output voltage VREGULATED from smoothing regulator 24 follows changes in VCONTROL, but is offset from VCONTROL by two volts. Smoothing regulator 24 requires that its input voltage (i.e. VSELECTED on line 30) be equal to, or greater than, its output voltage (VREGULATED on line 32). The above-described operation of comparators 20 1 -20 4 and switches 22 1 -22 4 insure that the input voltage VSELECTED on line 30 to the smoothing regulator 24 (i.e. the voltage at terminal I 1 ) is always at least slightly greater than the output voltage level VREGULATED of the smoothing regulator 24.
Referring now to FIG. 2, controller 18, and more particularly, comparators 20 1 -20 4 and switches 22 1 -22 4 , thereof, is shown in more detail. It is first noted that each one of the comparators 20 1 -20 4 is identical in construction and include: NPN transistors Q 1A -Q 4A , respectively; PNP transistors Q 1B -Q 4B , respectively; resistors R 1A -R 4A , respectively; resistors R 1B -R 4B , respectively; resistors R 1C -R 4C , respectively; and diodes D 1A -D 4A , respectively, as shown. It is next noted that each one of the switches 22 1 -22 4 is identical in construction and include: resistors R 1D -R 4D , respectively; resistors R 1E -R 4E , respectively; resistors R 1F -R 4F , respectively; and FETs Q 1C -Q 4C , respectively, as shown. The operation of comparator 20 1 will be described, it being understood that the operation of comparators 20 2 -20 4 is identical to that of 20 1 . As shown, the signal VCONTROL is coupled via line 15, to positive input B 1 of comparator 20 1 , more particularly to the anode of diode D 1A . The cathode of D 1A is coupled to the base of transistor Q 1A through resistor R 1A . The emitter of transistor Q 1A , which is the negative input A 1 of comparator 20 1 , is coupled to the voltage tap 16 1 providing voltage potential V 1 , while the collector of Q 1A is coupled to the base of transistor Q 1B through resistor R 1B . The base of transistor Q 1B is coupled to voltage V 3 (via tap 16 3 ) through resistor R 1C . The collector of transistor Q 1B acts as the output of comparator 20 1 and is coupled to terminal S 1 of switch 22 1 , as shown.
In operation, when the voltage of signal VCONTROL is lower than V 1 , transistor Q 1B is in the "off" state. That is, no current flows from the emitter of Q 1B through to the collector of Q 1B . As the voltage of signal VCONTROL increases beyond the voltage V 1 , the voltage of signal VCONTROL reaches a point at which it is large enough to induce a current through diode D 1A and resistor R 1A which turns "on" transistor Q 1A . Transistor Q 1A then draws a current from voltage potential V 3 through resistors R 1A and R 1C . As the voltage across resistor R 1C increases, transistor Q 1B is turned "on" and provides a current flowing out from the collector of transistor Q 1B to input S 1 of switch 22 1 . Thus, a signal is output from comparator 20 1 indicating to switch 22 1 that VCONTROL is greater than V 1 .
The structure and operation of switch 22 1 will now be described, with the understanding that, as noted above, switches 22 2 -22 4 have identical operation and structure as switch 22 1 . Thus one end of resistor R 1D acts as the switching control input of switch 22 1 . The opposite end of resistor R 1D is coupled to resistors R 1E and R 1F . The opposite end of resistor R 1E is coupled to the gate of transistor Q 1C , while the opposite end of resistor R 1E is coupled to the source of transistor Q 1C . The drain of transistor Q 1C , which is the input C 1 of switch 22 1 , is coupled to the cathode of diode D 2 , whose function was described above. The anode of diode D 2 is coupled to tap 16 2 providing the voltage potential V 2 . The source of Q 1C is the output O 1 of switch 22 1 .
When a current flows into the input C 1 of switch 22 1 , as a result of transistor Q 1b of comparator 16 1 being turned on and having its output current limited by resistors R 1D and R 1F , the current flows through resistor R 1D and R 1F , creating a voltage at their junction, J 1 , which is always greater than the voltage at the output O 1 of switch 22 1 . The large resistance of the gate of transistor Q 1C permits only a negligible amount of current to flow through resistor R 1E , whose main function is to dampen or prevent any oscillations caused by the gate capacitance of transistor Q 1C and any inductance inherent in the connection between R 1E and the gate of transistor Q 1C , or any other instability inherent in transistor Q 1C at its gate terminal. The voltage at the junction, J 1 , is at virtually the same voltage potential as the voltage potential at the gate of transistor Q 1C . This voltage at the gate of transistor Q 1C not only turns "on" transistor Q 1C , but forces transistor Q 1C to operate in its saturation, or low internal resistance, region as well. As a result, if the very small voltage drop across the drain to source junction of Q 1C due to its low internal resistance is ignored, the voltage at the source of Q 1C , the output O 1 of switch 22 1 , will virtually be the same as the voltage at the drain of Q 1C , the input C 1 of switch 22 1 . As a result, very little power will be dissipated in transistor Q 1C . The voltage potential provided at the output O 1 of switch 22 1 will then be voltage potential V 2 , minus any forward bias voltage drop across diode D 2 .
The combination of comparator 20 1 and switch 22 1 works as follows: As VCONTROL increases to a point beyond voltage potential V 1 , comparator 20 1 turns "on" and comparator 20 1 then supplies a current to the input S 1 of switch 22 1 , this current being sufficient to close switch 22 1 . Thus, voltage potential V 2 , minus the voltage drop across diode D 2 , is coupled to the input I 1 (FIG. 1) of smoothing regulator 24 via line 30. That is, the voltage level of the signal VSELECTED on line 30 equals V 2 minus the voltage drop across diode D 2 . The only difference between comparator 20 1 and comparator 20 4 is that the emitter of Q 4B is coupled to voltage level V 5 , which is the same voltage as that which switch 20 4 , when closed, couples to the input of smoothing regulator 24. Each emitter of transistors Q 1B -Q 3B of comparators 20 1 -20 3 respectively, is coupled to the next higher voltage potential than the voltage potential its corresponding switch 22 1 -22 3 , when closed, couples to smoothing regulator 24. Each emitter of transistors Q 1B -Q 3B is coupled to the next higher voltage potential to insure sufficient voltages at the gates of transistors Q 1C -Q 3C so that these transistors Q 1C -Q 3C operate in their saturation, or low internal resistance, mode. (Thus, referring to FIG. 1, the emitters of transistors Q 1B -Q 3B of comparators 20 1 -20 3 respectively, are coupled to voltages V 3 -V 5 ). For example, the emitter of transistor Q 1B of comparator 20 1 is coupled to V 3 , which is the next higher voltage potential from V 2 , which is coupled to smoothing regulator 24 by corresponding switch 22 1 . The result is that the highest voltage potential attainable at the output of comparator 20 4 , is V 5 . This results in the voltage potential at the gate of transistor Q 4C of switch 22 4 being smaller than V 5 ; therefore, transistor Q 4C will not, absent the configuration used and described hereinafter, be forced into saturation. Thus, if transistor Q 4C were not to go into saturation there will be a voltage drop across transistor Q 4C from its drain to its source and the largest attainable voltage potential at the output of switch 22 4 would be substantially less than V 5 .
In order to overcome the above problem and make the saturation of transistor Q 4C possible, another input has been added to switch 22 4 , and this additional input is the only difference between switches 22 4 and 22 1 . This additional input and its function will now be described. Referring also to FIG. 1, it is noted that a diode D 5 has its anode coupled to the signal VCONTROL, via line 15, and its cathode coupled to the junction, J 4 , between resistors R 4D and R 4F of switch 22 4 . When the voltage level of the signal VCONTROL is less than the voltage at the junction J 4 , diode D 5 is reversed biased, and prevents a short circuit between VCONTROL and the aforementioned junction, J 4 . As VCONTROL increases above the voltage level at the junction J 4 and diode D 5 turns "on", the voltage level of the signal VCONTROL, reduced by the voltage drop across diode D 5 , is applied to the junction, J 4 . As described above, a negligible amount of current flows through resistor R 4E due to the high impedance of the gate of transistor Q 4C . As a result, the voltage potential at the junction, J 4 is virtually equal to the voltage potential at the gate of transistor Q 4C . As the voltage level of the signal VCONTROL increases still further beyond the voltage level of V 5 , Q 4C will now be forced into saturation, and the voltage potential V 5 will be coupled to the input of smoothing regulator 24 via line 30. With this arrangement, the maximum voltage level available from the voltage source 12 is coupled to the input of smoothing regulator 24.
Referring now to FIG. 3, smoothing regulator 24 is here the series voltage regulator type. The input I 2 of smoothing regulator 24 is the drain of transistor Q 5 , which, referring briefly to FIG. 2 is coupled to the collective outputs of switches 22 1 -22 4 via line 30, as well as to voltage level V 1 through diode D 1 . The source of transistor Q 5 provides the output signal VREGULATED on line 32. Resistor R 7 is coupled between input I 1 (signal VCONTROL) and the gate of transistor Q 5 . Capacitor CAP 1 is coupled between input I 1 and ground, as shown. Resistor R 8 is coupled between input I 1 and the source of transistor Q 5 , as shown. A Zener diode ZD 1 is included, having its anode coupled to the source of Q 5 and its cathode coupled to input I 1 , as shown.
Transistor Q 5 is configured as a source follower. That is, an increase in the voltage potential at the gate of transistor Q 5 will result in a corresponding increase in voltage potential at the source of transistor Q 5 . Likewise, a decrease in voltage potential at the gate of transistor Q 5 will result in corresponding decrease in voltage potential at the source of transistor Q 5 . The gate of transistor Q 5 has a relatively high impedance, so the amount of current flowing through R 7 into the gate of transistor Q 5 is negligible. As a result, the signal VCONTROL provides the voltage potential at the gate of transistor Q 5 . An increase or decrease in the voltage level of the signal VCONTROL will induce a corresponding, respective increase or decrease in the level of the output voltage on line 32 (i.e. in the voltage of the signal VREGULATED from smoothing regulator 24). There will, however, always be a relatively fixed difference of approximately two volts between the smoothing regulator 24 output voltage VREGULATED and the level of the voltage of signal VCONTROL. That is, the voltage of signal VREGULATED will always be smaller than the voltage of the signal VCONTROL by approximately two volts. This two volt difference is the "turn-on" voltage required between the gate and source of transistor Q 5 in order to enable transistor Q 5 to conduct current from its drain to its source. Zener diode ZD 1 protects the gate to source junction of transistor Q 5 from voltage levels which might damage transistor Q 5 . For example, such voltage levels as might occur without the presence ZD if the source of Q 5 , which is the output of smoothing regulator 24, became short circuited to ground. Resistor R 7 acts to dampen or prevent any oscillations due to the combination of the gate capacitance of transistor Q 5 and the stray inductance in the connection between R 7 and the gate of Q 5 , and to otherwise stabilize Q 5 . Resistor R 8 and capacitor CAP 1 serve to provide proper impedance termination to any transmission line which would couple smoothing regulator 24 output voltage on line 30 (i.e. VREGULATED) to another circuit where power is needed. Referring now to FIG. 4, a graph is shown of a plot of the voltage of the signal VSELECTED on the vertical axis versus the voltage of the signal VCONTROL on the horizontal axis. As noted, the voltage of the signal VSELECTED is switched to the next highest tap voltage potential V 2 -V 5 when the voltage of the signal VCONTROL becomes two diode drops, or about 1.4 volts, greater than the voltage at the tap voltage V 1 -V 4 presently providing VSELECTED. For example, when the voltage of the signal VCONTROL equals 98 volts, the voltage of signal VSELECTED equals voltage V 2 , which is 100 volts. When the voltage of signal VCONTROL increases to equal approximately 101.4 volts, the voltage of signal VSELECTED is switched from the potential V 2 , which is 100 volts to potential V 3 , which is 110 volts.
When the voltage of signal VCONTROL equals 121.4 volts, the voltage of signal VSELECTED is switched to approximately 127 volts because Q 4C is not saturated, as explained previously. As the voltage of signal VCONTROL increases, it is coupled to the gate of Q 4C through the previously described second input of switch 22 4 (i.e. through diode D 5 ). Thus, when the voltage of signal VCONTROL equals approximately 132 volts, Q 4C begins to saturate, and the voltage of signal VSELECT becomes equal to V 5 , which is 130 volts. The 2 volt difference is the turn on voltage required for transistor Q 4C .
Referring now to FIG. 5, a graph is shown of the voltage of the signal VREGULATED along the vertical axis plotted against the voltage of the signal VCONTROL on the horizontal axis. The voltage of the signal VREGULATED is always approximately 2 volts less than the voltage of the signal VCONTROL. For example, when the voltage of the signal VCONTROL is 92 volts, the voltage of the signal VREGULATED is approximately 90 volts. This is due to the turn on voltage required by transistor Q 5 .
In this example, the maximum voltage of the signal VREGULATED is the voltage potential V 5 , which is 130 volts. That is, once the voltage of the signal VCONTROL reaches approximately 132 volts, the voltage of the signal VREGULATED will remain at approximately 130 volts, even as the voltage of the signal VCONTROL increases further.
This concludes the Description of the Preferred Embodiments. A reading of those skilled in the art will bring to mind many modifications and alternatives without departing from the spirit and scope of the invention. For example, an AC voltage source may be used to generate the plurality of successively increasing voltage levels at a corresponding plurality of output taps. Accordingly, it is intended that the invention only be limited by the following claims.
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A voltage regulator is provided for producing a predetermined output voltage level. The voltage regulator has a voltage source for providing a plurality of successively increasing voltage levels at a corresponding plurality of output terminals, or taps. A controller is provided for automatically selecting, in response to an electrical control signal, the one of the taps providing a voltage level above the predetermined output voltage level. In a preferred embodiment of the invention, the selected tap is the one of the plurality of taps producing a voltage level closest to, and greater than, the predetermined output voltage level. With such an arrangement, the electronic control signal allows a convenient way to select an output voltage level closest to, and greater in magnitude than, the predetermined voltage level, thereby improving the efficiency of the regulator.
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RELATED APPLICATIONS
This application is a divisional of U.S. patent application Ser. No. 11/512,877, entitled “‘All In One’ Spring Process For Cost-Effective Spring Manufacturing And Spring Self-Alignment” filed Aug. 29, 2006.
BACKGROUND
Stressed metal devices have become increasingly important for fabricating interconnects, probes, inductors and the like. However, fabrication of the stressed metal devices is a difficult and expensive process. One reason for the extra expense is the use of multiple lithography steps.
Prior art spring formation techniques typically use at least two lithography operations. A first lithography operation patterns a stressed or bimorph metal to form a general spring structure. A second lithography operation defines a spring release area (the release area is defined as the region that uplifts from a substrate). The second lithography operation may also be used to plate additional metal onto the stressed metal spring. A detailed description of the entire process is provided in U.S. Pat. No. 6,528,350 which is hereby incorporated by reference in its entirety.
These two basic lithographic operations have remained the same for about ten years. The cost associated with two lithographic operations has kept spring interconnect technology more expensive then some competing interconnect technologies. Thus a more efficient and thus less expensive way of fabricating a stressed metal device is needed.
SUMMARY
A method of making a spring structure with only a single lithographic operation is described. The method includes the operations of depositing a release layer over a substrate. A resist pattern is formed over the release layer and a spring material deposited in an opening in the resist. The spring material includes an internal stress gradient. After deposition of the spring material, the resist and spring material are exposed to an etchant that penetrates an interface between the resist and spring material. The etchant etches the release layer under a release portion of the spring material to allow a release area of the spring to curl out of the plane of the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1-9 show a side cross sectional view of the operations involved in forming a stressed metal spring using a single lithographic operation.
FIGS. 10-13 show the use of an optional adhesion and cementation layer underneath the release layer.
FIG. 14 shows a front cross sectional view of a spring prior to exposure to an etchant.
FIGS. 15-16 show the front cross sectional view of FIG. 5 as an etchant penetrates the interface between a spring material and a surrounding mask material.
FIG. 17 shows the front cross sectional view of FIG. 5 after the etchant releases the spring from the substrate.
FIGS. 18-21 show the process used in FIGS. 14-17 when the rate of etching is enhanced by a gap widening etch that increases the size of a gap between the mask and the spring material.
FIGS. 22-24 show the use of a negative side profile resist to delay spring uplift.
FIG. 25 shows a side schematic view of example resulting spring structures.
FIG. 26 shows a top view of the spring and anchor region with the unreleased portion of the anchor outlined.
FIGS. 27-28 show perforating the release region to facilitate etching the release layer underneath the spring release region.
FIGS. 29-30 show alternate spring structure patterns.
DETAILED DESCRIPTION
A method of creating a stressed metal spring structure using a single lithographic operation will be described. The spring structures are typically used to interconnect circuit devices such as integrated circuits. As used herein, stressed metal is defined as a spring structure with an internal stress gradient typically formed by the deposition of multiple sublayers, each sublayer deposited at a different a different temperature or pressure such that the density in each sublayer is different resulting in an the internal stress gradient. A detailed description of forming a stressed metal spring is provided in U.S. Pat. No. 6,528,350 entitled “Method for Fabricating a Metal Plated Spring Structure” by David Fork which is hereby incorporated by reference.
FIGS. 1-9 provide a schematic side view of a one lithography operation or an “all-in-one” process for forming a stressed metal spring. In FIG. 1 , a release layer 104 and a seed layer 108 are deposited over a substrate 100 . Release layer 104 is selected to be a material that can be easily etched to “release” a spring that will be subsequently deposited over the release layer. In one embodiment, release layer 104 is a sputtered titanium (Ti) layer.
Seed layer 108 is deposited over the release layer. Seed layer 108 facilitates growth or deposition of masking materials (typically a resist) and spring materials deposited over seed layer 108 . An example seed layer is a gold (Au) layer deposited by sputtering techniques.
It is sometimes advantageous to combine release layer 104 and seed layer 108 into a single layer or use a single material for both layers. Combining the two layers reduces the number of deposition operations during fabrication. Examples of a combined seed/release layer are titanium (Ti), copper (Cu) and nickel (Ni) deposited in a single layer over substrate 100 .
In FIG. 2 , a lithographic process is used to deposit a mask, typically a hard mask, such as a resist 204 . Resist 204 may be any common commercial photoresist used in semiconductor processing. A method of using this same resist mask for spring patterning, release and overplating will be described. Multiple use of the same mask reduces fabrication cost. Cost reductions arise from both mask count reductions and also elimination of resist spinning, baking developing, exposing and stripping associated with additional maskings.
In FIG. 3 , a spring material 304 is deposited in a resist material 204 opening. In one embodiment, spring material 304 is a nickel (Ni) plating deposited in a plurality of sublayers to create an internal stress gradient. Electroless or electroplating techniques may be used to deposit the spring material. In one embodiment, the built in stress gradient is obtained by plating from two baths with different stress characteristics or by varying the current density during plating. A detailed description of forming such stress gradients is provided in Kenichi Kataoka, Shingo Kawamura, Toshihiro Itoh, Tadatomo Suga, “Low contact-force and compliant MEMS probe card utilizing fritting contact,” IEEE Proceedings of Micro Electro Mechanical Systems (MEMS) 2002, pp. 364-367, 2002 which is hereby incorporated by reference.
Although FIG. 3 shows a stressed metal spring material, it should be understood that the spring material is not limited to stressed metals. For example, a bimorph or bimetallic material may be used. Temperature or other parameter changes induce stresses in the bimorph or bimetallic material causing the spring release portion to curl out of the plane of the resist.
After spring material deposition, the entire structure is exposed to a series of interface penetrating etches. The etchant penetrates interface 404 , 408 between spring material 304 and resist material 204 . The first etchant removes portions of the seed layer near interfaces 404 and 408 . In one example, the seed layer is a gold layer, and a typical etchant is an etchant containing potassium iodide (KI) and iodide (I).
In FIG. 5 , a second interface penetrating etchant follows the seed layer etch. The second interface penetrating etch etches release layer 104 . In one example, the release layer is a titanium layer and the second interface penetrating etchant is hydrofluoric acid (HF) or buffered hydrofluoric acid (BHF). The release layer etch starts from the interface region and laterally etches outward from interfaces 404 and 408 . Over time, the etchant removes most or all of the release layer underneath a release portion 504 of the spring material. The release layer removal allows the spring release portion 504 to uplift out of the plane in which it was deposited.
Although the preceding has been described as a two step operation of first etching a seed layer followed by etching of a release layer, it should be understood that the seed layer and the release layer may be combined into a single layer as previously described. When the seed layer and resist layer are combined, a single etchant solution penetrates the spring material/resist interface and etches the combination seed/release layer.
FIGS. 6-9 show optional spring material treatments to further enhance spring performance. FIG. 6 , shows an example of spring overplating with a cladding layer 604 . Example spring overplating materials include NiP plating, NiP+Au plating, or Cu+NiP+Au plating. The particular plating chosen depends on the spring characteristics desired which usually depends on how the spring will be used. Spring characteristics improved by plating include spring conductivity, hardness, wear resistance and stiffness.
In FIG. 7 remaining resist is stripped or otherwise removed. FIG. 8 shows the removal of the seed layer and FIG. 9 shows the removal of the release layer. A clear-etch containing potassium iodide (KI) and iodide (I) is one common method for removing a gold (Au) seed layer. A clear-etch containing hydrofluoric acid (HF) is one common method for removing a titanium (Ti) release layer.
FIGS. 10-13 show an alternative spring structure wherein a cementation layer 1004 and adhesion layer 1008 are deposited prior to release layer 104 and substrate 100 deposition. Cementation layer 1004 is typically gold (Au) or nickel (Ni) and the adhesion layer may typically be Mo, MoCr, Ti, or Cr. FIG. 13 shows cementation layer 1004 enabling selective deposition of metal 1304 under the spring. Metal 1304 enables a stronger anchoring of the spring to the substrate as well as a higher spring constant.
The process of forming a cementation and adhesion layer under a spring approximately follows the process illustrated in FIGS. 1-5 except that initially, a cementation layer 1004 and adhesion layer 1008 is deposited between release layer 104 and substrate 100 as shown in FIG. 10 . FIG. 11 shows the spring structure that results after a series of processing operations similar to that described in FIG. 2 through FIG. 5 . Those processing operations include removal of a portion of release layer 104 thereby exposing the cementation layer and adhesion layers. FIG. 12 shows the exposed cementation layer 1004 adhering to cladding material in the region immediately underneath the spring. FIG. 13 shows the final structure after resist stripping and clear etch of the seed and release layers.
FIGS. 14-18 shows a front cross sectional view of an example spring formation process. FIG. 14 shows a resist material 1404 deposited over a combination release and seed layer 1408 . Resist material 1404 is typically deposited using a photolithographic process. Once deposited, the resist serves as a mask, usually a hard mask that defines spring material 1412 deposition. As previously described, the spring material is typically deposited such that metal density gradually decreases as distance from substrate 1400 increases. The changing density helps produce the internal stress gradient.
FIG. 15 shows exposing resist material 1404 and seed layer 1408 to an interface penetrating etch. Arrows 1504 , 1508 indicate where the etchant passes between resist material 1404 and spring material 1412 . The etchant may penetrate this interface due to the loose contact between resist material 1404 and spring material 1412 . Alternatively, the etchant might overcome the adhesion forces between the resist material and the spring material. In one embodiment, a “natural gap” of less than 20 microns naturally forms between spring material 1412 and resist material 1404 during device fabrication facilitating the flow of etchant between the resist and spring interface. One mechanism for the formation of a gap is through the shrinkage of the resist after plating. This can occur by a variety of means. For example, the resist can undergo a physical change such as drying, the loss of solvent, etc. The resist can also shrink relative to the metal simply by virtue of its comparatively larger temperature coefficient of expansion relative to the substrate and the plated material. If the interface between the plated material and the resist is not strongly bonded, it will not support very much tensile stress, and will open up a gap of nanometer scale dimensions with only minor amounts of shrinkage. This effect can be augmented by depositing the plated material at an elevated temperature relative to the release etch. Further, gap widening can be enhanced by using an additional plasma etching step (e.g. oxygen (O2) plasma) which isotropically etches the photoresist but does not attack metal.
FIG. 16 shows the beginning stages of etching the combination release and seed layer 1408 . The etching produces gaps 1604 in the release and seed layer 1408 immediately under the resist-spring interface region. The gap in the release layer soon exceeds the size of any natural gap that may exist at the resist spring interface. Over time, the release and seed layer 1408 under spring material 1412 is completely etched away. Upon complete removal of the release and seed layer 1408 underneath spring material 1412 , the internal stress gradient uplifts spring material 1412 as shown in FIG. 17 .
FIGS. 18-21 show a process similar to the process of FIGS. 14-17 except that a gap widening etch facilitates the interface penetrating etch. In FIG. 19 , a gap widening etch such as oxygen (O2) plasma is used to create or widen a gap 1904 , 1908 between the spring and the resist material. In an alternate implementation, exposure to rapid temperature changes produces different expansion rates in different materials. In particular, rapid temperature changes induce different expansions of the mask and the spring material resulting in expanding of the gap between the mask and the spring material. Larger mask/spring material gaps facilitate etchant flow to the release and seed layer 2004 . Eventually the release and seed layers underneath the spring are etched away allowing spring release in FIG. 21 .
During device fabrication, it is sometimes preferable to delay spring uplift or “pop-up” until a later time in device processing. For example, when springs are formed as interconnects on a wafer, handling a smooth wafer substrate is simpler then handling a wafer substrate with uplifted spring surfaces. In such cases, FIGS. 22-24 show a structure that delays spring uplift using a negative side resist profile at the resist and spring material interface. FIG. 22 shows depositing a stressed metal spring material 2204 in resist gap 2208 . Resist side walls 2216 form a negative profile, such a negative side profile may be achieved by various techniques such as the use of negative resist, or through a resist image reversal process. Spring material 2204 forms a complimentary positive profile interface that matches the negative side profile where spring material 2204 is wider at a base and narrows toward a top layer of the spring material.
In FIG. 23 , an interface penetrating etch penetrates spring material 2204 /resist 2212 interface removing release and seed layer material 2216 under spring material 2204 . After release layer removal, an internal stress gradient provides an uplift force that tends to lift spring material 2204 . The negative profile interface along resist 2212 edge counters the uplift force and keeps down spring material 2204 . When uplift is desired, the resist is removed in FIG. 24 allowing the internal stress gradient to uplift spring material 2204 .
FIG. 25 shows an example array of spring structures 2504 , 2508 formed by the described methods. Anchor region 2512 of each spring formed by the described single step lithography method is typically larger than traditional stressed metal spring anchors. Larger anchors prevent the etch that undercuts and releases the uplift portion of the spring from undercutting the entire anchor region.
FIG. 26 shows a schematic view of an example spring 2604 including an anchor region 2608 and a release or uplift region 2612 . In order to allow complete undercutting of the release region while not completely undercutting the anchor region, the distance from the anchor region center to the nearest anchor region edge should be substantially greater than the distance from any point in the release region to the nearest release region edge. Typically, after release of the uplift portion, only a subset region, attached anchor release layer 2616 of spring anchor 2608 , remains bonded to the underlying substrate. Thus, when distance “d” represents the widest portion of release region 2612 and when a minimal interface penetrating etch releases the release region 2612 , the outer perimeter of attached spring anchor 2608 is typically at least a distance d/2 from the resist-spring interface. Another way to look at it is that the spring anchor 2608 perimeter extends approximately d/2 beyond the anchor release layer 2616 perimeter.
Although the spring dimensions may vary considerably, one typical use for the spring structure is to interconnect integrated circuit elements. Thus the springs are typically quite small. Typical dimensions for “d” are often less than 200 microns. Typical spring lengths are less than 1000 microns.
When smaller anchors are desired, (or faster release times needed), perforations incorporated into the spring release portion facilitates the etch process. FIG. 27 shows a rectangular perforation 2704 in a spring release portion while FIG. 28 shows circular perforations 2804 in a similar spring release portion.
FIGS. 29 and 30 show alternate spring structures although many other shapes will come to those of ordinary skill in the art. The one common criterion of the various shapes is that a larger wider region of the structure serves as a spring anchor and one or more narrower and longer regions of the structure serve as springs.
The preceding specification includes numerous examples and details such as geometries, materials used and the like. Such examples and details are provided to facilitate understand of the invention and its various embodiments and should not be interpreted to limit the invention. Instead, the invention should only be limited by the claims, as originally presented and as they may be amended, to encompass variations, alternatives, modifications, improvements, equivalents, and substantial equivalents of the embodiments and teachings disclosed herein, including those that are presently unforeseen or unappreciated, and that, for example, may arise from applicants/patentees and others.
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A method of forming spring structures using a single lithographic operation is described. In particular, a single lithographic operation both defines the spring area and also defines what areas of the spring will be uplifted. By eliminating a second lithographic operation to define a spring release area, processing costs for spring fabrication can be reduced.
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BACKGROUND OF THE INVENTION
The present invention relates to a phenylenediamine derivative suitable for an electric charge transferring material in a photosensitive material, and also relates to a photosensitive material using such a derivative.
As a photosensitive material in an image forming apparatus such as an electrophotographic copying apparatus, there has recently and widely been used an organic photosensitive material which is excellent in machinability and advantageous in production cost and which offers a great degree of freedom for design of performance.
For forming a copied image with the use of a photosensitive material, the Carlson process is widely used. The Carlson process comprises the steps of uniformly charging a photosensitive material with electricity by corona discharge, exposing the charged photosensitive material to a document image, thereby to form an electrostatic latent image corresponding to the document image, developing the electrostatic latent image by a toner containing developer, thereby to form a toner image, transferring the toner image to paper or the like, fixing the toner image thus transferred, and cleaning the photosensitive material to remove toner remaining thereon after the toner image has been transferred. To form an image of high quality in the Carlson process, it is required that the photosensitive material is excellent in charging and photosensitive characteristics and presents a low residual potential after exposed to light.
Conventionally, there have been known inorganic photoconductive materials such as selenium, cadmium sulfide and the like as photosensitive materials. However, these inorganic photoconductive materials are toxic and need great production costs.
There has been proposed a so-called organic photosensitive material using various organic substances in place of the above-mentioned inorganic substances. Such an organic photosensitive material has a photosensitive layer comprised of an electric charge generating material for generating electric charges by light exposure and an electric charge transferring material having a function of transferring the electric charges thus generated.
To meet various requirements for the organic photosensitive material, it is necessary to properly photosensitive material, it is necessary to properly select the electric charge generating material and the electric charge transferring material. As the electric charge transferring material, there have been proposed and put on the market a variety of organic compounds such as polyvinyl carbazole, oxadiazole compounds, pyrazoline compounds, hydrazone compounds and the like. By way of example, there have been known hydrazone compounds disclosed in Japanese Unexamined Patent Publications Nos. 59143/1979 and 210451/1990.
In the electric charge transferring materials above-mentioned, however, the drift mobility representing the electric charge transferring ability is relatively small. Further, since the dependency of the drift mobility upon the electric field intensity is great, the movement of an electric charge in a low electric field is small. This makes it difficult that the residual potential disappears. Further, such materials are disadvantageously apt to be deteriorated due to irradiation of ultraviolet rays.
In view of the problems above-mentioned, there has been proposed N,N,N',N'-tetraphenyl-1,3-phenylenediamine as an example of a m-phenylenediamine derivative of which dependency of the drift mobility upon the electric field intensity is small and which has a good compatibility with respect to a resin (Japanese Unexamined Patent Publication No. 142642/1989). Such a m-phenylenediamine derivative presents good light-exposure properties with respect to ultraviolet rays and the like. When actually used in an electrophotographic copying apparatus, this derivative presents stable characteristics. However, if this derivative is exposed to light for a long period of time or at a high temperature in case of trouble of the copying apparatus, this derivative is disadvantageously damaged in an irrecoverable extent. Further, this derivative does not have sufficient sensitivity and repeat characteristics.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a phenylenediamine derivative suitable for an electric charge transferring material.
It is another object of the present invention to provide a photosensitive material excellent in sensitivity and repeat characteristics.
The decrease in characteristics of a photosensitive material due to light exposure is generally caused by the formation, in the photosensitive material, of impurities which constitute a trap for the electric charge transferring material. In the m-phenylenediamine derivative, a ring-closure reaction made between the center benzene ring and other phenyl groups is considered to be such a photo-deterioration reaction. It is believed that this ring-closure reaction is apt to take place because the electron density of molecules in the phenylenediamine derivative is biased to the center benzene ring. Accordingly, the inventors of the present invention have considered that, when a phenyl group added to a nitrogen atom of the center benzene ring is substituted for a predetermined substituting group, or the center benzene ring is substituted for a substituting group, the reactivity of the phenylenediamine derivative may be restrained, thereby to improve photostability. After having conducted a variety of tests, the inventors have found the novel fact that, when the phenyl group or the center benzene ring is substituted for a predetermined substituting group, the photosensitive material can effectively be improved in photostability without injury to the electric charge transferring characteristics such as drift mobility and the like.
Accordingly, the phenylenediamine derivative of the present invention is represented by the following general formula (1): ##STR3## [wherein R 1 , R 2 , R 3 , R 4 and R 5 are the same as or different from one another, and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a heterocyclic group; the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the heterocyclic group may have respective substituting groups; o, p, q, r and s are the same as or different from one another, and each is an integer from 0 to 2.
Each of A 1 and A 2 is a hydrogen atom or the following group: ##STR4## (wherein R 6 and R 7 are the same as or different from each other, and each is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a heterocyclic group; the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the heterocyclic group may have respective substituting groups; n is 0 or 1. A 1 and A 2 are not hydrogen atoms simultaneously. R 6 and R 7 are not hydrogen atoms simultaneously.)]
In the phenylenediamine derivative (1) of the present invention, a phenyl group is added to each nitrogen atom of the center benzene ring. Accordingly, a reaction point is protected, causing the derivative to be hardly attacked by an oxide or the like. This restrains the ring-closure reaction between the center benzene ring and other groups to improve the photostability.
The photosensitive material containing the phenylenediamine derivative represented by the general formula (1) is less damaged by light-exposure for a long period of time or at a high temperature, than a conventional photosensitive material, and is therefore excellent in photostability.
Further, the phenylenediamine derivative represented by the general formula (1) is excellent in electric charge transferring ability. Accordingly, the phenylenediamine derivative is contained in a photosensitive layer as an electric charge transferring material, so that there may be obtained a photosensitive material excellent in sensitivity, charging ability and repeat characteristics.
DETAILED DESCRIPTION OF THE INVENTION
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the alkyl group include a lower alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl and hexyl groups.
Examples of the alkoxy group include a lower alkoxy group having 1 to 6 carbon atoms in its alkyl portion, such as methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, pentyloxy and hexyloxy groups.
Examples of the aryl group include phenyl, biphenyl, naphthyl, anthryl and phenanthryl groups.
Examples of the aralkyl group include benzyl, α-phenethyl, β-phenethyl, 3-phenylpropyl, benzhydryl, and trityl groups.
Examples of the heterocyclic group include thienyl, pyrrolyl, pyrrolidinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, 2H-imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyranyl, pyridyl, piperidyl, piperidino, 3-morpholinyl, morpholino, and thiazolyl groups. Further, the heterocyclic group may be condensed with an aromatic ring.
Examples of the substituting group include a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterificated, a cyano group, an alkyl group having straight-chain or branched 1 to 6 carbon atoms, an alkoxy group having straight-chain or branched 1 to 6 carbon atoms, and an alkenyl group having straight-chain or branched 2 to 6 carbon atoms which sometimes has an allyl group.
Preferably, the phenylenediamine derivative (1) of the present invention has a nitrogen atom added to the center benzene ring in a metha position in order to obtain a photosensitive material excellent in sensitivity and repeat characteristics.
As specific examples of the phenylenediamine derivative of the general formula (1), the following compounds (2) to (23) are mentioned. ##STR5##
The phenylenediamine derivative of the present invention may be composed in any of a variety of manners, and may be composed, for example, by the following reaction formula. ##STR6## (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same as mentioned above.)
In the reaction formula above-mentioned, an aldehyde compound of the formula (a) and a dialkyl phosphorous acid compound of the formula (b) are reacted in an organic solvent such as DMF, nitrobenzene, THF or dioxane in the presence of basishes compounds (for example, C 6 H 5 Li, NaOH or the like), thereby to give the phenylenediamine derivative of the formula (1') in accordance with the present invention.
The aldehyde compound (a) and the dialkyl phosphorous acid compound (b) are reacted at about 10° to 150° C. at equal molar quantities, thereby to give the phenylenediamine derivative of the formula (1') in accordance with the present invention.
The phenylenediamine compound of the general formula (1) serving as the electric charge transferring material may be contained, in a binding resin, alone or in combination with the other conventional electric charge transferring material, thereby to form a photosensitive layer. As the conventional electric charge transferring material, there may be used various electron attractive or donative compounds.
Examples of the electron attractive compound include a diphenoquinone derivative such as 2,6-dimethyl-2',6'-di(tert-dibutyl)diphenoquinone or the like, malononitrile, a thiopyran compound, tetracyanoethylene, 2,4,8-trinitrothioxanthene, 3,4,5,7-tetranitro-9-fluorenone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, dibromo maleic anhydride and the like.
Examples of the electron donative compound include nitrogen-containing cyclic compounds and condensed polycylic compounds which include oxadiazole compounds such as 2,5-di(4-methylaminophenyl), 1,3,4-oxadiazole and the like, styryl compounds such as 9-(4-diethylaminostyryl)anthracene and the like, carbazole compounds such as polyvinyl carbazole and the like, pyrazoline compounds such as 1-phenyl-3-(p-dimethylaminophenyl)pyrazoline and the like, hydrazone compounds, triphenylamine compounds, indole compounds, oxazole compounds, isooxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds and the like.
These examples of the electric charge transferring material may be used alone or in combination of plural types. When there is used the electric charge transferring material having film-forming properties such as polyvinyl carbazole or the like, a binding resin is not necessarily required.
The photosensitive layer of the present invention can be applied to both a single-layer type including an electric charge generating material, a compound of the general formula (1) serving as an electric charge transferring material and a binding resin, and a multi-layer type in which an electric charge generating layer and an electric charge transferring layer are laminated.
To form a single-layer type photosensitive material, there may be formed, on a conductive substrate, a photosensitive layer containing the compound of the general formula (1) serving as an electric charge transferring material, an electric charge generating material, a binding resin and the like.
To form a multi-layer type photosensitive material, an electric charge generating layer containing an electric charge generating material is formed on the conductive substrate by vapor deposition, coating or the like, and an electric charge transferring layer containing the compound of the general formula (1) serving as the electric charge transferring material and a binding resin is then formed on the electric charge generating layer. On the contrary, the electric charge transferring layer similar to that above-mentioned may be formed on the conductive substrate, and the electric charge generating layer containing an electric charge generating material may then be formed on the electric charge transferring layer by vapor deposition, coating or the like. Alternately, the electric charge generating layer may be formed by coating a binding resin containing an electric charge generating material and an electric charge transferring material as dispersed therein.
Examples of the electric charge generating material include selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, pyrylium salt, azo compounds, disazo compounds, phthalocyanine compounds, anthanthrone compounds, indigo compounds, triphenylmethane compounds, threne compounds, toluidine compounds, pyrazoline compounds, perylene compounds, quinacridon compounds, pyrrolopyrrole compounds and the like, which have conventionally been used. These examples may be used alone or in combination of plural types to present an absorption wavelength in a desired range.
As the binding resin of the single- or multi-layer type photosensitive layer, any of a variety of resins may be used. Examples of the binding resin include various polymers which include: thermoplastic resins such as a styrene polymer, a styrene-butadiene copolymer, a styrene-acrylonitrile copolymer, a styrene-maleic acid copolymer, an acrylic copolymer, a styrene-acrylic acid copolymer, polyethylene, an ethylene vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, a vinyl chloridevinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyallylate, polysulfon, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin and the like; crosslinking thermosetting resins such as silicone resin, epoxy resin, phenol resin, urea resin, melamine resin and the like; photosetting resins such as epoxy-acrylate, urethane-acrylate and the like. These polymers may be used alone or in combination of plural types.
When the electric charge generating layer and the electric charge transferring layer are formed with coating means, a solvent is used for preparing a coating solution. As such a solvent, there may be used any of a variety of organic solvents. Examples of such organic solvents include: alcohols such as methanol, ethanol, isopropanol, butanol and the like; aliphatic hydrocarbons such as n-hexane, octane, cyclohexane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene and the like; ethers such as a dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like; ketones such as acetone, methylethyl ketone, cyclohexanone and the like; esters such as ethyl acetate, methyl acetate and the like; dimethylformaldehyde; dimethylformamide; dimethylsulfoxide and the like. These solvents may be used alone or in combination of plural types.
To improve the electric charge generating layer in sensitivity, there may be used a conventional sensitizer such as tert-phenyl, halonaphtoquinone, acenaphthylene or the like, together with the electric charge generating material.
To improve the electric charge transferring and generating materials in dispersibility, aplicability and the like, there may be used a surfactant, a levelling agent and the like.
As the conductive substrate, any of a variety of conductive materials may be used, which include: single metal such as aluminium, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, paradium, indium, stainless copper, brass and the like; plastic material vapor-deposited or laminated with any of the metals above-mentioned; glass material coated with aluminium iodide, tin oxide, indium oxide or the like.
The conductive substrate may be made in the form of a sheet or a drum. The substrate itself may be conductive or only the surface of the substrate may be conductive. Preferably, the conductive substrate has a sufficient mechanical strength when used.
In the multi-layer type photosensitive material, the electric charge generating material forming the electric charge generating layer and the binding resin may be used at a variety of ratios. Preferably 5 to 500 parts by weight and more preferably 10 to 250 parts by weight of the electric charge generating material may be used for 100 parts by weight of the binding resin. The thickness of the electric charge generating layer is optional, but is preferably from 0.01 to 5 μm and more preferably from 0.1 to 3 μm.
The phenylenediamine derivative (electric charge transferring material) of the general formula (1) forming an electric charge transferring layer and the binding resin may be used at a variety of ratios within such a range as not to prevent the transmission of the electric charge and as to prevent the crystallization of the electric charge transferring material. Preferably 25 to 200 parts by weight and more preferably 50 to 150 parts by weight of the phenylenediamine derivative of the general formula (1) may be used for 100 parts by weight of the binding resin such that electric charges generated on the electric charge generating layer can easily be transferred by light radiation. The thickness of the electric charge transferring layer is preferably from 2 to 100 μm and more preferably from 5 to 30 μm.
In the single-layer type photosensitive material, preferably 2 to 20 parts by weight and more preferably 3 to 15 parts by weight of the electric charge generating material, and preferably 40 to 200 parts by weight and more preferably 50 to 150 parts by weight of the phenylenediamine derivative (electric charge transferring material) of the general formula (1) may be used for 100 parts by weight of the binding resin. The thickness of the single-layer type photosensitive layer is preferably from 10 to 50 μm and more preferably from 15 to 30 μm.
A barrier layer may be formed, in such a range as not to injure the characteristics of the photosensitive material, between the conductive substrate and the photosensitive layer in the single-layer type photosensitive material, or between the conductive substrate and the electric charge generating layer, between the conductive substrate and the electric charge transferring layer and between the electric charge generating layer and the electric charge transferring layer in the multi-layer type photosensitive material. Further, a protective layer may be formed on the surface of the photosensitive material.
When the electric charge generating layer and the electric charge transferring layer are formed by a coating method, the electric charge generating material, the binding resin and the like may be prepared as dispersed and mixed with the use of any of conventional methods, for example, a roll mill, a ball mill, an atriter, a paint shaker, a supersonic dispenser or the like, thereby to prepare a coating solution. Then, the coating solution may be applied with the use of any of conventional coating methods, and then allowed to dry. As mentioned earlier, the electric charge generating layer may be formed by vapor-depositing the electric charge generating material.
EXAMPLES
The following description will discuss in detail the present invention with reference to examples and comparative examples thereof.
(1) Synthesis Examples of Electric Charge Transferring Material
EXAMPLE 1
Synthesis of a phenylenediamine derivative represented by the formula (2)
In the presence of 20 g of basishes compounds (t-butoxypotassium), 44.1 g of an aldehyde compound of the following formula (24) and 24.2 g of a dialkyl phosphorous acid compound of the following formula (25) were reacted in 2,000 ml of DMF at 50° C. for 12 hours. The resultant product was isolated by recrystallizing operation to give a phenylenediamine derivative of the formula (2). ##STR7##
The resultant phenylenediamine derivative had a yield of 26%. The following shows the results of elemental analysis.
In C 39 H 31 N 2 : Calculation Values-C:86.16%, H:5.75%, N:5.15%; Measured Values-C:86.32%, H:5.66%, N:5.08%.
EXAMPLE 2
Synthesis of a phenylenediamine derivative represented by the formula (4)
A phenylenediamine derivative of the formula (4) was prepared in the same manner as in Example 1 except that 37.8 g of a dialkyl phosphorous acid compound of the following formula (27) was used in place of a dialkyl phosphorous acid compound of the formula (25). ##STR8##
The resultant phenylenediamine derivative had a yield of 20%. The following shows the results of elemental analysis.
In C 49 H 41 N 2 : Calculation Values-C:90.33%, H:5.46%, N:4.21%; Measured Values-C:90.28%, H:5.54%, N:4.18%.
EXAMPLE 3
Synthesis of a phenylenediamine derivative represented by the formula (5)
A phenylenediamine derivative of the formula (5) was prepared in the same manner as in Example 1 except that 28.0 g of a dialkyl phosphorous acid compound of the following formula (29) was used in place of a dialkyl phosphorous acid compound of the formula (25). ##STR9##
The resultant phenylenediamine derivative had a yield of 30%. The following shows the results of elemental analysis.
In C 44 H 29 N 2 : Calculation Values-C:89.46%, H:5.80%, N:4.74%; Measured Values-C:89.32%, H:5.87%, N:4.81%.
EXAMPLE 4
Synthesis of a phenylenediamine derivative represented by the formula (6)
A phenylenediamine derivative of the formula (6) was prepared in the same manner as in Example 1 except that 46.7 g of an aldehyde compound of the following formula (30) was used in place of an aldehyde compound of the formula (24), and 28.0 g of a dialkyl phosphorous acid compound of the following formula (31) was used in place of a dialkyl phosphorous acid compound of the formula (25). ##STR10##
The resultant phenylenediamine derivative had a yield of 36%. The following shows the results of elemental analysis.
In C 52 H 50 N 2 : Calculation Values-C:89.20%, H:6.37%, N:4.43%; Measured Values-C:89.33%, H:6.30%, N:4.37%.
EXAMPLE 5
Synthesis of a phenylenediamine derivative represented by the formula (12)
A phenylenediamine derivative of the formula (12) was prepared in the same manner as in Example 1 except that 46.7 g of an aldehyde compound of the following formula (32) was used in place of an aldehyde compound of the formula (24), and 30.6 g of a dialkyl phosphorous acid compound of the following formula (33) was used in place of a dialkyl phosphorous acid compound of the formula (25). ##STR11##
The resultant phenylenediamine derivative had a yield of 22%. The following shows the results of elemental analysis.
In C 54 H 54 N 2 : Calculation Values-C:89.05%, H:6.71%, N:4.24%; Measured Values-C:88.97%, H:6.70%, N:4.33%.
EXAMPLE 6
Synthesis of a phenylenediamine derivative represented by the formula (18)
A phenylenediamine derivative of the formula (18) was prepared in the same manner as in Example 1 except that 44.1 g of an aldehyde compound of the following formula (34) was used in place of an aldehyde compound of the formula (24), and 30.8 g of a dialkyl phosphorous acid compound of the following formula (35) was used in place of a dialkyl phosphorous acid compound of the formula (25). ##STR12##
The resultant phenylenediamine derivative had a yield of 36%. The following shows the results of elemental analysis.
In C 40 H 34 N 2 : Calculation Values-C:88.53%, H:6.31%, N:5.16%; Measured Values-C:88.64%, H:6.24%, N:5.12%.
EXAMPLE 7
Synthesis of a phenylenediamine derivative represented by the formula (19)
A phenylenediamine derivative of the formula (19) was prepared in the same manner as in Example 1 except that 44.1 g of an aldehyde compound of the following formula (36) was used in place of an aldehyde compound of the formula (24), and 28.0 g of a dialkyl phosphorous acid compound of the following formula (37) was used in place of a dialkyl phosphorous acid compound of the formula (25). ##STR13##
The resultant phenylenediamine derivative had a yield of 32%. The following shows the results of elemental analysis.
In C 44 H 34 N 2 : Calculation Values-C:89.46%, H:5.80%, N:4.74%; Measured Values-C:89.60%, H:5.70%, N:4.70%.
EXAMPLE 8
Synthesis of a phenylenediamine derivative represented by the formula (20)
A phenylenediamine derivative of the formula (20) was prepared in the same manner as in Example 1 except that 44.1 g of an aldehyde compound of the following formula (38) was used in place of an aldehyde compound of the formula (24), and 29.4 g of a dialkyl phosphorous acid compound of the following formula (39) was used in place of a dialkyl phosphorous acid compound of the formula ##STR14##
The resultant phenylenediamine derivative had a yield of 26%. The following shows the results of elemental analysis.
In C 46 H 36 N 2 : Calculation Values-C:89.57%, H:5.88%, N:4.55%; Measured Values-C:89.41%, H:5.76%, N:4.59%.
(2) Preparation of Electrophotosensitive Material
Preparation of Multi-Layer Type Electrophotosensitive Material
EXAMPLES 9 to 13 AND COMPARATIVE EXAMPLES 1 AND 2
2 Parts by weight of the electric charge generating material, 1 part by weight of a polyvinyl butyral resin ("S-lecBM-5" manufactured by Sekisui Kagaku Kogyo Co., Ltd.) and 120 parts by weight of tetrahydrofuran were dispersed for 2 hours by means of a paint shaker using zirconia beads (having a diameter of 2 mm). The dispersing solution thus prepared was applied, by means of a wire bar, to an aluminium sheet, which was then dried at 100° C. for 1 hour. Thus, an electric charge generating layer with a thickness of 0.5 μm was formed. The electric charge generating materials which were used are shown in Tables 1 and 2. In Tables 1 and 2, the electric charge generating materials A, B and C of the examples are compounds represented by the following formulas (A), (B) and (C). ##STR15##
1 Part by weight of the electric charge transferring material and 1 part by weight of a polycarbonate resin ("Z-300" manufactured by Mitsubishi Gas Kagaku Kogyo Co., Ltd.) were dissolved in 9 parts by weight of toluene. The solution thus prepared was applied, by means of the wire bar, to the electric charge generating layer, which was then dried at 100° C. for 1 hour. Thus, an electric charge transferring layer with a thickness of 22 μm was formed. In Tables 1 and 2, the electric charge transferring materials used in Examples 9 to 13 are represented by compound numbers shown in the above-mentioned specific examples. The electric charge transferring materials I and II used in Comparative Examples 1 and 2 are compounds represented by the following formulas (I) and (II). ##STR16##
Preparation of Single-Layer Type Electrophotosensitive Material
EXAMPLES 14 TO 16 AND COMPARATIVE EXAMPLES 3 AND 4
1 Part by weight of the electric charge generating material and 60 parts by weight of tetrahydrofuran were dispersed for 2 hours by means of a paint shaker using zirconia beads (having a diameter of 2 mm). To the dispersing solution thus prepared are added 50 parts by weight of a tetrahydrofuran solution of a polycarbonate resin having 20% by weight of a solid content ("Z-300" manufactured by Mitsubishi Gas Kagaku Kogyo Co., Ltd.) and 10 parts by weight of the electric charge transferring material, which were further dispersed for 1 hour. The dispersing solution thus prepared was applied, by means of a wire bar, to an aluminum sheet, which was then dried at 100° C. for 1 hour. Thus, a photosensitive layer with a thickness of 20 μm was formed. The electric charge generating and transferring materials which were used are indicated at respective chemical constitutional formula numbers in Tables 1 and 2 in the same manner as in the above-mentioned examples.
(3) Evaluation of the Electrophotosensitive Material
The surface potential, half-life light exposure (E 1/2 ) and residual potential of the photosensitive material obtained in the above-mentioned examples and comparative examples were measured by means of an evaluation tester ("EPA8100" manufactured by Kawaguchi Denki Co., Ltd.).
Measuring conditions are as follows.
Light Intensity: 50 lux
Exposure Intensity: 1/15 second
Surface Potential: A flowing current value was adjusted so as to approximate (±)700 V.
Light Source: Tungsten lamp
Electric Removal: 200 lux
Measurement of Residual Potential: Measurement was started after exposure continued for 0.2 second.
The test results of Examples 9 to 13 and Comparative Examples 1 and 2 for the multi-layer type photosensitive material and those of Examples 14 to 16 and Comparative Examples 3 and 4 for the single-layer type photosensitive material are shown in Tables 1 and 2, respectively.
TABLE 1______________________________________Electric Electriccharge chargetransfer- gen- Surface Residualring erating potential E.sub.1/2 potentialmaterial material (V) (lux · sec) (V)______________________________________Example 2 A -705 1.13 -110 9Example 6 A -695 1.26 -12010Example 12 A -710 1.29 -11511Example 19 B -700 1.03 -10012Example 20 C -705 1.34 -12013Compar- I A -705 5.33 -230ativeExampleCompar- II A -695 4.72 -195ativeExample2______________________________________
TABLE 2______________________________________Electric Electriccharge chargetransfer- gen- Surface Residualring erating potential E.sub.1/2 potentialmaterial material (V) (lux · sec) (V)______________________________________Example 4 A +710 1.44 +12514Example 5 A +715 1.52 +13015Example 18 A +710 1.37 +12516Compar- I A +700 4.67 +255ativeExampleCompar- II A +700 5.26 +265ativeExample4______________________________________
As seen from these test results, the photosensitive material of each of Examples 9 to 16 has almost the same surface potential as the conventional photosensitive material (Comparative Examples 1 to 4), but is more excellent in half-life light exposure and residual potential and has its sensitivity remarkably improved.
|
The present invention provides a phenylenediamine derivative of the following general formula (1). This derivative is excellent in photostability. Accordingly, when this derivative is contained in a photosensitive layer as an electric charge transferring material, there may be obtained an electrophotosensitive material excellent in photostability. ##STR1## [wherein R 1 , R 2 , R 3 , R 4 and R 5 are the same as or different from one another.
Each of A 1 and A 2 is a hydrogen atom or the following group: ##STR2## (wherein R 6 and R 7 are the same as or different from each other, and each is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a heterocyclic group; the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the heterocyclic group may have respective substituting groups; n is 0 or 1. A 1 and A 2 are not hydrogen atoms simultaneously. R 6 and R 7 are not hydrogen atoms simultaneously.)]
| 6
|
FIELD OF THE INVENTION
[0001] This invention relates to the field of chemical-pharmaceutical industry, specifically a new antituberculous (TB) treatment that contains, as an active ingredient, 4-thioureido-iminomethylpyridinium perchlorate in a therapeutically effective and safe level and with pharmaceutically acceptable excipients. In addition, this new product relates to a method of preparation and a method of treating and preventing all forms of pulmonary and extrapulmonary TB by use in combination with other TB drugs.
BACKGROUND
[0002] The high mortality rate from TB is an urgent health issue. Globally, there were an estimated 9.27 million incident cases of TB in 2007, according to World Health Organization (WHO) data. This is an increase from 9.24 million cases in 2006, 8.3 million cases in 2000, and 6.6 million cases in 1990. Most of the estimated total cases in 2007 were in Asia (55%) and Africa (31%), with a small proportion in the Eastern Mediterranean (6%), Europe (5%), and the Americas (3%). The five top countries in terms of total incidence in 2007 were India (2.0 million), China (1.3 million), Indonesia (0.53 million), Nigeria (0.46 million), and South Africa (0.46 million). Of the 9.27 million incident cases, an estimated 1.37 million (15%) were HIV-positive; 79% of these HIV-positive cases were in the Africa and 11% were in South-East Asia.
[0003] Although the total number of incident cases of TB is increasing in absolute terms as a result of population growth, the number of cases per capita is falling. The rate of decline is slow, at less than 1% per year. Globally, rates peaked at 142 cases per 100,000 population in 2004. In 2007, there were an estimated 139 incident cases per 100,000 population. Incidence rates are falling in five of the six WHO regions (the exception is Europe, where rates are approximately stable).
[0004] There were an estimated 0.5 million cases of multidrug-resistant TB (MDR-TB). There are 27 countries (of which 15 are in Europe) that account for 85% of all such cases. The most prominent countries in terms of total numbers of MDR-TB cases are India (131,000), China (112,000), Russia (43,000), South Africa (16,000), and Bangladesh (15,000). By the end of 2008, 55 countries and territories had reported at least one case of extensively drug-resistant TB (XDR-TB) [World Health organization (WHO) Report 2009 [Guidelines for surveillance of drug resistance in tuberculosis. 4 th Ed. WHO/HTM/TB/2009.422, WHO Press, Geneva, CH].
[0005] Remarkable achievements in TB control are associated with drug treatments. There have already been a large number of such TB medications. The first chemical preparations (streptomycin, sodium para-aminosalicylate, and tibon) appeared at the end of 1940s. Then ftivazide, isoniazid, and new effective chemical preparations such as ethionamide, canamycin, florimycin, cycloserine, and prothionamide were developed, allowing the most appropriate and effective individual treatment. Then rifampicin, ethambutol, and mycobutin, which are very effective TB drugs, became available. However, Mycobacterium tuberculosis with extensive resistance to these new drugs then emerged.
[0006] In standard TB therapy (for all forms of TB), the basic and most effective TB drugs are isoniazid (isonicotinic acid hydrazide, INH) [M. D. Mashkovsky: Pharma Products, vol. 2, Kharkov, Torsing, 1997, p. 332-333, 341-342.], a forerunner of this new development, and rifampicin [M. D. Mashkovsky: Pharma Products, vol. 2, Kharkov, Torsing, 1997, p. 332-333, 341-342; A. G. Khomenko: Chemotherapy of Pulmonary Tuberculosis, Moscow: Meditsina, 1980, 279 p.]. Although isoniazid shows a good therapeutic effectiveness, it is very toxic (LD 50 is 150 mg/kg), and its long-term administration is associated with digestive, renal, emotional, hematological, and allergic disorders and toxic hepatitis. The main disadvantage of isoniazid is that resistance in M. tuberculosis is rapidly developed in 70% of patients and up to 30% of TB patients become chronic carriers. The semisynthetic antibiotic rifampicin is also very active against M. tuberculosis , although it has high toxic effects. As with isoniazid, the main disadvantage of rifampicin is a rapid development of rifampicin resistance in M. tuberculosis , which is observed in 40-50% of TB patients and significantly decreases the drug's effectiveness. In cases of rifampicin-resistant TB, it is necessary to combine rifampicin with other TB drugs (streptomycin, isoniazid, ethambutol, etc.) [M. D. Mashkovsky: Pharma Products, vol. 2, Kharkov, Torsing, 1997, p. 332-333, 341-342]. Resistance of M. tuberculosis to available TB drugs necessitated the development of new types of treatment and their combination.
[0007] The object of the new preparation outlined here is to prepare a new highly effective TB treatment that has minimal toxic effects and is stable during storage.
SUMMARY OF THE INVENTION
[0008] The medicament is a new original TB treatment that contains, as an active ingredient, 4-thioureido-iminomethylpyridinium perchlorate in a therapeutically effective and safe level and pharmaceutically acceptable excipients.
[0009] The 4-thioureido-iminomethylpyridinium perchlorate is obtained by reacting (excess) 4-pyridine aldehyde with thiosemicarbazide in water-ethanol solutions of 48-55% perchloric acid at 80-85° C.
[0010] The TB drug contains an active ingredient 4-thioureido-iminomethylpyridinium perchlorate 5.0-90.0% w/w and pharmaceutically acceptable auxiliary substances 100% w/w (% expressed by weight of the total formulation).
[0011] The effective amount of active ingredient in the formulation is 5 to 1,000 mg.
[0012] The medicament preferably contains at least one more additional TB agent to produce a synergic effect. Exemplary additional TB agents include active ingredients such as isoniazid, pyrazinamid, rifampicin, rifabutin, amycacin, ethambutol, and fluoroquinolone antibiotic or their combinations.
[0013] Preparation preferably may be in the form of film-coated tablets (enteric coated modified release tablets), or combined tablets, capsules, granules, suppositories, and suspensions. The pharmaceutical dosage form of the present invention may be prepared using conventional technologies [Pharmaceutical Technology. Dosage Form technology, 2 nd ed., Moscow, 2006].
[0014] Administration may be oral or parenteral. The dose of the medication depends on the patient's age, condition and weight and the route of administration.
[0015] In addition to the active ingredient, the medicine may contain excipients such as binders, bulking materials, preservatives, glidants, softeners, humectants, dispersants, emulsifiers, diluents, antioxidants and/or propellents and prolongators [Sucker et al.: Pharmazeutische Technologie, Thieme-Verlag, Stuttgart, 1991].
[0016] The target additives are preferably sucrose, povidone, microcrystalline cellulose, colloidal silicon dioxide, ethylcellulose, copolymers of methacrylic acid and ethyl acrylate, triethyl citrate, macragol, talc, and ferric oxide dye, in amounts expressed as percent by weight of the active ingredient:
Sucrose: 3.1-50.4
Povidone: 0.9-14.4
[0017] Microcrystalline cellulose: 1.1-18.0
Colloidal silicon dioxide: 0.2-3.6
Ethylcellulose: 0.2-3.6
[0018] The most common techniques for the preparation of tablets are three technological processes: wet granulation, dry granulation, and direct compression.
[0019] However, described herein is a novel formulation based on the 4-compound. The methods for preparing the novel composition using the steps described herein are not disclosed in the prior art.
[0020] For this the optimum technique is the wet granulation procedure, including mixing, wetting, granulation, drying, dusting, and tabletting [Dosage Form technology, Ed. L. A. Ivanova, Moscow: Meditsina, 1991, vol. 2, p. 142, 223.].
[0021] The method involves the following steps:
[0000] (a) Powders of 4-thioureido-iminomethylpyridinium perchlorate, colloidal silicon dioxide, crosspovidone, magnesium stearate, povidone, microcrystalline cellulose, hypromellose (hydroxypropyl methylcellulose), talc, polyethylene glycol, propylene glycol, titanium dioxide, and yellow ferric oxide are independently sifted through sieves;
(b) To prepare a humectant, purified cold water (either deionized or distilled) and povidone are put into a reactor and mixed for 30 min at 60° C. until a clear homogenous solution of light-yellow colour is obtained;
(c) To prepare the mass for tabletting, 4-thioureido-iminomethylpyridinium perchlorate and microcrystalline cellulose are mixed for 15 min, then the humectant is added and mixed for at least 15 min until a uniform homogenous mass is obtained;
(d) The mass obtained at step (c) is subjected to wet granulation, such as low-shear granulation, high-shear granulation and fluid bed granulation;
(e) The wet granulated material obtained at the stages (d) is dried for 20 min at 0.2 mPa and 55±2° C. until the residual moisture content is 1.0-2.0%;
(f) The dried granulated material obtained at step (e) is subjected to dusting and dry granulation, wherein it is placed into a vibrosieve hopper and then with an antiadherent (aerosil, crosspovidone, magnesium stearate) put into a mixer, avoiding dust generation, and mixed for 15 min to obtain mass for tabletting;
(g) The mass for tabletting obtained at step (f) is compressed in a tablet press;
(h) Tablet cores are coated with aqueous suspension comprising a hypromellose mixture, yellow ferric oxide, macrogol, talc, propylene glycol, and titanium dioxide to obtain the final product.
[0022] The final tablets are oval, biconvex, and coated with yellow to dark yellow film.
[0023] When broken, the fracture zone of each tablet is of a light yellow to green-yellow colour.
[0024] The drug yield is 99.47%. Using this method, it is possible to obtain the maximum such yield.
[0025] A second method for the preparation of the new TB treatment is also proposed.
[0026] This involves direct compression and wet granulation procedures, including mixing, wetting, granulation, rolling until a desired size, coating, and drying [Dosage Form technology, Ed. L. A. Ivanova, Moscow: Meditsina, 1991, vol. 2, p. 142, 223].
[0027] In this 4-thioureido-iminomethylpyridinium perchlorate is combined with colloidal silicon dioxide, microcrystalline cellulose, and ethylcellulose; the mixed material mixed with aqueous solution of 3.0-5.0% povidone and 30.0-35.0% sugar syrup; granulated; and rolled. The granules are dried at 40-45° C. until the residual moisture content is 1.5-4.5%.
[0028] The granule cores are coated using an established technique, wherein a 20% aqueous solution of methacrylic acid-ethyl acrylate copolymers and pigment suspension of talc and ferric oxide are used.
[0029] A method for treating and preventing all forms of pulmonary and extrapulmonary TB in combination with other TB drugs is detailed in the new medicine outlined here.
[0030] Under this treatment regimen of 4-thioureido-iminomethylpyridinium perchlorate without excipients, the drugs may be administered by oral or parenteral (subcutaneously, intravenously, intramuscularly, intraperitoneally) at a single daily dose of 20 mg/kg (1,200 mg/kg), with maximum single dose of 30 mg/kg (1,800 mg/day).
[0031] To slow the development of drug resistance in M. tuberculosis , the drug is prescribed together with other TB drugs or their combinations (isoniazid, pyrazinomide, rifampicin, rifabutin, amycacin, ethambutol, fluoroquinolone antibiotics).
Biological Activity of the New Treatment
Materials and Methods for Studying Antituberculosis Activity of the New Treatment
1. Assessment of In Vitro Activity (Cultures of Microorganisms and Methods)
[0032] The following strains of microorganisms were used:
[0033] 1) Laboratory test strains from Mycobacterium tuberculosis complex, which are obtained from Tarasevich State Scientific Research Institution for Standardization and Control of Biomedical Preparations and are sensitive to the current TB drugs:
M. tuberculosis Erdman; M. tuberculosis H37Rv; M. tuberculosis “Academia”; M. bovis bovinus 8;
[0038] 2) Cultures with multiple drug resistance isolated from patients with newly diagnosed TB (14 strains):
no. 5419 StPIP 1 , resistant to isoniazid (10 μg/ml), rifampicin (40 μg/ml), and streptomycin (50 μg/ml); 1 StPIP=St. Petersburg Institute of Phthisiopulmonology no. 2483 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (40 μg/ml), streptomycin (5 and 10 μg/ml), rifabutin (40 μg/ml), ethambutol (2 μg/ml); no. 3485 and no. 3589 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (20 and 50 μg/ml), streptomycin (50 μg/ml), canamycin (30 μg/ml), ethambutol (2 μg/ml), ethionamid (30 μg/ml); no. 3019 StPIP, resistant to isoniazid (1 [[ ]] and 25 μg/ml), rifampicin (20 and 50 μg/ml), streptomycin and canamycin (30 and 50 μg/ml, respectively), ethionamid (30 μg/ml); no. 3655 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (20 and 50 μg/ml), streptomycin (50 μg/ml), canamycin and ethambutol (30 μg/ml); no. 3689 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (20 and 50 μg/ml), streptomycin (50 μg/ml), canamycin (30 μg/ml); no. 3910 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (20 and 50 μg/ml), streptomycin (50 μg/ml), canamycin and ethionamid (30 μg/ml); no. 1201 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (20 μg/ml), streptomycin (50 μg/ml), canamycin (30 μg/ml), ethambutol (2 μg/ml); no. 41 and no. 779 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (20 and 50 μg/ml), streptomycin (50 μg/ml); no. 1081 StPIP, resistant to rifampicin (20 μg/ml), streptomycin (50 μg/ml); no. 1719 and no. 1279 StPIP, resistant to isoniazid (1 μg/ml), rifampicin (20 μg/ml), streptomycin (50 μg/ml), canamycin and ethionamid (30 μg/ml);
[0050] 3) Nonspecific microorganisms sensitive to antimicrobial preparations (from collection of StPIP, Roszdrav):
gram-negative bacilli: E. coli; gram-positive cocci: Staphylococcus aureus, Streptococcus aureus, Corynebacterium pseudodiphtericum (diphtheroid).
[0053] The antimicrobial activity of 4-thioureido-iminomethylpyridinium perchlorate was studied using a common method of double serial dilution in nutrient media depending on the biological properties of the test strains:
Soton's synthetic medium with 10% normal serum (for mycobacteria); sugar broth (for gram-positive and gram-negative bacteria).
[0056] Microbial suspension was prepared ex tempore at working concentration of 5×10 6 cells/ml.
[0057] The 4-thioureido-iminomethylpyridinium perchlorate doses were studied in range of 100-0.19 μg/ml (without excipient), and 3 repeated tests were performed for each culture. A 0.2 ml sample of suspension of test strains was added to each test and control tubes: a surface plating method was used for mycobacterial suspension, and a deep plating method was used for suspension of nonspecific bacteria. The nonspecific bacterial growth and mycobacterial growth were measured following 24 h and 7-10 days, respectively. The criterion of activity was the lowest concentration of the new treatment in the media to completely inhibit bacterial growth (minimal inhibitory concentration, MIC, μg/ml).
[0058] The strain M. bovis bovinus 8 sensitive to TB drugs was used in experimental models of tuberculosis.
2. Assessment of Therapeutic Effect of the New Treatment.
[0059] For this purpose, the index of treatment effectiveness (ITE) (%) was used. The ITE is relative change, which involves comparing the severity of TB infection in control groups and in animals receiving the new treatment. It is calculated by the following formula:
[0000]
I
T
E
(
%
)
=
n
c
-
n
t
n
c
×
100
,
[0000] where n c and n t are the mean values in the control and test groups, respectively.
[0060] The positive ITE (plus-effect) indicates either a decrease in prevalence or an increase in therapeutic activity of TB drugs combined with the new treatment.
[0061] The negative ITE (minus-effect) indicates either an increase in prevalence or a decrease in therapeutic activity of the TB drug combined with the new treatment.
[0062] When assessing the activity of comparator drugs, the ITE was calculated in a similar way and was designated using common symbols (first letter of the drug name).
[0063] The degree of relationships in variations of therapeutic effects was measured using the rank correlation coefficient (r) and regression coefficient of Y and X. For this purpose, the Student-Fisher methods were used.
2. Antimicrobial Activity In Vitro of the New Treatment
[0064] Data on the effect of the new treatment on the growth of test strains from Mycobacterium tuberculosis complex, which are sensitive to the current TB drugs, are given in Table 1.
[0000]
TABLE 1
Effect of the new treatment on the growth of drug-sensitive test
strains of mycobacteria (mycobacterial suspension density is
10 6 cells/ml)
Concentration
Degree of mycobacterial growth
of the new
M. tuber-
M. tuber-
M. tuber-
treatment in
M. bovis
culosis
culosis
culosis
medium (μg/ml)
bovinus 8
H37RV
Erdman
“Academia”
100
−−−
−−−
−−−
−−−
50
−−−
−−−
−−−
−−−
25
−−−
−−−
−−−
−−−
12.5
−−−
−−−
−−−
−−−
6.25
−−−
−−−
−−−
−−−
3.125
−−−
++
−−−
++
1.56
−−−
+++
+
+++
0.78
+
+++
++
+++
0.39
++
+++
++
+++
0.19
++
+++
++
+++
Culture control
+++
+++
+++
+++
[0065] As can be seen from Table 1, the new treatment inhibited the growth of the test strains at concentration ranging from 1.56 μg/ml to 6.25 μg/ml. The drug showed the highest inhibiting activity against M. bovis bovinus 8. The primary inhibition of mycobacterial growth (++) was detected at concentration of 0.19 μg/ml; and complete inhibition (MIC), at concentration of 1.56 μg/ml. The following strains are given in descending order of inhibitory effect:
M. tuberculosis Erdman (MIC=3.125 μg/ml) M. tuberculosis H37RV and M. tuberculosis “Academia” (MIC=6.25 μg/ml)
[0068] The activity of 4-thioureido-iminomethylpyridinium perchlorate against gram-positive cocci ( Staphylococcus aureus, Streptococcus aureus) and gram-positive and gram-negative bacilli ( E. coli and diphtheroid) was studied to determine the range of antimicrobial activity of 4-thioureido-iminomethylpyridinium perchlorate. The results of the study are given in Table 2.
[0000]
TABLE 2
Effect of the new treatment on the growth test strains of gram (+) and
gram (−) microorganisms (microbial suspension density is 10 6 cells/ml)
Concentration
of the new
treatment in
Degree of the growth of test strains
medium
Staphyl.
Strept.
(μg/ml)
aureus
aureus
E. coli
Diphtheroid
100
+++
+++
+++
+++
50
+++
+++
+++
+++
25
+++
+++
+++
+++
12.5
+++
+++
+++
+++
6.25
+++
+++
+++
+++
3.125
+++
+++
+++
+++
1.56
+++
+++
+++
+++
0.78
+++
+++
+++
+++
0.39
+++
+++
+++
+++
0.19
+++
+++
+++
+++
Culture control
+++
+++
+++
+++
[0069] As can be seen from Table 2, even at high concentrations (100 μg/ml) in the medium, the new treatment did not affect the growth of gram-positive and gram-negative microorganisms.
[0070] The inhibiting activity of the new treatment against drug-sensitive mycobacteria was studied in 14 clinical isolates, of which 2 (14.3%) isolates were resistant to 6 TB drugs, 7 (50%) to 5 TB drugs, 1 (7.1%) to 4 TB drugs, 3 (21.4%) to 3 TB drugs, and 1 (7.1%) to 2 TB drugs (see Table 3).
[0000]
TABLE 3
Effect of the new treatment on the growth of drug-resistant clinical
isolates of M. tuberculosis (mycobacterial suspension density
is 5 × 10 6 microbial cells/ml)
Minimal inhibitory concentration
(MIC, μg/ml) of 4-thioureido-
iminomethylpyridinium perchlorate
Test isolates of M. tuberculosis
(without excipient)
Resistant to 6 TB drugs no. N3485
6.25
Resistant to 6 TB drugs no 3589
6.25
Resistant to 5 TB drugs no 2485
50
Resistant to 5 TB drugs no 1201
6.25
Resistant to 5 TB drugs no 3019
3.125
Resistant to 5 TB drugs no 3655
3.125
Resistant to 5 TB drugs no 3910
3.125
Resistant to 5 TB drugs no 1719
3.125
Resistant to 5 TB drugs no 1279
3.125
Resistant to 4 TB drugs no 3689
6.25
Resistant to 3 TB drugs no 5419
3.125
Resistant to 3 TB drugs no 779
1.56
Resistant to 3 TB drugs no 41
3.125
Resistant to 2 TB drugs no 1081
1.56
[0071] The tests showed that the new treatment inhibited the growth of all drug-resistant clinical isolates:
14.3% (2 strains)—at a dose of 1.56 μg/ml; 50.0% (7 strains)—at a dose of 3.125 μg/ml; 28.6% (4 strains)—at a dose of 6.25 μg/ml; 7.1% (1 strain)—at a dose of 50.0 μg/ml.
[0076] Notably, the new treatment was effective against strains resistant to 5-6 TB drugs, where MIC for 88.8% of cultures was 3.125-6.25 μg/ml.
[0077] Thus, in vitro studies showed that the new treatment:
[0078] showed a selective antimicrobial activity only against M. tuberculosis;
[0079] had a marked antituberculosis activity against both drug-sensitive and drug-resistant strains of M. tuberculosis.
1.2 Effectiveness of the New Treatment Used as Monotherapy in Experimental Tuberculosis in Mice
[0080] The study was performed in 200 white non-breed male mice weighing 18 to 20 g. In these mice, the strain M. bovis bovinus 8 caused a clinical picture of generalized tuberculosis, and specific foci of inflammation were visualized on day 11 after infection. Beginning from this day, the drugs studied were administered to the test animals.
[0081] On day 52 after infection, the fatality rate in the control group (infected animals without treatment) was 95.8% (Table 4).
[0082] At a dose of 10, 20, and 30 mg/kg the new treatment reduced lethality by 31.6%, 73.9%, and 97.5%, respectively (Table 4). The protective effect of the drug was also seen in reducing the weight loss in infected mice. At a dose of 10, 20, and 30 mg/kg the drug decreased the weight loss by 5.3%, 21.5%, and 19.0%, respectively (Table 4).
[0000]
TABLE 4
Protective effect of the new treatment, as measured by lethality rate and
changes in body weight in mice infected with M. bovis bovinus 8
Body weight
No. of
Lethality
% of
group
Experimental conditions
%
ITE %
initial
ITE %
2
Infected animals without
95.8
0
77.8
0
treatment
n = 24
3
New treatment
62.5
+31.6
81.9
+5.3
10 mg/kg, per os, per day
n = 16
4
New treatment
25.0
+73.9
94.5
+21.5
20 mg/kg, per os, per day
n = 16
5
New treatment
2.4
+97.5
92.6
+19.0
30 mg/kg, per os, per day
n = 16
Note:
ITE = index of treatment effectiveness
[0083] Thus the high protective and therapeutic characteristics of the drug used as monotherapy in mice with experimental tuberculosis indicate that it can be regarded an effective antimycobacterial remedy. These results are in line with capacity of the drug to inhibit in vitro growth of the strain M. bovis bovinus 8 (Table 1).
Effectiveness of the New Treatment Used as Monotherapy in Experimental Tuberculosis in Rabbits
[0084] The study was performed in 18 male chinchilla rabbits infected with M. bovis bovinus 8 in marginal auricular veins. Beginning from the day of infection, the new treatment was administered to rabbits (n=6) per os at a dose of 20 mg/kg for 2 months. Groups for comparison: infected rabbits without treatment (infection control, n=6) and infected rabbits treated with isoniazid (15 mg/kg, per os, n=6). The results of experiment are given in Table 5.
[0000]
TABLE 5
Protective effect of the new treatment, as measured by lethality rate and
changes in body weight in rabbits infected with M. bovis bovinus 8
Lethality
Body weight
No. of
Experimental
% of initial
% of
group
conditions
number
ITE (%)
initial
ITE (%)
1.
Infection control
100
0
−27.6
—
n = 6
2.
Isoniazid
0
+100.0
−6.99
+74.67
15 mg/kg per os
n = 6
3.
New treatment
0
+100.0
−7.13
+77.17
20 mg/kg per os,
n = 6
[0085] As can be seen from Table 5, the drug, compared to isoniazid, was more effective in preventing rabbit death from TB infection and in increasing their body weight (on average by 77.17% versus 74.67%).
2.1. Effect of the New Treatment on the Therapy of TB Drugs in Experimental Tuberculosis in Mice
[0086] The study was performed in 250 white non-breed male mice. Six combinations were compared of the new treatment (20 mg/kg, per os) with TB drugs of different specific activity. Treatment groups received monotherapy with the test TB drugs at mean therapeutic doses. In all groups, treatment was started on day 12 after infection, when specific inflammatory changes in lungs were confirmed by autopsy in mice from the infection control group. The results were assessed following 42 days (6 weeks) of treatment.
[0087] The effect of the new treatment on the therapeutic effectiveness of TB drugs, as measured by the severity of organ damage, varied depending on the properties of the test drugs ( FIGS. 1 and 2 ). TB drugs were divided into 3 groups depending on interactions with the new treatment.
[0000] Group 1. TB Drugs Having Synergic Interactions with the New Treatment (Increased Therapeutic Effectiveness Reflected by Indices of Organ Damage):
[0088] Isoniazid: Therapeutic effectiveness was increased on average by 13.9%, varying from 3.6% (a decrease in the coefficient of liver weight) to 25% (a decrease in CFU levels in the spleen);
[0089] Amycacin: Therapeutic effectiveness was increased on average by 11.34%, varying from 34.6% (a decrease in the coefficient of liver weight, p<0.001) to 1.8% (a decrease in the index of lung damage).
Group 2. TB Drugs Providing Increased Therapeutic Effectiveness, as Measured by Most Indices of Organ Damage (Three of Five):
[0090] Rifampicin: Therapeutic effectiveness was increased by 9.66% owing to a decrease in coefficients of lung (by 18.2%, p<0.05), spleen (by 34.6%, p<0.01), and liver (by 1.6%) weights, although with an increase in CFU levels by 6.19%;
[0091] Rifabutin: Therapeutic effectiveness was increased by 7.68% owing to a decrease in coefficients of lung (by 12.4%) and spleen (by 20.6%, p<0.05) weights and in isolation rates of M. tuberculosis , although with an increase in both the coefficient of liver weight and the index of lung damage (by 0.4% and 7.4%, respectively);
[0092] Ethambutol: Therapeutic effectiveness was increased by 11.44% owing to a decrease in coefficients of spleen (by 22.1%) and liver (8.9%) weights and in CFU levels in the spleen (by 33.3%), although with an increase in both the index of lung damage and the index of lung weight (by 4.0 and 3.1%, respectively).
[0000] Group 3. TB Drugs Acting with the New Treatment in an Antagonistic Way:
[0093] Ofloxacin: Therapeutic effectiveness was decreased by 6.2%, with a decrease in indices varying from 4.65% to 11.9%, except for an increase in the index of lung damage by 2.6%.
[0094] The phagocytic activity of peritoneal macrophages (pMP) in the test groups is given in Table 7. As can be seen from this table, the mean macrophagal activity of pMP during monotherapy with the new treatment was similar to that in the intact mice (132.41 versus 154.97). The new treatment activated those drugs which decreased the effectiveness of phagocytosis during monotherapy. Phagocytosis was activated when the new drug was used in combination with rifampicin (1.4-fold increase, from 71.43 to 99.12), rifabutin (1.3-fold increase, from 66.88 to 83.55), and ofloxacin (1.2-fold increase, from 95.14 to 111.66). The pMP activity was decreased when the new drug was used in combination with isoniazid (1.2-fold decrease, from 77.66 to 66.54), ethambutol (1.3-fold decrease, from 106.35 to 81.95), and amycacin (2.8-fold decrease, from 193.42 to 68.29).
[0095] Morphological indices obtained for six TB drugs, which were used as monotherapy and in combination with the new treatment, are given in Table 7. The latter, when combined with rifampicin, isoniazid, ofloxacin, ethambutol, and amycacin, improved the indices of lung damage by 16.9, 10.1, 3.24, 3.19, and 2.56%, respectively. The index of lung damage was increased (by 15.9%) only when the new treatment was used in combination with rifabutin.
[0096] TB drug classification depending on the therapeutic effectiveness of these drugs used in combination with the new treatment, as measured by the comprehensive tests using correlation analysis, is given in Table 8. There were three combinations with maximum positive effect in seven damage tests (20 cases). Of these combinations, the leading combinations were rifabutin+the new treatment and rifampicin+the new treatment (each in 7 cases). Less frequent combinations were amycacin+the new treatment (4 cases) and isoniazid+the new treatment (2 cases). A weak therapeutic effectiveness was observed for the combination of the new treatment with ofloxacin or ethambutol.
[0000]
TABLE 7
Effect of the new treatment on the activity of TB drugs, as measured by
morphological activity
Scored sum of area
Breathing
Dense
Polymorpho
Total
No. of
lung
lymphocytic
Desquamative
cellular
lung
group
Drug
tissue
infiltrate
pneumonia
infiltrate
tissue
4
Rifampicin
19.65
2.37
1.94
0
23.96
5
Rifampicin + new
17.9
3.63
2.7
0
24.23
treatment
% ITE
−8.9
+53.1
+39.2
0
+1.1
8
Rifabutin
23.27
0.53
0.16
0
23.96
9
Rifabutin + new
23.24
0.64
0
0
23.88
treatment
% ITE
−0.13
+20.7
−100.0
—
—
6
Isoniazid
17.5
1.59
3.52
0.86
23.47
7
Isoniazid + new
19.23
3.01
1.81
0
24.05
treatment
% ITE
+9.89
+89.3
−48.6
—
—
9
Amycacin
17.7
3.12
2.94
0
23.76
10
Amycacin + new
17.32
2.98
3.51
0.07
23.88
treatment
% ITE
−2.1
−4.5
+19.4
—
—
12
Ethambutol
9.78
6.8
6.93
0.27
23.78
13
Ethambutol +
14.49
4.65
4.68
0.14
23.96
new treatment
% ITE
+48.14-5
−31.6
−32.5
—
—
14
Ofloxacin
7.32
6.32
10.49
0.04
24.17
15
Ofloxacin + new
8.95
3.47
11.18
0.42
24.02
treatment
% ITE
+22.3
−45.1
+6.6
—
—
[0000]
TABLE 8
TB drug classification depending on therapeutic effectiveness of these
drugs used in combination with the new treatment
Effect of TB drug
used in combination
with the new treatment
Damage test
Potentiate
Attenuate
Coefficient of lung
Rifampicin
Ofloxacin
weight
Amycacin
Ethambutol
Rifabutin
Coefficient of
Rifampicin
Ofloxacin
spleen weight
Amycacin
Ethambutol
Rifabutin
CFU level in the
Rifampicin
Ofloxacin
spleen
Amycacin
Rifabutin
Breathing lung
Rifabutin
Ofloxacin
tissue score
Rifampicin
Ethambutol
Dense lymphocytic
Rifabutin
Ethambutol
infiltrate score
Amycacin
Rifampicin
Desquamative
Rifabutin
Ofloxacin
pneumonia score
Isoniazid
Ethambutol
Rifampicin
[0097] Therefore, the new treatment exhibits a marked, strictly selective inhibiting activity against Mycobacteria tuberculosis either sensitive or resistant to current TB drugs. The new treatment is a low toxic agent and causes neither a significant structural and functional damage to vital organs and systems nor irritation of gastrointestinal mucosa.
[0098] The new treatment exhibits moderate embryo toxicity, mainly if administered during organogenesis, and has a selective activity depending on individual sensitivity of animals. The new treatment appears to have a teratogenic effect, in the form of non life-threatening skeletal malformations, delay in the ossification of the sternum and extremities, edema, and subcutaneous hemorrhage, only at a dose of 100 mg/kg (five times the therapeutic dose) when administered during organogenesis. It causes no alterations in placenta development and sex formation. Continued administration of the new treatment has no effect on the reproductive function and offspring development in animals.
[0099] The new treatment has no allergenic, immunotoxic, and mutagenic properties.
[0100] Based on the above data, it is reasonable to conclude that a new medication with higher tuberculostatic activity (200 times as high) and lower toxicity (2.4 times as low) has been developed in comparison with the prototype drug.
[0101] When used in combination with other TB drugs (rifabutin, rifampicin, isoniazid, amycacin, and ethambutol), the new treatment increased the therapeutic effectiveness, as compared to monotherapy with the new treatment alone.
[0102] The new treatment is stable during storage, and its appearance, physical characteristics, and biological properties are stable for 3 years.
BRIEF DESCRIPTION OF THE DRAWINGS
[0103] For a fuller understanding of the invention, reference should be made to the following detailed description, taken in connection with the accompanying drawings, in which:
[0104] FIG. 1 is a table showing the effect of the new treatment on therapeutic effectiveness of TB drugs when used in combination (42 days of treatment).
[0105] FIG. 2 is a table showing the effect of the new treatment on therapeutic effectiveness of TB drugs when used in combination (42 days of treatment).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0106] The following examples serve to illustrate (without limiting the scope of claims) the most preferable variants of the embodiment of the invention and prove the possibility to prepare the new treatment.
[0107] As used herein, a “therapeutically effective amount” refers to that amount of the compound of the invention or other active ingredient sufficient to provide a therapeutic benefit in the treatment or management of tuberculosis or to delay or minimize symptoms associated with tuberculosis.
[0108] As used herein, a “therapeutically safe amount” refers to that amount of the compound of the invention or other active ingredient sufficient to induce a positive benefit while concurrently avoiding serious side effects, in particular avoiding unacceptable drug related adverse events, as determined within the scope of sound judgment of a skilled artisan.
[0109] A “prophylactically effective amount” refers to that amount of compound of the invention sufficient to result in the prevention, recurrence, or spread of disease. The prophylactically effective amount may refer to the amount sufficient to prevent initial disease, recurrence or spread of the disease or the occurrence of the disease in a patient, including, but not limited, to patients particularly susceptible to the disease, or occurrence of disease in another patient, i.e. spread of disease.
Example 1
[0110] The formulation is in tablet dosage form and has the following composition (expressed as percent by weight of the tablet core).
Composition Per Tablet:
[0111]
[0000]
% (mg)*
Core composition:
4-thioureido-
8.0 (23.2)
50.0 (145.0)
68.97 (200.0)
90 (261.0)
iminomethylpyridinium
perchlorate
Colloidal silicon dioxide
5.1 (14.9)
2.78 (8.05)
1.72 (5.0)
0.56 (1.61)
Crosspovidone
17.9 (51.8)
9.72 (28.19)
6.03 (17.50)
1.94 (5.64)
Magnesium stearate
2.59 (7.5)
1.39 (4.03)
0.86 (2.50)
0.28 (0.81)
Povidone
5.1 (14.9)
2.78 (8.05)
1.72 (5.0)
0.56 (1.61)
Microcrystalline cellulose
61.3 (177.7)
33.34 (96.68)
20.69 (60.0)
6.66 (19.3)
Tablet core weight (mg):
290.0
290.0
290.0
290.0
Coating composition:
Hypromellose E 5
0.12 (0.35)
0.12 (0.35)
0.12 (0.35)
0.12 (0.35)
Hypromellose E 15
2.07 (6.0)
2.07 (6.0)
2.07 (6.0)
2.07 (6.0)
Yellow ferric oxide
0.14 (0.40)
0.14 (0.40)
0.14 (0.40)
0.14 (0.40)
Macrogol 6000
0.43 (1.25)
0.43 (1.25)
0.43 (1.25)
0.43 (1.25)
Talc
0.35 (1.0)
0.43 (1.25)
0.43 (1.25)
0.43 (1.25)
Propylene glycol
0.17 (0.50)
0.17 (0.50)
0.17 (0.50)
0.17 (0.50)
Titanium dioxide
0.17 (0.50)
0.17 (0.50)
0.17 (0.50)
0.17 (0.50)
Coated tablet weight (mg)
300.0
300.0
300.0
300.0
*expressed as percent by weight of the tablet core
Modified Release Tablets 100, 200, 400, 800, and 1000 mg
Composition Per Tablet, mg:
[0112]
[0000]
4-thioureido-
100.0
200.0
400.0
800.0
1000.0
iminomethylpyridinium
perchlorate
Colloidal silicon dioxide
1.5
3.0
6.0
12.0
15.0
Calcium hydrophosphate
12.5
25.0
50.0
100.0
125.0
Povidone
2.5
5.0
10.0
20.0
25.0
Magnesium stearate
1.5
3.0
6.0
12.0
15.0
Ammonium methacrylate
12.5
25.0
50.0
100.0
125.0
copolymers
Talc
1.5
3.0
6.0
12.0
15.0
Microcrystalline
17.5
35.0
70.0
140.0
175.0
cellulose
Ethylcellulose
0.5
1.0
2.0
4.0
5.0
Tablet weight (mg)
150.0
300.0
600.0
1200.0
1500.0
Enteric Coated Tablets 200, 400, 500, 600, and 800 mg
Composition Per Tablet, mg:
[0113]
[0000]
Core composition:
4-thioureido-
200.0
400.0
500.0
600.0
800.0
iminomethylpyridinium
perchlorate
Colloidal silicon dioxide
5.0
10.0
12.5
15.0
20.0
Crosspovidone
17.50
35.0
43.75
52.5
70.0
Magnesium stearate
2.50
5.0
6.25
7.5
10.0
Povidone
5.0
10.0
12.5
15.0
20.0
Microcrystalline
60.0
120.0
150.0
180.0
240.0
cellulose
Tablet core weight ± 5%
290.0
580.0
725.0
870.0
1160.0
Coating composition:
Methacrylic acid-ethyl
16
32
40
48
64
acrylate copolymers
Yellow ferric oxide
2
4
5
6
8
Macrogol
0.75
1.5
1.875
2.25
3
Talc
7
14
17.5
21
28
Triethyl acetate
4.25
8.5
10.625
12.75
17
Enteric coated tablet
320.0
640.0
800.0
960.0
1280.0
weight (mg):
Example 2
[0114] The formulation is in solid dosage form: coated granules. The coating is applied to provide stability of composition during storage and enhance the appearance and organoleptic properties.
Coated Granule Dosage Form
Composition Per 100 g:
[0115]
[0000]
Core composition:
4-thioureido-
5
50
70
80
90
iminomethylpyridinium
perchlorate
Sucrose
50.4
25.2
14
8.4
2.8
Colloidal silicon dioxide
3.6
1.8
1
0.6
0.2
Povidone
14.4
7.2
4
2.4
0.8
Microcrystalline
18
9
5
3
1
cellulose
Ethylcellulose
3.6
1.8
1
0.6
0.2
Granule core weight:
95
95
95
95
95
Coating composition:
Methacrylic acid
3.0
3.0
3.0
3.0
3.0
copolymers
Macrogol
0.2
0.2
0.2
0.2
0.2
Yellow ferric oxide
0.2
0.2
0.2
0.2
0.2
Talc
0.85
0.85
0.85
0.85
0.85
Triethyl acetate
0.75
0.75
0.75
0.75
0.75
Coated granule weight
100
100
100
100
100
(mg):
[0116] The coating composition (expressed as percent by weight of the granule core) may be as follows:
[0000] Methacrylic acid and ethyl acrylate copolymers: 3.0-4.0
Triethyl acetate: 0.8-1.2
Macragol: 0.2-0.4
Talc: 0.9-1.3
[0117] Ferric oxide dye: 0.2-0.3.
Example 3
Pills 100, 200, 300, and 400 mg
Composition Per Pill:
[0118]
[0000]
4-thioureido-
100.0
200.0
300.0
400.0
iminomethylpyridinium
perchlorate
Colloidal silicon dioxide
2.5
5.0
10.0
10.0
Sucrose
21.0
42.0
63.0
84.0
Magnesium stearate
1.2
2.4
3.6
4.8
Povidone
6.0
12.0
18.0
24.0
Microcrystalline
22.0
44.0
66.0
88.0
cellulose
Macrogol
1.3
2.6
3.9
5.2
Yellow ferric oxide
1.0
2.0
3.0
4.0
Talc
3.5
7.0
10.5
14
Titanium dioxide
1.5
3.0
4.5
6.0
Coated pill weight
160.0
320.0
480.0
640.0
(mg):
Example 4
Capsules 50, 100, 200, 300, and 400 mg
Composition Per Capsule:
[0119]
[0000]
Unit,
Ingredient name
mg
4-thioureido-
mg
50.0
100.0
200.0
300.0
400.0
iminomethylpyridinium
perchlorate
Potato or corn starch
mg
4.0
8.0
16.0
24.0
32.0
Colloidal silicon
mg
0.5
1.0
2.0
3.0
4.0
dioxide
Crosspovidone
mg
2.0
4.0
8.0
12.0
16.0
Magnesium or calcium
mg
0.5
1.0
2.0
3.0
4.0
stearate
Microcrystalline
mg
3.0
6.0
12.0
18.0
24.0
cellulose
Capsule content weight:
mg
60.0
120.0
240.0
360.0
480.0
Gelatin capsule
pcs.
1
1
1
1
1
[0000]
Unit,
Ingredient name
mg
% (mg)
4-thioureido-
mg
75 (180.0)
83.33
91.7 (220.0)
iminomethylpyridinium
(200.0)
perchlorate
Potato or corn starch
mg
13.3 (24.0)
8.0 (16.0)
3.6 (8.0)
Colloidal silicon
mg
1.7 (3.0)
1.0 (2.0)
0.45 (1.0)
dioxide
Crosspovidone
mg
6.7 (12.0)
4.0 (8.0)
1.82 (4.0)
Magnesium or calcium
mg
1.7 (3.0)
1.0 (2.0)
0.45 (1.0)
stearate
Microcrystalline
mg
10.0 (18.0)
6.0 (12.0)
2.73 (6.0)
cellulose
Capsule content weight:
mg
240.0
240.0
240.0
Gelatin capsule
pcs.
1
1
1
Example 5
Suspension Dosage Form
[0120] 4-thioureido-iminomethylpyridinium perchlorate powder for oral suspension (100 ml vials) 200 mg/5 ml, 300 mg/5 ml, 400 mg/5 ml
Composition Per 100 ml:
[0121]
[0000]
Unit,
200 mg/
300 mg/
400 mg/
Ingredient name
mg
5 ml
5 ml
5 ml
4-thioureido-
mg
4,000.0
6,000.0
8,000.0
iminomethylpyridinium
perchlorate
Colloidal silicon dioxide
mg
40.0
60.0
80.0
β-cyclodextrin
mg
400.0
600.0
800.0
Citric acid
mg
200.0
300.0
400.0
Povidone
mg
1,400.0
2,100.0
2,800.0
Sucrose (or sorbitol)
mg
3,950.0
5,925.0
7,900.0
Vanilla , apple, or banana
mg
10.0
15.0
20.0
flavor
Weight of powder for
mg
10,000.0 ±
15,000.0 ±
20,000.0 ± 3%
suspension:
3%
3%
[0000]
Unit,
Ingredient name
mg
% (mg)
4-thioureido-
mg
36
40.0
44
iminomethyl-
(3600.0)
(4000.0)
(4400.0)
pyridinium perchlorate
Colloidal silicon
mg
1.19
1.0
0.82
dioxide
(43.0)
(40.0)
(36.0)
β-cyclodextrin
mg
11.94
10.0
8.18
(430.0)
(400.0)
(360.0)
Citric acid
mg
5.83
5.0
4.09
(210.0)
(200.0)
(180.0)
Povidone
mg
41.39
35.0
28.64
(1490.0)
(1400.0)
(1260.0)
Sucrose (or sorbitol)
mg
116.94
98.8
80.91
(4210.0)
(3950.0)
(3560.0)
Vanilla , apple, or
mg
0.31
0.25
0.2
banana flavor
(11.0)
(10.0)
(9.0)
Weight of powder for
mg
10,000.0
10,000.0
10,000.0
suspension
For suspension:
Purified water
mg
90,000.0
90,000.0
90,000.0
Suspension weight:
mg
100,000.0
100,000.0
100,000.0
[0122] All components and ratios of components are determined experimentally and are optimal, which makes it possible to prepare a TB treatment meeting the requirements of the state pharmaceutical authorities.
Example 6
Rectal Suppositories 50, 100, 200, and 300 mg
[0123]
[0000]
Unit,
Ingredient name
mg
4-thioureido-
mg
50.0
100.0
200.0
300.0
iminomethylpyridinium
(46.0-54.0)
(95.0-105.0)
(190.0-210.0)
(285.0-315.0)
perchlorate
β-cyclodextrin
mg
40.0
80.0
160.0
240.0
Glycerol
mg
10.0
20.0
40.0
60.0
Macragol
mg
100.0
200.0
400.0
600.0
Witepsol
mg
400.0
800.0
1,600.0
2,400.0
suppository basis
Suppository
mg
600.0
1,200.0
2,400.0
3,600.0
weight
(570.0-630.0)
(1,140.0-1,260.0)
(2,280.0-2,520.0)
(3,420.0-3,780.0)
Example 7
Target Additives: 4-Thioureido-Iminomethylpyridinium Perchlorate 44.5% w/w
[0124] Sieved powders of 4-thioureido-iminomethylpyridinium perchlorate at the level of 70.0 g, microcrystalline cellulose 5.0 g, colloidal silicon dioxide 1.0 g, and ethylcellulose of 1.0 g are put into a mixer and mixed for 5-10 min at the rate of 25 rpm. To the resulting mixture is added an aqueous solution of povidone and sucrose, which consists of 4.0 g of povidone, 14.0 g of sucrose, and 28 ml of water; the wet mass is passed through a granulator; the wet granules are rolled to make them of desired size and dried at 40-45° C. until the residual moisture content in granules is 1.5-4.5%. The resulting granule cores are passed through 1.0-3.0 mm sieves. The granule cores of 1.0-3.0 mm in diameter are film-coated with suspension prepared on the basis of methacrylic acid copolymers.
[0125] A total of 0.85 g of talc and 0.2 g of ferric oxide dye are mixed with 0.2 g of macrogol and 5 ml of water to obtain a cream-like consistency and then are mixed with 3.0 g of copolymer of methacrylic acid dispersed in 15 ml of water. The granule cores, when heated up to 45-50° C., are film-coated, with constant mixing and simultaneous drying with hot air to obtain 100.0 g of granules with uniform coating. The granules obtained meet the requirements of the state pharmaceutical authorities.
Example 8
Target Additives: 4-Thioureido-Iminomethylpyridinium Perchlorate 11.0% w/w
[0126] Target additives are the same as in Example 6, although amounts of components are different.
[0127] Sieved powders of 4-thioureido-iminomethylpyridinium perchlorate of 90.0 g, microcrystalline cellulose of 1.0 g, colloidal silicon dioxide of 0.2 g, and ethylcellulose of 0.2 g are put into a mixer and mixed for 5-10 min at the rate of 25 rpm. To the resulting mixture is added an aqueous solution of povidone and sucrose, which consists of 0.8 g of povidone, 2.8 g of sucrose, and 6 ml of water; the wet mass is passed through a granulator; the wet granules are rolled to make them of desired size and dried at 40-45° C. until the residual moisture content in granules is 1.5-4.5%. The resulting granule cores are passed through 1.0-3.0 mm sieves. The granule cores of 1.0-3.0 mm in diameter are film coated with suspension prepared on the basis of methacrylic acid copolymers.
[0128] A total of 0.85 g of talc and 0.2 g of ferric oxide dye are mixed with 0.2 g of macrogol and 5 ml of water to obtain a cream-like consistency and then are mixed with 3.0 g of copolymer of methacrylic acid dispersed in 15 ml of water. When the granule cores are heated up to 45-50° C., film coating is performed, with constant mixing and simultaneous drying with hot air to obtain 100.0 g of granules with uniform coating. The granules obtained are of yellow or red colour, are round or irregular in shape, and meet the requirements of the state pharmaceutical authorities.
Example 9
Target Additives: 4-Thioureido-Iminomethylpyridinium Perchlorate 100% w/w
[0129] Target additives are the same as in Example 6, although amounts of components are different. Sieved powders of 4-thioureido-iminomethylpyridinium perchlorate of 50.0 g, microcrystalline cellulose of 9.0 g, colloidal silicon dioxide of 1.8 g, and ethylcellulose of 1.8 g are put into a mixer and mixed for 5-10 min at the rate of 25 rpm. To the resulting mixture is added an aqueous solution of povidone and sucrose, which consists of 7.2 g of povidone, 25.2 g of sucrose, and 50 ml of water; the wet mass is passed through a granulator; the wet granules are rolled to make them of desired size and dried at 40-45° C. until the residual moisture content in granules is 1.5-4.5%. The resulting granule cores are passed through 1.0-3.0 mm sieves. The granule cores of 1.0-3.0 mm in diameter are film coated with suspension prepared on the basis of methacrylic acid copolymers. A total of 0.85 g of talc and 0.2 g of ferric oxide dye are mixed with 0.2 g of macrogol and 5 ml of water to obtain a cream-like consistency and then are mixed with 3.0 g of copolymer of methacrylic acid dispersed in 15 ml of water.
[0130] When the granule cores are heated up to 45-50° C., film coating is performed, with constant mixing and simultaneous drying with hot air to obtain 100.0 g of granules with uniform coating. The granules obtained meet the requirements of the state pharmaceutical authorities.
Example 10
[0131] Powders of 4-thioureido-iminomethylpyridinium perchlorate, colloidal silicon dioxide, crosspovidone, magnesium stearate, povidone, microcrystalline cellulose, hypromellose, talc, macrogol, propylene glycol, titanium dioxide, and yellow ferric oxide, all taken in required amounts as in Example 1, are independently sifted through sieves.
[0132] To prepare a humectant, estimated amounts of purified cold water and povidone are introduced into a reactor and mixed for 30 min at 60° C. until a clear, homogenous solution of light-yellow colour is obtained. Estimated amounts of 4-thioureido-iminomethylpyridinium perchlorate and microcrystalline cellulose are put into a mixer and mixed for 15 min, and then a humectant is added and mixed for at least 15 min until a uniform homogenous mass is obtained. The mass is subjected to wet granulation in a fluidized bed. Wet granulated material is dried for 20 min at 0.2 mPa and 55±2° C. until the residual moisture content is 1.0-2.0. The dried granulated material is subjected to dusting and dry granulation and is poured into the vibrosieve hopper; then the dried granulated material and dusting powder (aerosil, crosspovidone, and magnesium stearate) are put into the mixer, avoiding dust generation; the semi-product is mixed for 15 min to obtain mass for tabletting. The resulting mass is compressed in the tablet press.
[0133] Tablet cores are film coated with aqueous suspension containing hypromellose mixture, yellow ferric oxide, macrogol, talc, propylene glycol, and titanium dioxide to obtain the new treatment as in claim 1 .
Example 11
Target Additives: 4-Thioureido-Iminomethylpyridinium Perchlorate 20.0% w/w
[0134] Sieved powders of 4-thioureido-iminomethylpyridinium perchlorate of 200.0 g, dry potato starch of 16.0 g, microcrystalline cellulose of 12.0 g, crosspovidone of 8.0 g, colloidal silicon dioxide of 2.0 g, and magnesium stearate of 2.0 g are put into a mixer and mixed for 5-10 min at the rate of 50 rpm until a uniform distribution of the active ingredient is obtained. The moisture content in the mixture is 1-3%. The resulting mass is put into automatic capsule filling machines and filled into capsules. Loose dust adhered to the capsules is removed, and the capsules are packed either in plastic bottles or in blister packs. The yield is 1,000 capsules of the new treatment with a total weight of 240.0 g or 0.24 g±10%, each capsule contains 0.20 g±10% of active ingredient. The capsules obtained meet all requirements for pharmaceutical products.
Example 12
Target Additives: 4-Thioureido-Iminomethylpyridinium Perchlorate 33.3% w/w
[0135] Target additives are in the same amount as in Example 1, but corn starch is taken instead of potato starch and 4-thioureido-iminomethylpyridinium perchlorate is taken in amount of 180 g. The yield is 1,000 capsules of the new treatment with a total weight of 240.0 g or 0.24 g±10%, each capsule contains 0.20 g±10% of active ingredient. The capsules obtained meet all requirements for pharmaceutical products.
Example 13
Target Additives: 4-Thioureido-Iminomethylpyridinium Perchlorate 9.1% w/w
[0136] Target additives are in the same amount as in Example 1, but calcium stearate is taken instead of magnesium stearate and 4-thioureido-iminomethylpyridinium perchlorate is taken in amount of 220 g.
[0137] The yield is 1,000 capsules of the new treatment with a total weight of 240.0 g or 0.24 g±10%, each capsule contains 0.20 g±10% of active ingredient. The capsules obtained meet all requirements for pharmaceutical products.
Example 14
[0138] Manufacture of suppositories involves a molding process. Amounts of ingredients are calculated to have a yield of 100 suppositories. A total of 5.0 g of 4-thioureido-iminomethylpyridinium perchlorate, 4.0 g of 3-cyclodextrin, and 1.0 g of glycerol are put into a miller and are ground for 30 min. The resulting suspension is mixed in a reactor with 15.0 g of suppository base and macrogol heated up to 45° C. The resulting concentrate is cooled and then is ground for 3 h in a three-roller ointment grinder to obtain a required dispersion of the new treatment. The finished concentrate is mixed with 35.0 g of suppository base and macrogol at 48° C. until a uniform mass is obtained. The resulting mixture is poured into molds and packed. The yield is 100 suppositories meeting the following requirements: mean mass and uniformity of mass: 0.60 g±5%; melting temperature: not higher than 37° C.; amount of 4-thioureido-iminomethylpyridinium perchlorate per suppository: 0.05 (0.046-0.054).
Example 15
[0139] Sieved powders of 4-thioureido-iminomethylpyridinium perchlorate of 4.0 g, β-cyclodextrin of 0.40 g, and povidone of 1.40 g are put into a ball mill and are ground for 3 h. To the resulting complex, sieved powders of sucrose of 3.95 g, citric acid of 0.20 g, and vanilla flavour of 0.01 g are added and ground for 1 h. The ground powder is put into a mixer and is mixed with 0.04 g of colloidal silicon dioxide for 5-10 min at the rate of 50 rpm until a uniform mixture is obtained. The resulting mixture is automatically filled into vials, 10.0 g per each vial. Vials are hermetically sealed with caps and are packed into a box, with a 5 ml spoon. The obtained suspension meets the following requirements: variation of the vial content: 9.7 g to 10.3 g; water content in powder: not more than 2%; pH: 5-8; sedimentation stability of suspension: not less than 24 h.
[0140] For oral administration, dissolve the powder with 90 ml of water to the mark and use 5 ml spoon. Each 100 ml of suspension contains 20 doses, each containing 200 mg of active ingredient 4-thioureido-iminomethylpyridinium perchlorate.
Example 16
Combined Preparation in the Form of Capsules 100 mg+100 Mg, 150 mg+200 mg (Rifampicin+Perchlozone)
Composition Per Capsule:
[0141]
[0000]
Unit,
Ingredient name
mg
4-thioureido-iminomethylpyridinium
mg
100.0
200.0
perchlorate
Rifampicin
mg
100.0
150.0
Potato or corn starch
mg
38.0
76.0
Colloidal silicon dioxide
mg
1.0
2.0
Crosspovidone
mg
4.0
8.0
Magnesium or calcium stearate
mg
1.0
2.0
Microcrystalline cellulose
mg
6.0
12.0
Capsule weight:
mg
250.0
450.0
Gelatin capsule
pcs
1
1
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This invention relates to the field of chemical-pharmaceutical industry, specifically a new tuberculosis treatment that contains, as an active ingredient, 4-thioureido-iminomethylpyridinium perchlorate at a therapeutically effective and safe level and pharmaceutically acceptable excipients. In addition, this treatment relates to a method of the preparation of the new drug, providing a high yield of the new treatment. The new treatment has a higher tuberculostatic activity (200 times as high) and lower toxicity (2.4 times as low), as compared to a prototype drug, and is stable during long-term storage. This medicament may be used for treating and preventing all forms of pulmonary and extrapulmonary TB by using the new treatment in combination with other TB drugs.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] NONE
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Research and development of this invention and Application have not been federally sponsored, and no rights are given under any Federal program.
REFERENCE TO A MICROFICHE APPENDIX
[0003] NOT APPLICABLE
BACKGROUND OF THE INVENTION
[0004] 1. Field of the Invention
[0005] This invention relates to pleasure boat, fishing boat and yacht marine craft, in general, and to onboard systems employed for cooling their engines and for operating their onboard toilets and refrigerators, in particular.
[0006] 2. Description of the Related Art
[0007] As will be understood, rivers, large lakes and open waters where these craft may travel typically contain natural weed growth, algae, leaves and like accumulations—as well as unnatural debris such as plastic bags, cloth rags, paper products, etc. Although attempts are taken to prevent the entry of all these materials into the intake conduits of the craft to prevent them from fouling pumps and filters, oftentimes, the thruhole fittings become clogged. On such occasions, it is not unusual for an occupant of the vessel to enter the water himself/herself to try to unclog the water intake conduit by hand. When no one on the craft is willing to enter the water where, for example, extensive weed growth is present, the solution is to call for a tow to bring the craft to a service area where an experienced technician would attempt to clear the fitting. On the other hand, where the clogging takes place while the craft is in the bay or on the sea, almost no one is ever willing to go into the very deep water to try to clear the fitting from below; there, the call for assistance is almost always made. This is especially the situation where the water intake conduit becomes clogged by barnacles which grow inside the conduit.
[0008] In all these situations of clogging, depending on the conditions, the marine engine shuts off, the onboard toilet does not flush or the refrigerator stops working. In each instance, it becomes necessary to manually clear the intake conduit, and from outside the craft.
OBJECTS OF THE INVENTION
[0009] It is an object of the present invention, therefore, to provide a new and improved manner of clearing a clogged thruhole fitting regardless of the cause of its blockage.
[0010] It is an object of the present invention, also, to provide apparatus to enable the clearing to be accomplished from inside the craft, without having to enter the water.
[0011] It is an object of the present invention, furthermore, to provide an apparatus to enable the clearing to take place in substantially the same manner, utilizing the same type of operation, for a variety of water intake conduits, realizing that some of the conduits may be of different diameters to satisfy a variety of onboard uses on the craft.
[0012] It is an object of the present invention, additionally, to allow these clearings of clogged intake conduits to be had without any need for retrofitting an existing craft design—as would be needed in those manufactures, for example, which recommend the use of a compressed air utilization to clear clogged filters employed to prevent coarse material entry to begin with.
[0013] As will be appreciated, satisfying these objectives enables the marine craft to continue on its way, without the need for any occupant entering the water, without any need for seeking assistance to tow the craft to a staging area for service to be addressed, and without any need for redesigning or altering the existing craft structure.
SUMMARY OF THE INVENTION
[0014] As will become clear from the following description, the present invention attains all these objectives through the use of a male hose coupler, having an open-end cap with an inner gasket having central orifice of predescribed diameter through which a shaft is force-fitted to extend beyond the thruhole fitting valve into the water, yet with the gasket being flexible and resilient to accept manual rotation of the shaft through the orifice and about the gasket by way of an included handle in substantially 360° rotation to force-free the valve of any clogging material. As will be described, the hose coupler joins with the nipple or elbow coupled to the valve, from which the hose to the pump is first disconnected from the nipple or elbow with the valve closed—the valve being once again opened when the hose coupler and shaft are in place. As will also become apparent, these objectives are satisfied with the described kit of the invention serving as a separate, stored article of repair aboard the boat or marine craft until its component parts are needed to clean the clogging of the thruhole fitting valve.
[0015] In a preferred embodiment, a hollow, substantially cylindrical male hose coupler is employed having four outwardly extending flanges of progressively smaller diameter in linear progression from the first, or, cap end to a second, opposite end in allowing the use of the invention with up to four nipple or elbow hose connections as may be present in service with different sized pumps aboard the boat or marine craft. Such male hose coupler will be seen to have external threads at the first end, to which the open-end cap secures through its construction of internal threads to receive the coupler. As will be appreciated, a one, two or three flange hose coupler could instead be employed for boats or craft where a lesser number of pump interconnections are present.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] These and other features of the present invention will be more clearly understood from a consideration of the following description, taken in connection with the accompanying drawings, in which:
[0017] FIGS. 1 a , 1 b and 1 c are illustrations of typical prior art components found in water intake systems of pleasure boats, fishing boats and yacht marine craft—of a thruhole fitting valve, a nipple coupler and an elbow coupler, respectively;
[0018] FIGS. 2 a , 2 b , 2 c , 2 d , 2 e and 2 f are illustrations of component parts of a prior art male hose coupler useful in the attainment of the objectives of the present invention; and
[0019] FIGS. 3 a , 3 b , 3 c and 3 d are illustrations of the shaft and gasket interrelationships helpful in understanding the teachings of the invention.
[0020] FIG. 4 illustrates a storage compartment for the component parts employed to clear a valve blockage; and
[0021] FIG. 5 illustrates a manner of assembling the component parts for use.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The prior art nipple coupler (or “nipple”) 10 of FIG. 1 b includes external threads 12 at its lower end 14 to connect with the internal threads 16 of the prior art thruhole fitting valve 18 of FIG. 1 a . A handle 20 serves to open the valve 18 when rotated vertically and serves to close the valve 18 when rotated to a horizontal position. In use, a plastic or rubber hose (not shown) couples over the upper end 22 of the nipple 10 to connect the valve 18 with a pump (not shown) to provide marine water to cool the boat or yacht's engine, or to operate the onboard toilets and refrigerators. A clamp (also not shown) typically is used to secure that hose at the upper end 22 of the nipple 10 . An orifice is provided in the bottom of the valve 18 to receive another hose serving as a conduit for the river, lake or open waters to be drawn in and utilized in these manners when the valve is opened and the pump turned “on”.
[0023] In those instances where insufficient room exists on the craft to run a hose vertically from the upper end 22 of the nipple 10 to the pump, the elbow 24 of FIG. 1 c is employed instead. There, the external threads 26 of the elbow at its one end 28 connect with the internal threads 16 of the thruhole fitting valve 18 and the hose to the pump couples over in similar manner to its right angle-bent end 30 . A clamp (similarly not shown) secures the hose at the elbow end 28 in its path to the pump.
[0024] FIG. 2 a illustrates a hollow, substantially cylindrical prior art male hose coupler 32 having external threads 34 at an upper end 36 . A pair of outwardly extending flanges 38 , 40 of progressively smaller diameter extend linearly from the upper end 36 of the coupler 32 to an opposite second, or lower end 42 . An open end cap 44 ( FIG. 2 b ) is provided with internal threads 48 to secure the cap 44 with the upper end 36 of the coupler 32 . As will be appreciated, in its usage as a coupler, a first hose (not shown) is clamped about an input port 50 of the cap 44 , and a further hose is clamped to either of the flanges 38 and 40 in forming a water conduit. The lower end 42 of the male hose coupler 32 then serves as its output port 43 .
[0025] Additionally, and in a typical construction, a coupler extension 52 is available for insertion at the upper end 36 of the coupler 32 to protrude beyond the coupler's lower end 42 ( FIG. 2 c ). In such manner, two additional outwardly extending flanges 54 , 56 are so provided, as to allow the clamping of ever smaller diameter hoses on to the coupler. The extender 52 includes a pair of washers 58 , 60 within walled channels 62 , 64 in providing a water sealant in the coupling which follows. FIG. 2 d shows the coupler extension being inserted, with FIG. 2 e showing the result with the full insertion and with the open-end cap 44 secured'“on”.
[0026] In accordance with the teachings of the present invention, a kit is provided which includes, as an example, this prior art coupler 32 , the coupler extension 52 with its washers 58 , 60 , the open-end cap 44 , and four hoses, each having an inner diameter to fit around and over the input port 50 of the cap 44 , and the others having inner diameter hoses to fit over the appropriate flange 38 , 40 of the coupler 32 or of the flange 54 , 56 of the extension 52 . Such hoses may be of a plastic or rubber composition. A pair of clamps as in FIG. 2 f are also included in the kit, of any appropriate construction—one ( 90 ) to be positioned near where the hose (a portion shown at 92 ) is to overlap a flange (as shown) and the other ( 94 ) where it is to secure to either the upper end 22 of the nipple 10 or the right angle bent end 30 of the elbow 24 (as at 96 ).
[0027] As will become clear from the following description, the kit is included within a package to be stored aboard the pleasure boat, fishing boat or yacht, awaiting time for its need in clearing the valve when it becomes clogged with natural weed growth, algae, leaf and like accumulations—as well as such unnatural debris as plastic bags, cloth, rags and paper products when traveling through rivers, large lakes and open waters. In accordance with the teachings of the present invention, the open-end cap 44 of FIG. 2 b is modified to include a flexible gasket 66 ( FIG. 3 a ) preferably of a neoprene rubber composition press-fitted within the cap between side surfaces 68 , 70 . Additionally, a substantially central orifice 72 is provided in the gasket 66 . To finalize the construction, the kit of the invention also includes a shaft 74 ( FIG. 3 b ) of a diameter greater than that of the orifice 72 but able to be force fitted through the orifice. Such shaft 74 , additionally, is of a length to extend through the open-end cap 44 through its input port 50 , through the hose coupler 32 , through the hose secured at its lower end 42 and through the nipple 10 or elbow 24 , through the valve 18 in this manner, with the shaft being of a composition sufficiently strong to force-free the valve 18 of any matter clogging it. The shaft then becomes effective to clear whatever clogging exists in the valve 18 from inside the boat or craft, without requiring anyone to leave the vessel and enter the water. FIG. 4 illustrates a schematic arrangement of how the kit of the invention can be taken from storage for use in attaining this objective. Rotating the shaft 74 will be understood to free the clogging of the valve.
[0028] As more particularly shown in FIGS. 3 b and 3 c , to optimize this, the shaft 74 is provided with a slanted groove cut-out 76 at a lower end 78 and a handle 80 at an upper end 82 . Such slotted cut-out 76 facilitates the use of the shaft in additionally clearing barnacles that may form in the hose coupling the marine water to the valve 18 , while the handle 80 is of a substantially circular knob configuration 84 with a flat portion 86 in alignment with the cut-out 76 so as to assist a user in determining the orientation of the shaft at any time in clearing barnacles from the sides of the input hose ( FIG. 3 d ). In this embodiment, the gasket 66 is selected of a resilience to accept the manual rotation of the shaft 74 in and about the orifice 72 in the force-freeing of the valve in a substantial 360° plane of orientation from side-to-side and front-to-back.
[0029] In use of the invention, while everything is operating normally aboard the boat or craft, the kit of the invention is included in a storage compartment 90 ( FIG. 4 ). Once it is determined that a clog exists, the hose connected to the engine, toilet, refrigerator, etc. is released from the upper end 22 of the nipple or from the right-angle bend end 30 of the elbow where it is connected. The components of the kit are then set up for assembly, as shown in FIG. 5 , one of the provided hoses is fitted and secured over the appropriate flange 38 , 40 , 54 or 56 depending upon the diameter of the nipple end 22 or elbow end 30 , and then clamped into securement. The shaft 74 is then force-fit through the gasket orifice 72 and the handle 80 grasped, pushed and rotated in a circular plane through the coupler, the extension and through the valve to clear whatever clogging is present. As will be appreciated by those skilled in the art, however, before disconnecting the pump hose from the nipple or elbow, and connecting the assembled components of the invention, the handle 20 of the thruhole fitting valve 18 is first rotated to the horizontal position to close the valve—and once everything is in place for the shaft 74 to be inserted, the handle 20 is rotated to the vertical position for opening the valve 18 so the shaft can be pushed through the valve 18 to clear the blockage. Once it is determined that the clogging has been cleared, the shaft can be withdrawn, the valve 18 closed by rotating the handle 20 back to its horizontal position, the coupler 32 , and its connecting hose removed from the nipple or elbow, and the hose from the pump then reconnected. The component parts of the kit are then broken down for placement back into the compartment 90 for use at a later time, when needed again.
[0030] While there has been described what is considered to be a preferred embodiment of the present invention, it will be readily appreciated by those skilled in the art that modifications can be made without departing from the scope of the teachings herein. Thus, for example, where a preferred embodiment may employ a pair of clamps at each end of the provided hose in securing the coupler to the nipple or elbow, the teachings of the invention would apply where only one such hose clamp is utilized. Similarly, while the use of the coupler extension 52 facilitates use of the invention for four different sized nipples or elbows, the operation of the invention will be seen to follow equally as well where the coupler extension 52 is not needed, and only nipples or elbows of two diameter selections are involved. In such instance, the kit of the invention need only include two, instead of four, provided hoses. For at least such reasons, therefore, resort should be had to the claims appended hereto for a true understanding of the scope of the invention.
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A kit for cleaning clogged conduits and thruhole fitting valves in water intake systems of pleasure boats, fishing boats and yacht marine craft includes a hollow, substantially cylindrical male hose coupler connected to a nipple or elbow joined with the valve, and an open-end cap having a flexible, resilient press-fitted inner gasket configured with a central orifice to receive a shaft of larger diameter able to be force-fitted through the cap, the coupler and the valve when opened, and of a strength sufficient to force-free any matter clogging the input hose to the valve from acceptable performance usage.
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BACKGROUND OF THE INVENTION
The present invention relates to a novel process of preparing a 2-methyl-3-aminobenzotrifluoride (MA-BTF) which is useful as an intermediate of some medicines, agricultural chemicals and other chemical products. For example, U.S. Pat. Nos. 3,891,761 and 3,839,344 disclose the N-methyl-D-glucamine salt of 2-(2'-methyl-3'-trifluoromethylanilino) nicotinic acid which is derived from MA-BTF and particularly suitable as a parenterally administered analgesic agent.
There have been some proposals of process for preparing MA-BTF. For example, U.S. Pat. No. 4,209,464 discloses a process of preparing MA-BTF from 3-amino-4-chlorobenzotrifluoride. In this method, at first, 3-amino-4-chlorobenzotrifluoride is reacted with dimethylsulfoxide in the presence of phosphorus pentoxide and triethylamine to produce N-(2-chloro-5-trifluoromethyl) phenyl-S,S-dimethylsulfimide. Then, the dimethylsulfimide is converted to 3-amino-4-chloro-2-methylthiomethylbenzotrifluoride by a chemical rearrangement. Then, this trifluoride is reduced with Raney nickel to form MA-BTF. However, in this process, due to the use of a large amount of phosphorus pentoxide, there are some problems in the recovery method and the processing method of the product. Therefore, this process is not suitable for operation in an industrial scale.
GB-B-2194533 discloses another process of preparing MA-BTF. In this process, at first, 3,4-dichlorotoluene is converted to 2-methyl-4,5-dichlorobenzotrichloride by carbon tetrachloride in the presence of aluminum chloride. Then, this trichloride is fluorinated to form 2-methyl-4,5-dichlorobenzotrifluoride. Then, this trifluoride is nitrated to form 2-methyl-3-nitro-4,5-dichlorobenzotrifluoride. Then, this trifluoride is hydrogenated to form MA-BTF. However, this process is not recommendable from an environmental point of view because carbon tetrachloride which is considered to destroy the ozone layer of the earth is used as a raw material.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a novel process of preparing MA-BTF, which is free from the above-mentioned drawbacks.
According to the present invention, there is provided a process of preparing a 2-methyl-3-aminobenzotrifluoride, comprising the steps of:
(a) halogenating o-trifluoromethylbenzalhalide to form a 2-trifluoromethyl-4-halogenobenzalhalide;
(b) hydrogenating said 2-trifluoromethyl-4-halogenobenzalhalide to form a 2-methylmonohalogenobenzotrifluoride;
(c) nitrating said 2-methylmonohalogenobenzotrifluoride to form a 2-methyl-3-nitro-5-halogenobenzotrifluoride; and
(d) hydrogenating said 2-methyl-3-nitro-5-halogenobenzotrifluoride to form said 2-methyl-3-aminobenzotrifluoride.
By a process according to the present invention, MA-BTF can be produced with high yields and high productivity through 2-trifluoromethyl-4-chlorobenzalchloride and 2-methyl-3-nitro-5-chlorobenzotrifluoride which are novel compounds without using a process which is industrially hard to be conducted and without using a raw material which would be possibly prohibited to be used.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A process according to the present invention for preparing MA-BTF comprises first, second, third and fourth steps as follows: ##STR1## wherein X and Y are the same or different halogen atoms and selected from the group consisting of Cl, Br and I.
The first step of the process is a mono-halogenation reaction in which o-trifluoromethylbenzalhalide is brought into contact with a halogen in the presence of a catalyst. The reaction liquid after the first step is washed with water. The product of the first step is a mixture of nuclear mono-halogenated compounds in which a main product is 2-trifluoromethyl-4-halogenobenzalhalide. Examples of o-trifluoromethylbenzalhalide are o-trifluoromethylbenzalchloride, o-trifluoromethylbenzalbromide and o-trifluoromethylbenzaliodide. In an industrial operation of the first step, the most preferable combination of o-trifluoromethylbenzalhalide and the halogen are o-trifluoromethylbenzalchloride and chlorine, respectively. Preferable examples of the catalyst in the first step are ferric chloride, ferric bromide, aluminum chloride, aluminum bromide and antimony pentachloride. It is optional to add a promoter such as iodine. It is preferable that the reaction temperature of the first step is from 60° to 100° C. If it is lower than 60° C., the reaction proceeds too slowly. If it is higher than 100° C., the production of poly-halogenated compound(s) undesirably increases.
The second step of the process is a dehalogenation reaction to remove halogens bonded to the benzal group of 2-trifluoromethyl-4-halogenobenzalhalide. In the second step, the mono-halogenated compounds obtained by the first step are brought into contact with hydrogen under a liquid phase condition in the presence of a metal-carried catalyst and an optional basic substance. After the dehalogenation reaction, the catalyst and the salt are removed by filtration. Then, the filtrate is washed with water and then dried with a drying agent. Then, the drying agent is removed by filtration. The product of the second step is a mixture of 2-methylmonohalogenobenzotrifluoride in which a main product is 2-methyl-5-halogenobenzotrifluoride.
The reaction temperature of the second step is preferably from 0° to 100° C. If it is lower than 0° C., the reaction becomes too slow. If it is higher than 100° C., hydrogenation of the nuclear halogen undesirably occurs by super-hydrogenation.
In the third step of the process, 2-methylmonohalogenobenzotrifluoride obtained by the second step is nitrated by nitric acid in the presence of sulfuric acid. Then, the resultant solution is separated into two phases, and the organic phase is washed with water, then with a basic solution and then with water. The product of the third step is a mixture of nitrated compounds in which a main product is 2-methyl-3-nitro-5-halogenobenzotrifluoride.
It is preferable to use concentrated sulfuric acid, fuming sulfuric acid or anhydrous sulfuric acid as the sulfuric acid used in the third step. The reaction temperature of the third step is preferably from 0° to 80° C. If it is lower than 0° C., the reaction speed becomes too slow. If it is higher than 80° C., undesirable poly-nitration occurs. It is optional to conduct the reaction of the third step in an inactive organic solvent such as methylene chloride, chloroform, dichloroethane or trichloroethane.
In the fourth step of the process, the nitrated compounds obtained by the third step are brought into contact with hydrogen under a liquid phase condition in the presence of a metal-carried catalyst and an optional basic substance so as to reduce the nitro group of the nitrated compounds and to dehalogenate the nitrated compounds. After the reaction, the catalyst and the salt are removed by filtration. Then, the filtrate is washed with water and then dried with a drying agent. Then, the drying agent is removed by filtration. The product of the fourth step is a mixture of isomers in which a main product is MA-BTF. Only MA-BTF is isolated by recrystallization, crystallization or distillation after the fourth step.
The reaction temperature of the fourth step is preferably from 60° to 130° C. If it is lower than 60° C., the reaction becomes too slow. If it is higher than 130° C., hydrogenation of the trifluoromethyl group undesirably occurs by super-hydrogenation.
The metal-carried catalyst of the second and forth steps has a metal such as a noble metal (for example, Pd, Pt or Rh) or nickel which is carried by a carrier such as active carbon, alumina, zeolite or silica-alumina. Preferred examples of the metal-carried catalyst of the second and forth steps are a combination of Pd and active carbon (Pd/carbon), a combination of Pd and alumina (Pd/alumina), a combination of Pd and zeolite (Pd/zeolite) and a combination of Pd and silica-alumina (Pd/silica-alumina). It is preferable that the amount of the metal-carried catalyst of the second and forth steps is from 0.1 to 5.0 wt % of the substrate. If it is less than 0.1 wt %, the reaction becomes too slow. There is no strict upper limit to the amount of the metal-carried catalyst. However, it is not necessary to add the same which is more than 5.0 wt %. The amount of the metal of the catalyst is from 0.1 to 10 wt %. A commercial metal-carried catalyst containing 0.5-5.0 wt % metal can be used in the second and forth steps.
The optional basic substance of the second and forth steps is a hydroxide of an alkali metal or of an alkali earth metal, a carbonate of an alkali metal or of an alkali earth metal, an acetate of an alkali metal or of an alkali earth metal, a borate of an alkali metal or an alkali earth metal, or a phosphate of an alkali metal or an alkali earth metal. Preferable examples of the basic substance used in the second and forth steps are sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium borate, potassium borate, disodium phosphate and trisodium phosphate.
The pressure of hydrogen in the second and forth steps is preferably from 1 to 20 kg/cm 2 . If it is lower than 1 kg/cm 2 , the reaction speed becomes too slow. If it is higher than 20 kg/cm 2 , the reaction proceeds satisfactorily. However, the pressure higher than 20 kg/cm 2 is not preferable because apparatus becomes limited in terms of structure.
The reactions of the second and forth steps are gas-liquid reactions. Therefore, contact efficiency between the gas and the liquid influences the reaction speed significantly. Thus, it is preferable to use a special apparatus designed to improve contact efficiency, for example, by a sufficient stir. The reactions of the second and forth steps can be conducted in water or an inactive organic solvent such as diethyl ether, methanol, ethanol or isopropanol.
In the present invention, the main product of each step of the process may be concentrated or isolated through distillation, recrystallization or crystallization.
The present invention is further illustrated by the following nonlimitative example.
EXAMPLE
MA-BTF was produced by a process comprising the following first, second, third and fourth steps.
First Step (Production of 2-Trifluoromethyl-4-Chlorobenzalchloride)
A 500-ml four-necked round bottom flask equipped with thermometer, mechanical stirrer, Dimroth condenser and chlorine-introducing tube was charged with 570.0 g (2.5 mol) of o-trifluoromethylbenzalchloride, 11.5 g (2.5 mol %) of ferric chloride and 1.5 g (0.5 mol %) of iodine. Then, the reaction temperature was raised to 60° C. while the mixture was kept stirred. When the reaction temperature reached 60° C., chlorination was started by continuously introducing chlorine at a rate of 0.5 mol/hr. After the lapse of 2 hr, the reaction temperature was raised to 80° C., and then the reaction was continued for another 5 hr. After the 7-hr reaction, conversion was 97.0%. Then, the reaction liquid was put into a 1000-ml separating funnel, and washed two times with 500 ml of water. The mixed liquid was allowed to separate into two layers and the aqueous layer was removed. The organic phase was dried with magnesium sulfate, and then magnesium sulfate was removed by vacuum filtration. As the result, 634.2 g of 2-trifluoromethyl-4-chlorobenzalchloride (purity: 72.1%) was obtained. The yield of this product was 69.4%. The product was analyzed by gas chromatography, and the result is as follows.
bp: 86°-88° C. (4-5 mmHg)
MASS: m/z 262 (M+) 227 (M+--Cl) 192 (M+--Cl--Cl) 177 (M+--Cl--CF 3 ) 157 (M+--Cl--Cl--Cl)
NMR: (1H in CDCl 3 , TMS) δ7.02 ppm (S, 1H) 7.57-8.12 ppm (m, 3H) ( 19 F in CFCl 3 , TMS) -59.34 ppm (S, 3F)
Second Step (Production of 2-methyl-5-Chlorobenzotrifluoride)
A 1000-ml autoclave which is equipped with a mechanical stirrer and made of stainless steel (SUS-316) was charged with 263.6 g (1.0 mol) of the isomeric mixture (the product of the first step) containing 0.72 mol of 2-trifluoromethyl-4-chlorobenzalchloride as a main component, 84 g (2.1 mol) of sodium hydroxide and 420 g of water. Then, 5.3 g (2.0 wt %) of a metal-carried catalyst (5%-Pd/carbon) was added to the autoclave. The atmosphere of the autoclave was replaced by hydrogen, and the autoclave was put into oil bath to increase the temperature to 30° C. At the same time, stir was started while the hydrogen pressure was maintained at 5 kg/cm 2 . This started absorption of hydrogen. After the lapse of 4 hr, stir was stopped, and the reaction liquid was allowed to cool down. By analysis, conversion of 2-trifluoromethyl-4-chlorobenzalchloride (purity: 72.1%) was 99.9%. Then, the catalyst and the salt were removed by vacuum filtration. The resultant solution was put into a 1000-ml separating funnel, and then the aqueous phase was removed. The organic phase was washed with 500 ml of water and dried with magnesium sulfate. Then, magnesium sulfate was removed by vacuum filtration. As the result, 171.6 g of 2-methyl-5-chlorobenzotrifluoride (purity: 63.8%) was obtained. The yield of this product was 79.0%.
Third Step (Production of 2-Methyl-3-Nitro-5-Chlorobenzotrifluoride)
A 300-ml four-necked round bottom flask equipped with thermometer, mechanical stirrer, Dimroth condenser and 200-ml dropping funnel was charged with 144.4 g (0.75 mol) of an isomeric mixture (the product of the second step) containing 0.48 mol of 2-methyl-5-chlorobenzotrifluoride as a main component. Separately, an acid mixture was prepared by mixing 52.0 g (0.83 mol) of fuming nitric acid and 220.5 g (2.25 mol) of concentrated sulfuric acid. The total amount of the acid mixture was added by dropping to the flask by spending 1 hr while the reaction liquid was kept stirred and the reaction temperature was maintained at a temperature ranging from 20° to 30° C. After the addition of the acid mixture, the reaction was continued for 3 hr while the reaction temperature was maintained at a temperature ranging from 20° to 30° C. Then, stir was stopped. By analysis, conversion was 99.8%, and the purity of 2-methyl-3-nitro-5-chlorobenzotrifluoride was 52.2%. After the reaction, the resultant solution was put into a 1000 ml separating funnel, and the acid mixture phase was removed. Then, the organic phase was washed with 500 ml of water, and then dried with magnesium sulfate. Then, magnesium sulfate was removed by vacuum filtration. As the result, 97.2 g of 2-methyl-3-nitro-5-chlorobenzotrifluoride (purity: 89.0%, boiling point: 119°-125° C. at 21-26 mmHg) was obtained by the concentration through vacuum distillation. The yield was 75.9%. The product was analyzed by gas chromatography, and the result is as follows.
bp: 119°-122° C. (21-23 mmHg)
MASS: m/z 239 (M+) 222 (M+--O--H) 194 (M+--CH 3 --NO)
NMR: (1H in CDCl 3 , TMS) δ2.53 ppm (S, 3H) 7.57-7.91 ppm (m, 2H) ( 19 F in CFCl 3 , TMS) -61.56 ppm (S, 3F)
Fourth Step (Production of MA-BTF)
A 500-ml autoclave which is equipped with a mechanical stirrer and made of stainless steel (SUS-316) was charged with 71.1 g (0.3 mol) of the isomeric mixture (the product of the third step) containing 0.27 mol of 2-methyl-3-nitro-5-chlorobenzotrifluoride as a main component, 13.2 g (0.33 mol) of sodium hydroxide and 100 g of water. Then, 1.4 g (2.0 wt %) of a metal-carried catalyst (5%-Pd/carbon) was added to the autoclave. The atmosphere of the autoclave was replaced by hydrogen, and the autoclave was put into oil bath to increase the temperature to 80° C. At the same time, stir was started while the hydrogen pressure was maintained at 5 kg/cm 2 . This started absorption of hydrogen. After the lapse of 4 hr, stir was stopped, and the reaction liquid was allowed to cool down. By analysis, conversion of 2-methyl-3-nitro-5-chlorobenzotrifluoride was 99.9%. Then, the catalyst and the salt were removed by vacuum filtration. The resultant solution was put into a 1000-ml separating funnel, and then the aqueous phase was removed. The organic phase was washed with 500 ml of water and dried with magnesium sulfate. Then, magnesium sulfate was removed by vacuum filtration. As the result, 44.3 g of MA-BTF (purity: 94.4%) was obtained. The yield of MA-BTF was 88.5%. This product was put into a 200 ml beaker, and then 100 ml of n-hexane was put into the beaker. The liquid temperature was lowered to -10° C. so as to recrystallize MA-BTF while the mixture was kept stirred. The recrystallized product (purity: 99.5%) was isolated by filtration. The solvent remaining in the recrystallized product was removed by evaporation. As the result, 34.3 g of the purified product (MA-BTF) was obtained. The yield was 72.6% (yield in recrystallization: 82.0%).
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2-methyl-3-aminobenzo-trifluoride is prepared with high yields and high productivity by first halogenating o-trifluoromethylbenzalhalide, then secondly hydrogenating 2-trifluoromethyl-4-halogeno-benzalhalide formed by the first reaction, then thirdly nitrating 2-methyl-monohalogenobenzotrifluoride formed by the second reaction, and then fourthly hydrogenating 2-methyl-3-nitro-5-halogenobenzotrifluoride formed by the third reaction.
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BACKGROUND OF THE INVENTION
The invention relates to learning a foreign language and method, and, more particularly, to a foreign language learning device and method.
It has been customary, for language learning purposes, to use special notebooks for learning words/vocabulary, in which, for instance, the left column contains the foreign words to be learned, while the right column contains the corresponding words or translations in one's mother tongue.
Although, in modern times, other mediums, such as cassettes, CDs or even audio-visual media are increasingly used for languages learning purposes, the traditional way of learning as described above is still of major importance.
An aspect of the present invention is to create an improved foreign language learning device which is available to everybody, and which allows and facilitates learning a foreign language in everyday life.
Visualizations are very common in people's talks and thoughts. They enrich and facilitate many thought-processes. The visual sense, however, is only one area of the brain which can facilitate and support, for example, mnemonic processes involved in language learning. However, nowadays, the brain area “responsible” for visual perception is mostly working at full capacity, due to overstimulation. At the same time, a great variety of things and characteristics, e.g. the fragrance of a flower, the softness of fur, etc. can usually be much better perceived with other senses. Also mnemonic processes can be assisted very nicely by other areas of the brain which are less frequently used. The fact, that in addition to visual perception, other forms of perception, such as, for example, smell, sound, taste, warmth, pressure, etc. give additional impetus and complexity to our thought-processes is also confirmed by modern psychology.
BRIEF SUMMARY OF THE INVENTION
Based on this background, according to an aspect of the invention, a foreign language learning device in accordance with the invention provides a learning device for learning foreign languages in everyday life. In accordance with the invention, it is intended for individual terms (adjectives, nouns, verbs, etc. incl. whole groups of words or sentences) to be written on individual labels, which, corresponding to their meaning, are attached to the corresponding object. If, for example, the German word “Stuhl” for the English word “chair” is to be learned, the label with the word “Stuhl” printed on it can be removed and attached to a chair in one's home. In this case, the chair is consciously touched and felt for its characteristics (surface, temperature, weight, movement, etc.).
Every time the user sees the label/object, he will be motivated to recall the corresponding word.
The learning device in accordance with the invention allows the creation of a learning environment which, to a certain extent, can be compared to the learning conditions prevailing in the country where the corresponding language is spoken.
Other terms can be attached to other object, corresponding to the term.
For certain topics, also posters (pictures) can be provided on which the terms can be attached to the individual items represented on the poster.
Once somebody finds out that he/she remembers the word, the label can be removed again.
The foreign language learning device in accordance with the invention comprises preferably a vocabulary book or glossary in a similar form, which contains individual labels with the individual foreign language terms printed on them. The labels are either available individually, or can be removed from a common label sheet.
It is also possible that several individual labels are printed on a joint sheet to be cut out or torn out by means of prepared perforations.
It is however, preferred intention to provide the individual labels as self-adhesive labels which may be attached to a label carrier, e.g. oil paper. It is particularly advantageous to provide these labels with a holding area which does not stick to the label carrier paper, as the holding area, for example, is not provided with any sticking material or adhesive film at all, or because the adhesive film is covered up additionally.
In a particularly favoured form, the paper or sheets with the mother-tongue terms written or printed on them, are bound in the form of a notebook or book, while, between two paper sections containing the mother-tongue terms, the label carrier paper of reduced width or section is inserted, on which the removable, self-adhesive labels containing the foreign language terms to be learned are arranged.
After learning individual terms, the labels removed from the corresponding objects can be returned again to the notebook-like foreign language learning device. In order to allocate the labels to the corresponding locations, every label can contain the pertaining explanations or, for instance, the corresponding word in German or a number, etc., which serves as orientation as to what location in the notebook or book-like device the label can be returned. In this book-like device, however, notes can also be made as to where the corresponding label is located.
The labels do not necessarily have to be self-adhesive. Also non-adhesive labels can be used, which, for example, may have to be cut out or removed along a perforation or cutting line. They can be attached to the object by means of other suitable means, such as, for example, drawing pins, rubber bands, string, etc.
According to the invention, it is intended to use also additional information or label holders, to which the labels—when they are provided with an adhesive film—can be affixed or on which the labels, for instance, can also be attached in a different way, for instance by putting them into a slot fixture. These label or information holders, in turn, can be provided with an adhesive film on the back or with other suitable means, in order to attach to and detach these label holders from certain objects by means of string, wire, drawing pins, magnets, etc.
According to another aspect a label has an adhesive zone, a holding zone, and a reinforcement of the holding zone.
According to another aspect a kit includes a plurality of labels and an instruction manual for teaching a language.
According to another aspect the invention includes computer program software and method for preparing labels to facilitate learning a language.
According to another aspect the invention relates to a computer system for developing labels for learning or teaching a language.
According to another aspect the invention relates to a method of learning a language including applying to objects labels containing words related to such objects.
According to another aspect the invention relates to labels and use thereof for learning or teaching a language.
Another aspect relates to use of multiple senses to facilitate learning or teaching vocabulary concepts in a language.
Another aspect relates to coordinating multiple activities in association with the learning of a language to make the process more active than only passive memorization.
Another aspect relates to a method of using labels for learning words and concepts in a language.
The invention comprises the features described herein, including the description, the annexed drawings, and, if appended, the claims, which set forth in detail certain illustrative embodiments. These embodiments are indicative, however, of but a few of the various ways in which the principles of the invention may be employed.
Although the invention is shown and described with respect to illustrative embodiments, it is evident that equivalents and modifications will occur to others skilled in the art upon the reading and understanding hereof. The present invention includes all such equivalents and modifications.
It will be appreciated that although several embodiments are illustrated and described, features shown in one embodiment may be used in one or more of the other embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Hereinafter, the invention is explained in detail with examples by referring to the attached drawings. Here, the following details are explained:
FIG. 1 is a schematic view of one page of the foreign language learning device according to the invention;
FIG. 2 is an enlarged detail drawing of one individual label as located on the inserted label carrier sheet, as displayed under FIG. 1;
FIG. 3 is a modified application as compared to FIGS. 1 and 2 in form of a schematic top view;
FIG. 4 is a plan view of another modified label made without special processing of the label stock;
FIG. 5 is a side view of the label of FIG. 4;
FIG. 6 is a side view of the label of FIGS. 4 and 5 showing a folded over section of the touching zone;
FIG. 7 is an enlarged top plan view of an exemplary label;
FIG. 8 is a top view of a label or information holder or carrier;
FIG. 9 is a side view of the information or label holder or carrier according to FIG. 8;
FIG. 10 is a top view of a modified application as compared to FIG. 8;
FIG. 11 is a modified application example;
FIG. 12 is a schematic illustration of a poster with labels of the invention applied thereto;
FIG. 13 is a schematic view of a kit in accordance with the invention;
FIG. 14 is a schematic block diagram of a computer system for making labels; and
FIG. 15 is a flow chart of a computer program for making labels.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1, the whole page no. 1 of a vocabulary-book or notebook-like foreign language learning device is depicted.
This whole page 1 comprises a sheet of paper printed with mother-tongue terms, hereinafter called P-sheet 3 , which, in the example, are German terms.
On the left side of the whole page 1 as depicted in FIG. 1, a label carrier section 5 , subsequently called E-sheet 5 , is provided, which is much narrower and which extends over roughly the same height as the P-sheet 3 . So, every whole page 1 mentioned comprises two sheets forming a pair, i.e. one E-sheet 5 and one P-sheet 3 underneath.
The label sheets 5 contain several rows (lines) of individual labels 7 , i.e. self-adhesive or adhesive labels 7 —separate from each other in this example—arranged one below the other, which have the foreign language terms to be learned 9 printed on them.
In the same row, however not on label carrier sheet 5 , but on P-sheet 3 to the right, the mother-tongue terms, i.e. German terms 11 in our example, are printed, which correspond to the foreign language terms 9 . In this way, the layout can be compared to traditional vocabulary books.
As can be seen from the enlarged detail drawing according to FIG. 2, every label 7 preferably consists of two sections, one of which, in the example shown, is a more or less rectangular text zone 15 , while the back of text zone 15 may be an adhesive zone 17 , by means of which label 7 is affixed to label carrier sheet 5 . Adhesive zone 17 , as displayed in FIG. 2, may extend only as far as the broken line 19 , i.e. it may end before the right margin 21 of label carrier sheet 5 .
In the example shown, text zone 15 is followed by a circular holding area 23 , which in the example shown is set-off optically, e.g., by being printed in red or some other color or by otherwise being clearly identified to stand out, as is schematically represented by shading 23 a . Printing limit 25 of holding and signal area 23 , printed in red, in this example, roughly corresponds to the location of the right margin 21 of E-sheet 5 .
Preferably, holding area 23 is not provided with an adhesive film on the back, so that it cannot stick to P-sheet 3 underneath. Particularly, when the broken line 19 , from the right margin, is displaced to the left can it be guaranteed that the label is always completely affixed to E-sheet 5 , even if it is not positioned very exactly, and that no adhesive film on the label comes to rest to the right of the right margin 21 of E-sheet 5 and, therefore, cannot stick to P-sheet 3 underneath. By restricting the adhesive 17 to the area to the left of the line 19 as shown in FIG. 2, for example, helps to avoid getting adhesive on the fingers of a user while gripping the holding area 23 and/or getting dirt on the adhesive so the dirt would not be transferred to the object, e.g., avoiding smudges applied to a wall or an object.
Finally, the label may contain, as a rule in smaller print, either on the front, or if necessary also on the back, the German term or, for instance, an identification number, which allows the removed label to be returned to the original location at the zone or row 27 on the corresponding page provided for this term. An example of such numbering is shown at 29 where the number “256” is shown for such location correspondence.
Hereinafter, the function will briefly be explained.
In order to learn a term, the required label each is removed from the foreign language learning device, by taking the required label at the holding area 23 , removing it from label carrier sheet 5 and affixing it to the corresponding object, e.g. in one's home. These terms are encountered day after day and can, thereby, be memorized without any problems by seeing them again and again. Due to the optically emphasized holding area 23 the labels attract the attention even more.
Once you are sure to have memorized the term, the corresponding label can be removed from the object in one's home and returned to the original location in the foreign language learning device. The original location can easily be found, as the foreign language label, for example, (which is not shown in detail in the illustrations), next to the term “coffee” may contain, in small print and at a suitable position, the terms “Kaffee”—“Imbiss-Stube”, i.e. either on the front or on the back (before the adhesive film is applied to the label), or by giving a number in small print as at 29 (e.g. “256”), with the same number being printed on the page below the German term or at a corresponding position on label carrier sheet 5 . It is, however, also possible, that the corresponding word is printed below or next to the location where the label is affixed, i.e. on the P-sheet.
Under certain circumstances, particular themes, e.g. cars, travelling, may be displayed on posters, showing the individual objects or processes, so that the labels can be allocated and attached to them on the posters.
In order to facilitate affixing of labels and to increase the scope of applications, also label or information holders can be used in addition to the labels on their own, which are hereinafter also called label or information holders.
In FIG. 3, an invention variant of FIGS. 1 and 2 is displayed, on which the labels containing the foreign language terms (or the empty labels with the terms written on them) and the corresponding word in the mother tongue are located on the same self-adhesive sheet, with the labels being pre-cut or stamped out, which can, therefore, be removed without any problems.
In the example according to FIG. 3, there is only one label carrier sheet 5 , a so-called E-sheet 5 , on which a self-adhesive sheet 3 ′ or a self-adhesive paper foil 3 ′ are affixed more or less all-over.
This self-adhesive paper foil 3 ′, on the right side (right column), and similar to the example according to FIG. 1, contains several rows of the corresponding mother-tongue terms 11 (in the example German terms) one below the other.
On the left side, the actual labels 7 are pre-cut or stamped out via a stamping line or cutting line (or perforation line) 24 .
If required, the corresponding individual label 7 can now be removed from label carrier sheet 5 along cutting line 24 , and, if necessary, be returned to this location, as has been explained in the example according to FIG. 1 and 2.
In order to facilitate removing from and returning of labels 7 to the original location on label carrier sheet 5 , section 3 a of the self-adhesive paper foil 3 ′ is removed from label carrier sheet 5 around labels 7 . In order to separate it from the section containing the mother-tongue terms 11 , the removable section 3 a of the self-adhesive paper 3 ′ is separated from the right-hand side in FIG. 3 by means of a cutting line or stamping line 26 , so that the foreign language terms on the left can be separated from the mother-tongue terms on the right (without the label carrier sheet 5 being divided, too). Thus, section 3 a on the self-adhesive paper foil 3 ′ to the left of cutting or stamping line 26 can be removed, whereas labels 7 , separated by stamping and cutting lines 24 , remain affixed to the actual label carrier sheet 5 .
In order to facilitate removing the labels from label carrier sheet 5 and to take advantage of the holding area as described under FIGS. 1 and 2, in our example according to FIG. 3, section 28 , the area where the holding areas 23 are to be located, is either non-adhesive or the back of holding area 23 is provided with an additional intermediate cover in order to render the self-adhesive film ineffective.
In this example, every page 1 , therefore, only consists of two layers, i.e. the carrier sheet 5 called label carrier sheet 5 , also called E-sheet 5 , on which the self-adhesive paper foil 3 ′ with the removable section 3 a on the left, the labels 7 located in the section with stamping and cutting lines, and section 3 b located to the right of stamping or cutting line 26 , which is to remain permanently on E-sheet 5 and which contains the mother-tongue terms 11 . There may be an additional paper strip or a foil in zone 28 in order to render ineffective the adhesive film at the holding area on the back of labels 7 .
Referring to FIGS. 4-6, a modified label 7 ′ is illustrated. The label 7 ′ may be made or cut from conventional label stock material, such as that used to make decals or labels, having a base sheet sometimes referred to as a liner, and a face sheet, sometimes referred to as label material which has adhesive thereon. The face sheet can be die cut in the form of the desired label and can be removed from the liner for attachment to an object. The adhesive remains on the face sheet. If desired the adhesive for this and other embodiments hereof, can be of a type used with reusable labels, such as that employed in conventional Post-It™ type or other type notes/labels. An advantage of the label 7 ′ is that there is no need to make a special label stock material to obtain a touching zone 23 ′ (or manual holding zone) without adhesive. Rather, the label 7 ′ can be removed from the liner and an extension 23 b of the label can be folded along a fold line 23 c as to be under the touching zone 23 ′. Therefore, the adhesive 17 on the surface of the label 7 ′ in the areas of the touching zone 23 ′ and the extension 23 b will come into engagement and be sandwiched between the touching zone 23 ′ and the extension 23 b . Accordingly, the touching zone 23 ′ and the extension 23 b will be exposed to manual touching or grasping but will not have any exposed adhesive. This makes manual manipulation of the label 7 ′ easy without having to remove adhesive from the fingers when applying the label to an object. Also, the folded over extension 23 b , as is illustrated in FIG. 6 tends to reinforce the touching zone 23 ′ and to provide added bulk or substance of the label 7 ′, thus tending to make it easier to grasp, handle and manipulate than if the touching zone were less reinforced, stiff, etc.
Summarizing, then, the embodiment of label 7 ′ shown in FIGS. 4-6 discloses a relatively inexpensive technique to create a touching zone 23 ′ with a non-adhesive back of the touching zone. The fold back along the line 23 c also creates a double strength touching zone 23 ′ while neutralizing the adhesive in the area of the touching zone. The labels 7 ′ can be cut as to provide a plurality of such labels on a sheet, printing of words as described elsewhere herein, and the sheet preferably, although not necessarily, being reusable whereby the labels can be returned to the sheet for storage after use.
Briefly referring to FIG. 7, an enlarged view of a label 7 ″ is illustrated. The label 7 ″ is similar to the labels 7 and 7 ′ described above, except in the label 7 ″ the printed portion or portion intended to be printed with a word and which also has adhesive on the back, has curved corners 24 a and curved transition areas 23 d between the portion intended to be printed and the holding zone 23 ″. The curvatures illustrated help to avoid damage to the label which could too easily occur at sharp corners or transitions, e.g., due to bending at the areas 24 a and/or tearing at the transition areas 23 d . The curves tend to increase the strength of the material in the area thereof and avoids concentration of forces that could more easily cause damage to the label compared to a label having the illustrated curves.
FIGS. 8 and 9 give the top and side views of a label holder 30 , which is preferably made (cast) of plastic.
It comprises an information section 31 , which, in the example, corresponds to the form of text zone 15 . To the right of this, holder section 33 follows, which is circular and corresponds to the circular holding area 23 of label 7 .
The information section 31 may be closed, i.e. with a closed contact area or plate 35 with circumferential edge 36 , with holder section 33 which is located relatively to the right, having a circular or frame-like supporting edge 37 with circumferential boundary 39 , which, opposite information section 31 , is provided with a slot 43 formed by an overlap 41 .
The transition area 32 from information section 31 to the holder section 33 is formed by a zigzag section, i.e. the contact area 35 in the transition area to the holder section 33 is decreasing—in our example formed by a section by pointed tongues 45 . The side view according to FIG. 5 also shows that the contact area 35 in information section 31 is at a higher level as compared to the supporting edge 37 following it.
Individual labels 7 can, therefore, be removed from the foreign language learning device 1 and be affixed to such an information and label holder 30 .
Due to the fact that this information and label holder 30 also has an attachment section 47 on the back, which comprises an attachment plate 49 located parallel to the information section 31 , and which is connected to the base plate of the information holder via several struts 51 , 8 in our example, to which, for instance, string, wires etc. can be attached for an easy attachment of the information and label holder 30 to certain objects and pieces of furniture. In the same way, the information and label holder 30 can also be provided with magnets in this attachment plate 49 —or if no attachment plate 49 is provided, at the bottom of its information zone.
In order to use nails or drawing pins for attaching, for example, both in the information zone 31 and in the attachment plate 49 , which is in alignment with it, there are the openings 53 and/or 55 , respectively, so that a nail or a pin can be pushed through them from the top, thereby attaching the label holder to an object.
When a label is to be removed from the note-book like learning device and to be attached to an object by means of the label holder, the removed label is affixed to the information section 31 by its adhesive zone 17 , with the holding area 23 resting in holder section 33 . The right edge of the holding area 23 is, thereby, engaging in the above-mentioned slot 43 . The brightly coloured and eye-catching holding and signal zone is, therefore, still well visible. The label holder can then or before be attached to the required object.
When the label—once the term has been memorized—is to be removed again, a finger can quite easily be stuck from below through the opening formed by the supporting edge 37 in the holder section 33 and, thereby, the holding area 23 is lifted off from holder section 33 and can easily be taken, which allows easy removal of the label with its adhesive zone from the information section 31 . Lifting off is facilitated by the tongues 45 in the transition area 32 reducing the adhesive surface slowly and continuously, so that the label cannot be torn. Moreover, tearing of the label is also avoided by a continuous transition without any corners or edges from the boundary line 57 (also identified as 23 d in FIG. 7) at the transition between holding area 23 to text zone 15 .
In the example according to FIG. 10, a modified form of the example as compared to FIGS. 8 and 9, holder section 33 has a more or less closed supporting surface 33 a , which, in the example shown, is provided with two longitudinal openings 61 , which are displaced in transverse direction, thereby, as in this example, forming a longitudinal tongue 63 between, at the end of which again a slot 43 is formed. In order to remove a label affixed there, the longitudinal tongue 63 can easily be moved up or down, so as to release the edge of the holding area 23 , the label can then be taken and lifted off.
FIG. 11 is a schematic drawing of an information or label holder 30 , which in the area of the information section 31 , is provided with a viewing section 67 , which, for example, has longitudinal slots 69 at the opposite sides and a transverse slot 71 at one end. At the transition from the information to the holder section there may be a bridge-like cover 73 , forming a frame-like edge and, thus, a window 75 above the bottom surface 35 in the information section 31 . This information and label holder is particularly suitable for non-adhesive labels, which, one after the other, can be put into the label holder, as in the example, via a transverse slot, with the text zone 15 to be located below window 75 and the label being held via the longitudinal slots 69 and the transverse slot 71 , as well as the bridge-like cover 73 . In the holder section, there may also be a circular slot at the supporting edge 37 , extending at least to the semi-circle diameter 77 . Moreover, an additional attachment section 47 may be provided, which is similar to that described under FIGS. 4 and 5.
If such non-adhesive labels are used, they are preferably provided in a form similar to a vocabulary book, while the labels are preferably separated from each other to such an extent, that they can easily be removed from the vocabulary book via a common holding or attachment section (for example along a marked or at least perforated line) and be affixed to the object corresponding to the term, e.g. by using the above-mentioned information and label holder. The disadvantage of this method lies in the fact that the terms—once they have been memorized and are to be removed from the objects—cannot be returned to their original location on a particular page in the foreign language learning device without any extra aid.
For reasons of completeness, it must, however, be mentioned, that the individual labels can certainly be also provided independently from a vocabulary book, for example, in a sort of label box, to be taken out individually. These labels (adhesive or non-adhesive) can also be provided such that the foreign language term to be learned, is, for instance, depicted in larger print and different colour, whereas the German term, i.e. mother-tongue term, is only written in small print on the front or the back of the label. In this case, in the example according to FIG. 1, the so-called P-sheets 3 can be omitted, as only the labels themselves or the labels on the label carrier sheet 5 are used, which can be removed and returned again without separate measures or facilities being provided on which the German terms are printed in relatively the same size.
Briefly turning to FIG. 12, a poster 70 has several objects 71 , 72 printed thereon, such as, for example, an automobile and a tree, respectively. The poster may be placed in a room where there is not otherwise available images of an automobile or tree or where such objects can be seen only through a window, for example. Labels 7 according to the invention having the corresponding word for automobile or tree may be applied to the poster so the user has the opportunity to apply the invention to images of objects, especially objects which are relatively remote from the poster.
A kit 75 embodying the invention is represented in FIG. 13 . The kit includes several components, for example, an instruction manual 76 for practicing the invention and a supply 77 of labels 7 . The instruction manual describes the use of the labels and the method of practicing the invention. Thus, for example, the method includes using multiple senses to help memorize words of a language and to help learn the meaning of those words. The supply of labels may include individual sheets on which one or more labels are located; the labels may be pre-printed with words or one, more or all of the labels may be empty and available to have words written, printed, etc. thereon. Some pages may have printed labels and other pages may have unprinted labels. The labels may be on sheets fastened in a book or held in a loose-leaf notebook or some other retention mechanism that facilitates organization and maintaining of the labels. If desired, the labels may be organized or grouped by subject matter, e.g., household items, furniture, appliances, garden equipment, food products, etc.
According to a method of the invention, a label 7 with a word or phrase is selected and is applied to an object. For example, the object may be a chair. The person may say the word or phrase for chair as printed on the label, may sit in the chair, may feel the chair, may rub a hand on the chair, and may see the label and repeat the word each time encountering the particular chair. Thus, the view, sound, and feel of the chair can be associated with the word representing chair. Similarly for a flower or plant, the label on which the word “flower” is printed may be applied to a leaf, to a flower pot, or to one of the label holders and that attached by a string to the plant; and the person learning the language may not only say the word and, thus, hear it, but also may feel the flower, see the flower and smell the flower.
The kit 75 also may include a supply of the mentioned label holders and string, pins, magnets, etc. to attach the label holders to an object. Further, the kit may include posters 70 .
As is described further below, the invention includes computer software 78 to print labels for use according to the above described methods. Therefore, if desired, the kit 75 may include a computer readable medium 79 or other readable medium on which the software may be stored, such as a magnetic disk, optical disk, tape, or some other medium on which the program may be stored for use by a reader and associated electronic equipment, such as a computer, for printing or otherwise generating labels.
Referring, now, to FIG. 14, a system 80 for making labels 7 is illustrated in block form. The system includes a computer 81 or similar device which can be operated to control a printer 82 to print labels 7 . The printer 82 may be any of many types of printers, several examples including a laser printer, dot matrix printer, ink jet printer, bubble printer, or virtually any other printer. Sheets 1 of labels 7 may be fed to the printer. The printer may print the first language word, the foreign language word, a number organizer, and/or other information on the sheet 1 , on the labels 7 , etc. An exemplary computer 81 is that known as a personal computer, such as a K-6 microprocessor or Pentium microprocessor based computer; or the computer may be virtually any other computer, as may be desired. A keyboard 83 and monitor 84 are coupled to the computer 81 to provide manual input to the computer and to display information from the computer; exemplary information being settings and operation of the computer program, the words and/or other information to be printed, etc. A storage device 85 , such as a program reader and/or storage mechanism, examples being a floppy disk drive, fixed disk, cd-rom drive, tape drive, etc., and a storage medium 86 , such as a magnetic disk, optical disk, tape or other medium on which a computer program is stored, are coupled to the computer to provide computer program control of the computer and/or printer and/or to store information otherwise input to the computer, as is conventional in computer systems. A computer program 90 associated with the system 80 is illustrated schematically in flow chart form in FIG. 15 .
In using the system 80 , one or more sheets 1 containing labels 7 are provided the printer. The computer program 90 is provided the computer 81 to control operation thereof. Using the system 80 and program 90 , and, if necessary, with inputs provided by the user employing the keyboard 83 , the system 80 operates the printer 82 to print information on the sheets 1 and, in particular, on the labels 7 . Such information may be as was described above. For example, the printer 82 may print on a label 7 a particular language word intended to be learned or memorized as well as some other reference to that word, e.g., elsewhere on the sheet 1 , say adjacent the mentioned label. The printer also may print coordinating indicia to facilitate replacing labels on the sheets 1 . The mentioned reference to the subject word may be the word in the usual language of the person who would be using the program. Alternatively, or additionally, if desired the reference may be a picture; for example, if the word printed on a give label were the word “tree”, the image of a tree may be printed on the sheet 1 . This would facilitate using images to coordinate placing labels on objects and also would help the user further to associate the image of a tree with the word for “tree” without even having to think about the word as used in the usual language or origin language of the user.
Turning to FIG. 15, a computer program for practicing the invention to make labels is illustrated at 90 . The program 90 is presented in flow chart form; it will be appreciated that appropriate computer program source code, machine language, or some other machine useable implementation of the flow chart may be written by a person who has ordinary skill in the computer programming art so as to allow the system 80 , for example, to carry out the program and the invention. The actual computer program language used may depend on the particular computer 81 used in the system 80 .
In the program 90 illustrated in FIG. 15, at step 91 the program (and system 80 ) is initialized. At step 92 an input language is selected; for example, if the user's ordinary language were English, then the selected language would be English—similarly for French, German, Japanese or some other language. At step 93 the output language is selected; this is the language to be learned. At step 94 , a word is input to the computer 81 , e.g, using the keyboard 83 ; and at step 95 the computer determines the output word to be printed onto a label by the printer 82 . Thus, for example, if the input language were German and the output language were German, then the word “Stuhl” could be the input word, and the computer would select “chair” as the output word. The storage medium 86 may include a dictionary of terms in the respective languages to allow selecting the corresponding words in the input and output languages. Commercial computer based dictionaries currently are available and may be used for this purpose. The system 80 then causes printing at block 96 of both those words on the label and on the paper 1 adjacent the corresponding label 7 , or may print the output word (on the label) and a reference, such as a picture of a chair, proximate the label on the page 1 . At block 97 an inquiry is made whether the user is finished printing labels; if not then a loop line 98 is followed to block 94 . If the user has finished using the program 90 , then the program ends at block 99 . The labels then can be used according to the method of the invention as described above and equivalents thereof.
It will be appreciated that the labels 7 can be pre-printed or formed on the sheets 1 , for example. Alternatively or additionally, some or all of the labels 7 can be printed by the user, for example, using the system 80 and program 90 .
In using the invention a language can be learned and/or words associated with that language can be memorized. The words or phrases may be of the object itself, e.g., the word “tree”, or the words may concern a characteristic of the object, such as sweet smell of a tree, hardness of a steel beam, etc., or an abstract idea, such as happiness of an individual. The invention allows use of multiple senses as inputs to the brain in association with a word or object represented by the word, thus increasing the likelihood of remembering the word in issue.
It will be appreciated that although the invention is described with respect to several features and embodiments, the scope of the invention is to be limited only by the scope of the claims and equivalents thereof.
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An improved foreign language learning device, particularly in a form similar to a vocabulary book or note-book, giving the foreign language terms to be learned, is characterized by the following: it is intended for use a reproduction or depiction holder having several labels and/or information carriers or holders, wherein the labels and/or the information carriers or holders are at least provided with an adhesive or holder section, and wherein the labels and/or information or label holders or carriers have individual foreign-language terms or groups of terms, sentences or sentence parts written on them.
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RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119 to Japanese Patent Application No. 2011-013326 filed on Jan. 25, 2011, the entire content of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an output circuit, the output of one end of which has high impedance and, more particularly, to an output circuit which stably operates when a power supply voltage is low. The present invention further relates to a temperature switch IC and a battery pack, each of which is provided with the aforementioned output circuit.
[0004] 2. Description of the Related Art
[0005] The following will describe a conventional output circuit. FIG. 7 is a circuit diagram illustrating a conventional output circuit.
[0006] The conventional output circuit includes an inverter 97 connected to an input terminal, an NMOS transistor 93 , which is an output driver, a diode-connected NMOS transistor 95 and a capacitor 96 , which are provided between a power source and the ground, and an NMOS transistor 94 controlled thereby.
[0007] When the circuit is turned on, a power supply voltage VDD gradually rises. The NMOS transistor 95 remains nonconductive while the power supply voltage VDD is lower than a threshold voltage Vthn 95 . The NMOS transistor 94 turns off, because the gate voltage thereof becomes an earth voltage VSS due to the capacitor 96 . Hence, the output terminal of the output circuit is in a high-impedance state. This ensures that the output terminal of the output circuit is always set in the high-impedance state if the power supply voltage VDD at the time of, for example, turning the circuit on, is lower than a minimum operating voltage of the circuit.
[0008] When the power supply voltage VDD exceeds the threshold voltage Vthn 95 of the NMOS transistor 95 , the NMOS transistor 95 becomes conductive. The capacitor 96 is charged by the current supplied by the NMOS transistor 95 . When the gate voltage thereof gradually rises and exceeds a threshold voltage, the NMOS transistor 94 turns on. When the NMOS transistor 94 turns on, the function of the NMOS transistor 93 is rendered valid, transmitting an output of the inverter 97 to the output terminal. If the voltage of an input terminal of the output circuit is at a low level, then the NMOS transistor 93 turns on, and an output voltage VOUT of the output terminal becomes the earth voltage VSS. If the voltage at the input terminal of the output circuit is at a high level, then the NMOS transistor 93 turns off, causing the output voltage VOUT of the output terminal to be set in the high-impedance state (refer to, for example, patent document 1).
[Patent Document 1] Japanese Patent Application Laid-Open No. 06-075668
[0010] In the conventional output circuit, the NMOS transistor 94 is provided in series with the NMOS transistor 93 . The NMOS transistor 93 , which is an output driver, is required to provide a drive capability. For this reason, a large NMOS transistor is used for the transistor 93 . Thus, the NMOS transistor 94 is required to provide a drive capacity that is equivalent to or higher than that of the NMOS transistor 93 .
[0011] The conventional output circuit has been posing a problem that the large size of the NMOS transistor 94 inconveniently leads to a large area of the output circuit.
SUMMARY OF THE INVENTION
[0012] The present invention has been made in view of the problem described above, and an object of the invention is to provide an output circuit with a smaller area.
[0013] To this end, the present invention provides an output circuit with open-drain output including: an inverter circuit connected to an input terminal of the output circuit; an output MOS transistor having a gate thereof connected to an output terminal of the inverter circuit; a drain thereof connected to an output terminal of the output circuit, and a source thereof connected to a first supply terminal; a switch circuit provided between the inverter circuit and a second supply terminal; and a current source provided between the gate of the output MOS transistor and the first supply terminal, wherein the switch circuit turns off when a power supply voltage is lower than a minimum operating voltage of the output circuit.
[0014] The output circuit according to the present invention is configured such that, if a power supply voltage is lower than an operating voltage of the circuit, then the operation of the inverter is interrupted and the gate of an output driver is controlled to turn it off. Hence, a large MOS transistor is no longer required to be provided between the source of the output driver and a power source. This arrangement enables the output circuit to restrain unstable outputs even when the power supply voltage is lower than the operating voltage and to achieve a reduced area.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a circuit diagram illustrating an example of the output circuit according to an embodiment of the present invention;
[0016] FIG. 2 is a circuit diagram illustrating another example of the output circuit according to the embodiment;
[0017] FIG. 3 is a circuit diagram illustrating still another example of the output circuit according to the embodiment;
[0018] FIG. 4 is a block diagram illustrating a battery pack;
[0019] FIG. 5 is a block diagram illustrating a battery protection IC;
[0020] FIG. 6 is a block diagram illustrating a temperature switch IC; and
[0021] FIG. 7 is a circuit diagram illustrating a conventional output circuit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Embodiments of the present invention will be described below with reference to the accompanying drawings.
[0023] FIG. 1 is a circuit diagram illustrating an output circuit according to an embodiment of the present invention.
[0024] An output circuit 10 has PMOS transistors 11 and 12 , NMOS transistors 21 and 22 , and a current source 31 .
[0025] The PMOS transistor 11 has the gate thereof connected to the input terminal of the output circuit 10 , the source thereof connected to the drain of the PMOS transistor 12 , and the drain thereof connected to the gate of the NMOS transistor 22 . The NMOS transistor 21 has the gate thereof connected to the input terminal of the output circuit, the source thereof connected to an earth terminal (a power supply terminal at an earth voltage side), and the drain thereof connected to the gate of the NMOS transistor 22 . The PMOS transistor 12 has the gate thereof connected to the earth terminal and the source thereof connected to a supply terminal (the power supply terminal at a power supply voltage side). The PMOS transistor 12 is provided on a power supply line of an inverter 36 composed of the PMOS transistor 11 and the NMOS transistor 21 .
[0026] The current source 31 is provided between the drain of the PMOS transistor 11 and the earth terminal. The NMOS transistor 22 has the source thereof connected to the earth terminal and the drain thereof connected to the output terminal of the output circuit 10 . The NMOS transistor 22 is an open-drain output driver.
[0027] The absolute value |Vthp 12 | of the threshold voltage of the PMOS transistor 12 is higher than the absolute value |Vthp 11 | of the threshold voltage of the PMOS transistor 11 and indicates the minimum operating power supply voltage of the output circuit 10 . If a power supply voltage VDD is lower than the minimum operating power supply voltage, then the PMOS transistor 12 turns off so as not to supply the power supply voltage VDD to the inverter 36 . Further, the current source 31 turns the NMOS transistor 22 off.
[0028] The operation of the output circuit 10 will now be described.
[0029] When the power is turned on, the power supply voltage rises. At this time, if the power supply voltage VDD is lower than the absolute value |Vthp 12 | of the threshold voltage of the PMOS transistor 12 , then the PMOS transistor 12 turns off. This prevents the power supply voltage VDD from being supplied to the inverter 36 . Therefore, the output terminal of the inverter 36 is pulled down by the current source 31 , so that the output voltage of the inverter 36 is an earth voltage VSS. The NMOS transistor 22 , which is the output driver, turns off because the gate voltage thereof becomes the earth voltage VSS, thus setting the output terminal of the output circuit 10 in the high impedance state. Hence, the output terminal of the output circuit 10 is pulled up to the power supply voltage of a circuit in a subsequent stage, the aforementioned output terminal being connected to the input terminal of the circuit in the subsequent stage. This arrangement restrains the circuit in the subsequent stage from malfunctioning.
[0030] If the power supply voltage VDD becomes higher than the absolute value |Vthp 12 | of the threshold voltage of the PMOS transistor 12 , then the PMOS transistor 12 turns on. This causes the power supply voltage VDD to be supplied to the inverter 36 .
[0031] If the voltage at the input terminal of the output circuit 10 is a low level, then the gate voltage of the NMOS transistor 22 becomes a high level due to the inverter 36 , causing the NMOS transistor 22 to turn on and the output voltage VOUT to become the earth voltage VSS. The current source 31 is designed to have a drive capability that is lower than the drive capability of the PMOS transistor 11 .
[0032] If the voltage at the input terminal of the output circuit 10 becomes a high level, then the gate voltage of the NMOS transistor 22 becomes a low level due to the inverter 36 . This causes the NMOS transistor 22 to turn off, placing the output terminal of the output circuit 10 in the high-impedance state.
[0033] The output circuit according to the present embodiment is configured such that, when the power supply voltage is lower than the operating voltage of the circuit, the operation of the inverter is interrupted and the gate of the output driver is turned off by the current source, thus obviating the need for providing a large MOS transistor between an output driver and a power source. This permits a reduced area of the output circuit 10 .
[0034] Further, if the power supply voltage VDD at the time of, for example, turning the power on, is lower than the minimum operating power supply voltage of the output circuit 10 , then the output voltage VOUT always causes high impedance, thus restraining a circuit in a subsequent stage from malfunctioning.
[0035] FIG. 2 is a circuit diagram illustrating another example of the output circuit according to the present embodiment. The output circuit 10 in FIG. 2 further includes a current source 32 and a PMOS transistor 13 .
[0036] The PMOS transistor 13 and the current source 32 are connected in series between a supply terminal and an earth terminal. The PMOS transistor 13 has the gate and the drain thereof connected to the earth terminal. The connection point of the current source 32 and the source of the PMOS transistor 13 is connected to the gate of the PMOS transistor 12 .
[0037] According to the configuration described above, the minimum operating power supply voltage of the output circuit 10 is set by the current source 32 and the two PMOS transistors 12 and 13 . More specifically, when a power supply voltage VDD becomes higher than the total voltage of the absolute values of the threshold voltages of the two PMOS transistors 12 and 13 , the PMOS transistor 12 is turned on and the power supply voltage VDD is supplied to an inverter 36 .
[0038] At the output end in FIG. 2 , the diode-connected PMOS transistor 13 is provided between the gate of the PMOS transistor 12 and the earth terminal. Alternatively, however, a diode-connected NMOS transistor may be provided instead of the PMOS transistor 13 .
[0039] FIG. 3 is a circuit diagram illustrating another example of the output circuit according to the present embodiment. As illustrated in FIG. 3 , the gate of the NMOS transistor 22 may be connected to the drain of the PMOS transistor 11 through the intermediary of a resistor 33 .
[0040] In the aforementioned configuration, a low-pass filter is constituted by the resistor 33 and the capacitor between the gate and the source of the NMOS transistor 22 , thus reducing the malfunctions of the NMOS transistor 22 caused by a surge. The gate of the NMOS transistor 22 may be connected to the connection point of the resistor 33 and the drain of the NMOS transistor 21 .
[0041] In the output circuit shown in FIG. 1 , the NMOS transistor for controlling the supply of the power supply voltage VDD to the inverter 36 may be provided between the inverter 36 and the earth terminal. Further, in FIG. 1 , the open-drain NMOS transistor 22 is used, and the output voltage VOUT becomes the high impedance state in the case where the power supply voltage VDD is lower than the minimum operating power supply voltage of the output circuit 10 . However, although not shown, an open-drain PMOS transistor may alternatively be used. At this time, the gate of the NMOS transistor for controlling the supply of the power supply voltage VDD to the inverter 36 is connected to a supply terminal, the source thereof is connected to an earth terminal, and the drain thereof is connected to the source of the NMOS transistor 21 . The gate of the open-drain PMOS transistor is connected to the output terminal of the inverter 36 , the source thereof is connected to the supply terminal, and the drain thereof is connected to the output terminal of the output circuit 10 . The current source 31 is provided between the supply terminal and the output terminal of the inverter 36 .
[0042] When the power supply voltage VDD becomes higher than the threshold voltage Vthn of the NMOS transistor, the NMOS transistor turns on and the power supply voltage VDD is supplied to the inverter 36 .
[0043] If the power supply voltage VDD is lower than the absolute value |Vthp 12 | of the threshold voltage of the PMOS transistor 12 , then the PMOS transistor 12 turns off. Thus, the power supply voltage VDD is not supplied to the inverter 36 . Hence, the output terminal of the inverter 36 is pulled up by the current source 31 , so that the output voltage of the inverter 36 becomes the power supply voltage VDD. The PMOS transistor turns off, and the output voltage VOUT becomes the high impedance state.
[0044] An application example of the output circuit 10 will now be described. First, the construction of a temperature switch IC provided with the output circuit 10 and the construction of a battery pack provided with a battery protection IC will be described. The temperature switch IC detects an abnormal temperature. The battery protection IC protects a battery from overcharge/overdischarge. FIG. 4 is a block diagram illustrating the battery pack. FIG. 5 is a block diagram illustrating the battery protection IC. FIG. 6 is a block diagram illustrating the temperature switch IC.
[0045] As illustrated in FIG. 4 , a battery pack 50 includes a battery protection IC 51 , a temperature switch IC 52 , p-type FETs 53 to 55 , a resistor 57 , and a battery 58 . Further, the battery pack 50 has an external terminal EB+ and an external terminal EB−.
[0046] As illustrated in FIG. 5 , the battery protection IC 51 includes reference voltage generating circuits 61 and 62 , an overcharge detection comparator 64 , and an overdischarge detection comparator 63 . Further, the battery protection IC 51 has a supply terminal, an earth terminal, a charge control terminal CO, and a discharge control terminal DO.
[0047] As illustrated in FIG. 6 , the temperature switch IC 52 has a temperature voltage generating circuit 75 , reference voltage generating circuits 71 and 72 , a high temperature detection comparator 73 , a low temperature detection comparator 74 , a NOR circuit 76 , and an output circuit 10 . The temperature voltage generating circuit 75 is constituted of a PNP bipolar transistor and the like, although not shown. Further, the temperature switch IC 52 has a supply terminal, an earth terminal, and an output terminal DET.
[0048] The supply terminal of the battery protection IC 51 is connected to the positive terminal of the battery 58 , the earth terminal thereof is connected to the negative terminal of the battery 58 , the discharge control terminal DO is connected to the gate of the p-type FET 53 , and the charge control terminal CO is connected to the gate of the p-type FET 54 and the drain of the p-type FET 55 . The supply terminal of the temperature switch IC 52 is connected to the positive terminal of the battery 58 , the earth terminal thereof is connected to the negative terminal of the battery 58 , and the output terminal DET thereof is connected to the gate of the p-type FET 55 .
[0049] The resistor 57 is provided between the external terminal EB+ and the connection point of the output terminal DET and the gate of the p-type FET 55 . The source and the back gate of the p-type FET 53 are connected to the positive terminal of the battery 58 , and the drain thereof is connected to the drain of the p-type FET 54 . The source and the back gate of the p-type FET 54 are connected to the external terminal EB+. The source and the back gate of the p-type FET 55 are connected to the external terminal EB+. The external terminal EB− is connected to the negative terminal of the battery 58 . In other words, the p-type FETs 53 and 54 are provided in series in the charge/discharge path of the battery 58 .
[0050] The reference voltage generating circuits 61 and 62 , the overcharge detection comparator 64 , and the overdischarge detection comparator 63 are provided between the supply terminal and the earth terminal. The inverting input terminal of the overcharge detection comparator 64 is connected to the output terminal of the reference voltage generating circuit 62 , the non-inverting input terminal thereof is connected to the supply terminal, and the output terminal thereof is connected to the charge control terminal CO. The inverting input terminal of the overdischarge detection comparator 63 is connected to the supply terminal, the non-inverting input terminal thereof is connected to the output terminal of the reference voltage generating circuit 61 , and the output terminal thereof is connected to the discharge control terminal DO.
[0051] The reference voltage generating circuits 71 and 72 , the high temperature detection comparator 73 , the low temperature detection comparator 74 , the temperature voltage generating circuit 75 , the NOR circuit 76 , and the output circuit 10 are connected between the supply terminal and the earth terminal. The non-inverting input terminal of the high temperature detection comparator 73 is connected to the output terminal of the reference voltage generating circuit 71 , while the inverting input terminal thereof is connected to the output terminal of the temperature voltage generating circuit 75 . The non-inverting input terminal of the low temperature detection comparator 74 is connected to the output terminal of the temperature voltage generating circuit 75 , while the inverting input terminal thereof is connected to the output terminal of the reference voltage generating circuit 72 . The first input terminal of the NOR circuit 76 is connected to the output terminal of the high temperature detection comparator 73 , the second input terminal thereof is connected to the output terminal of the low temperature detection comparator 74 , and the output terminal thereof is connected to the input terminal of the output circuit 10 . The output terminal of the output circuit 10 is connected to the output terminal DET.
[0052] Upon detection of an abnormal temperature, the temperature switch IC 52 emits an output current. The resistor 57 generates a voltage on the basis of the output current. The voltage generated in the resistor 57 turns the p-type FET 55 on. This causes the p-type FET 54 for charge control to turn off, thus controlling charge. If the battery 58 is overcharged, then the battery protection IC 51 operates to turn the p-type FET 54 off. If the battery 58 is overdischarged, then the battery protection IC 51 operates to turn the p-type FET 53 for discharge control off.
[0053] The operation of the battery pack 50 will now be described.
[0000] [Operation Performed when the Battery 58 is Overcharged]
[0054] A charger (not shown) is connected to the battery pack 50 . The reference voltage generating circuit 62 generates a reference voltage VREF 2 based on an overcharge voltage indicating that the battery 58 is in an overcharged state. The overcharge detection comparator 64 compares a divided voltage of the voltage of the battery 58 with the reference voltage VREF 2 , and reverses an output voltage according to the comparison result. More specifically, if the divided voltage of the voltage of the battery 58 exceeds the reference voltage VREF 2 , then the output voltage of the overcharge detection comparator 64 is reversed to a high level. This turns the p-type FET 54 off, stopping the charging of the battery 58 .
[0000] [Operation Performed when the Battery 58 is Overdischarged]
[0055] A load (not shown) is connected to the battery pack 50 . The reference voltage generating circuit 61 generates a reference voltage VREF 1 based on an overdischarge voltage indicating that the battery 58 is in an overdischarged state. The overdischarge detection comparator 63 compares a divided voltage of the voltage of the battery 58 with the reference voltage VREF 1 , and reverses an output voltage according to the comparison result. More specifically, if the divided voltage of the voltage of the battery 58 drops to the reference voltage VREF 1 or lower, then the output voltage of the overdischarge detection comparator 63 is reversed to a high level. This turns the p-type FET 53 off, stopping the discharging of the battery 58 .
[Operation in Case of Abnormally High Temperature]
[0056] The temperature voltage generating circuit 75 generates a temperature voltage VTEMP based on a temperature. The temperature voltage generating circuit 75 is characteristic in that the temperature voltage VTEMP drops as the temperature rises. The reference voltage generating circuit 71 generates a reference voltage VREF 3 based on an abnormally high temperature to be detected. The high temperature detection comparator 73 compares the temperature voltage VTEMP with the reference voltage VREF 3 and reverses the output voltage according to the comparison result. More specifically, as the temperature rises, the temperature voltage VTEMP drops, and the output voltage of the high temperature detection comparator 73 switches to a high level when the temperature voltage VTEMP drops to the reference voltage VREF3 or less. In other words, if the temperature reaches an abnormally high temperature level or more, then the output voltage of the high temperature detection comparator 73 is switched to the high level. As a result, the output voltage of the NOR circuit 76 is set to a low level, the output circuit 10 is turned on to supply current to the resistor 57 , a voltage is generated at the resistor 57 , and the voltage of the output terminal DET is set to the low level. This causes the p-type FET 55 to turn on and the p-type FET 54 to turn off, thus stopping the charging of the battery 58 .
[Operation in Case of Abnormally Low Temperature]
[0057] The reference voltage generating circuit 72 generates a reference voltage VREF 4 based on an abnormally low temperature to be detected. The low temperature detection comparator 74 compares the temperature voltage VTEMP with the reference voltage VREF 4 and reverses the output voltage according to the comparison result. More specifically, as the temperature decreases, the temperature voltage VTEMP rises, and the output voltage of the low temperature detection comparator 74 switches to a high level when the temperature voltage VTEMP reaches the reference voltage VREF 4 or more. In other words, if the temperature decreases to an abnormally low temperature level or less, then the output voltage of the low temperature detection comparator 74 is switched to the high level. This causes the charging of the battery 58 to be stopped as described above.
[0058] Thus, the operation of the aforementioned output circuit 10 ensures that the output circuit 10 of the temperature switch IC 52 always turns off if the power supply voltage VDD is lower than the minimum operating power supply voltage of the output circuit 10 . As a result, the voltage at the output terminal of the output circuit 10 , i.e., the voltage at the output terminal DET of the temperature switch IC 52 is invariably pulled up to the voltage at the external terminal EB+ by the resistor 57 . Hence, if the power supply voltage VDD is lower than the minimum operating power supply voltage of the output circuit 10 , the p-type FET 55 invariably turns off, thereby invariably disabling the temperature switch IC 52 to control the p-type FET 54 through the intermediary of the p-type FET 55 . Accordingly, when, for example, the charging of the battery 58 is started from a state wherein the voltage thereof is in the vicinity of zero volt, it is possible to prevent the temperature switch IC 52 from malfunctioning to turn the p-type FET 54 off due to the low voltage (power supply voltage VDD) of the battery 58 and erroneously stopping the charging despite that the voltage of the battery 58 is low.
[0059] As illustrated in FIG. 6 , the overcharge detection comparator 64 and the overdischarge detection comparator 63 are required as the protective functions for the battery pack 50 . However, in the case where the specifications of the battery pack 50 do not require the overdischarge detection function as the protective function, the overdischarge detection comparator 63 may be deleted, although not shown. In this case, the p-type FET 53 would be also deleted.
[0060] Further, illustrated in FIG. 6 , the high temperature detection comparator 73 and the low temperature detection comparator 74 are required as the protective functions for the battery pack 50 . However, in the case where the specifications of the battery pack 50 do not require the low temperature detection function or the high temperature detection function as the protective function, the low temperature detection comparator 74 or the high temperature detection comparator 73 may be omitted.
[0061] Further, the resistor 57 , the p-type FET 55 or the like may be incorporated in the temperature switch IC 52 .
[0062] In FIG. 4 , the p-type FETs 53 and 54 for controlling charge/discharge are provided between the external terminal EB+ and the positive terminal of the battery 58 . Alternatively, however, two n-type FETs may be provided between the external terminal EB− and the negative terminal of the battery 58 , although now shown. In this case, the p-type FET 55 , the resistor 57 , the internal circuit of the battery protection IC 51 , and the internal circuit of the temperature switch IC 52 would be changed, as necessary.
[0063] In FIG. 4 , the temperature switch IC 52 controls only the p-type FET 54 for charge control. Alternatively, however, the temperature switch IC 52 may control only the p-type FET 53 for discharge control, although not shown, or may control both the p-type FETs 53 and 54 .
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An output circuit has a smaller area and restrains outputs from becoming unstable even if a power supply voltage is lower than an operating voltage. A supply terminal of an inverter circuit is provided with switch circuit, and the switch circuit stops the operation of the inverter circuit when the power supply voltage is lower than the operating voltage of the circuit. Further, the output terminal of the inverter circuit is provided with a current source to fix the output to the power supply voltage when the operation of the inverter circuit is stopped.
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[0001] This application claims the benefit under 35USC119 of the filing date of provisional application 60/610178 filed Sep. 16, 2004.
[0002] This application is a continuation in part of patent application Ser. No. 11/225881, filed Sep. 14, 2005 and now issued to U.S. Pat. No. 7,882,850.
[0003] The invention provides a new door and frame assembly to replace the common zipper door on camping tents, outdoor dining tents and screen rooms.
BACKGROUND OF THE INVENTION
[0004] The common camping, dining or screen tent typically utilizes a zippered flap of material or screen to act as the doorway into and out of the tent. To enter or exit the tent it is necessary to bend down, open the zipper, bend over and pass through the doorway, and then turn around and close the zipper. Because of the loose material, it often requires two hands, and is often difficult if a person is carrying something.
[0005] Considered broadly, tents disclosed herein are of a portable type, comprised of fabric roofs and walls and often including waterproof fabric floors. The tents are usually supported by rigid metal, fiberglass, or composite poles and frame. The entry method into and out of the tent is by means of a fabric zippered door.
SUMMARY OF THE INVENTION
[0006] It is one object of the invention to provide an improved fabric enclosure with an improved door construction providing an opening with a closure panel in one wall.
[0007] According to one aspect of the invention there is provided a fabric structure comprising:
[0008] a fabric wall panel of the fabric structure defining a plane of the panel and defining side edges of the wall panel and a bottom of the wall panel for resting along a ground surface;
[0009] an opening in the fabric wall panel;
[0010] a fabric closure panel for closing the opening having a hinge line along one side connecting the closure panel to the wall panel;
[0011] wherein the fabric wall panel at the opening and the fabric closure panel each define an edge thereof opposite to the hinge line with the edge of the fabric closure panel overlapping the edge of the fabric wall panel at the opening for closure thereon;
[0012] wherein the edge is curved;
[0013] a flexible bowing strip attached to the edge of the fabric closure panel opposite to the hinge line, which bowing strip is forced into a bowed shape from an initial different shape such that the flexible bowing strip tends to return to the initial shape generating forces in the bowing strip biasing ends of the bowing strip apart;
[0014] and wherein the flexible bowing strip is attached to the edge of the closure panel such that the forces in the bowing strip biasing the ends of the bowing strip apart act to apply tension to the closure panel tending to maintain the panel flat.
[0015] According to an important aspect, the curved edge extends from a top end at the hinge line around to an opposite end at position at a floor of the fabric wall panel, which position is spaced from the hinge line.
[0016] Preferably there is provided a straight non-flexible, stiff brace attached to the bottom edge of the closure panel from said position to the hinge line.
[0017] Preferably there is provided a connecting member attached to the closure panel at the position to receive an end of the brace and an end of the bowing strip.
[0018] Preferably the connecting member is a molded piece having a first receptacle for the end of the brace and a second receptacle for the end of the bowing strip.
[0019] Preferably the brace is attached to the edge of the closure panel by at least one sleeve on the edge of the closure panel.
[0020] Preferably there is provided a fabric door sweep attached to the bottom edge of the closure panel which engages the ground surface in the closed position.
[0021] Preferably the fabric wall panel is arranged to have no sill portion thereof extending upwardly from the ground surface at the bottom edge at the opening.
[0022] Preferably the fabric wall panel is arranged to lie substantially flat against the ground surface at the bottom edge at the opening.
[0023] Preferably the fabric wall panel includes a strap lying substantially flat against the ground surface at the bottom edge at the opening.
[0024] Preferably there is also a second flexible bowing strip attached to the edge of the opening opposite to the hinge line, which second bowing strip is forced into a bowed shape from an initial different shape such that the flexible bowing strip tends to return to the initial shape.
[0025] Preferably the flexible bowing strip is attached to the edge of the closure panel by a sleeve on the edge of the closure panel.
[0026] Preferably each end of the bowing strip is contained in a respective top and bottom retainer pockets attached to the fabric wall panel so as to transfer the tension from the bowing strip into the fabric wall panel.
[0027] Preferably the top retainer pocket is mounted on the fabric wall panel for pivotal movement of the retainer pocket relative to the fabric wall panel about the hinge line, where the hinge line lies at an angle to the bowing strip at the end of the bowing strip.
[0028] Preferably the bottom retainer pocket is attached to the fabric wall panel and defines a rigid pocket into which an end of the flexible bowing strip is inserted so as to be rigidly connected to the straight non-flexible door brace which is inserted into the other side of the pocket.
[0029] Preferably there is provided a fastening system for releasably fastening the overlapping edges together.
[0030] Preferably the hinge line lies in a plane of the fabric wall panel and is inclined in that plane in a direction such that, when viewed in a front elevation of the fabric closure panel, the hinge line is inclined to the vertical in a direction such that a top end of the hinge line is located to a side of a bottom end of the hinge line toward the closure panel.
[0031] The arrangement described in more detail hereinafter utilizes a fabric door panel with a rigid frame comprising straight and arched segmented metal, fiberglass, or composite rods. The door frame, as part of the tent wall, also utilizes a segmented metal, fiberglass, or composite rod to provide opening shape. The rods are assembled into one piece and when attached to the tent fabric form a combined straight and bent segment-of-a-circle arch. The rod is attached to the tent fabric by hoops of fabric around the periphery of the door and door opening. Overlapping fabric edges between the door and the frame in the tent wall prevent fly and mosquito egress. The door pivots on a reinforced fabric hinge. The door is opened in a conventional fashion, by pulling on a handle on one side, stepping through the doorway and closing the door behind. Velcro or magnetic closures keep the door closed. On most sloped wall tents, the door is also self-closing.
[0032] One variation of this invention would be the use of compressed gas tubes to provide the arched shape to the fabric door panel and door frame.
[0033] There is referenced a number of times herein the use of segmented rods for use as the bowing strip. Another variation would be the use of a continuous rod that rolled up for travel (somewhat like a tape measure). Another variation of this invention would be the use of non-segmented metal, fiberglass or composite flat bar to provide the arched shape to the fabric door panel and door frame.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] One embodiment of the invention will now be described in conjunction with the accompanying drawings in which:
[0035] FIG. 1 is an isometric view of a conventional pole supported tent showing the tent door and frame on one side of the tent and including the closure according to the present invention.
[0036] FIG. 2 is an elevational view of the embodiment of FIG. 1 showing the opening tension hoop with the door tension hoop not shown for clarity.
[0037] FIG. 3 is an elevational view of the embodiment of FIG. 1 showing the opening tension hoop and top bowing strip retainer, viewed from inside the tent looking out.
[0038] FIG. 4 is an elevational view of the embodiment of FIG. 1 showing the door tension hoop and top bowing strip retainer.
[0039] FIG. 5 is an elevational view of the embodiment of FIG. 1 showing the door tension hoop and bottom bowing strip retainer.
[0040] FIG. 6 is a section view of the embodiment of FIG. 1 showing the door tension hoop and bottom bowing strip retainer along the lines 6 - 6 of FIG. 5 .
[0041] FIG. 7 is a section through the opening tension hoop and door tension hoop along the lines 7 - 7 of FIG. 1 and showing the general relationship between the two when the door is closed.
[0042] FIG. 8 is an isometric view of a tent showing a second embodiment of the closure.
[0043] FIG. 9 is an elevational view of the door bottom brace and door bottom brace retainer.
[0044] FIG. 10 is an elevational view of the door tension hoop, door bottom brace and corner bowing strip retainer.
[0045] FIG. 11 is an elevational view of the opening in the tent showing the tension hoop and bottom bowing strip retainer, viewed from inside the tent looking out.
[0046] FIG. 12 is a cross-section along the lines 12 - 12 of FIG. 8 .
[0047] In the drawings like characters of reference indicate corresponding parts in the different figures.
DETAILED DESCRIPTION OF THE INVENTION
[0048] The embodiment comprises a number of components attached to the fabric tent wall 1 , which include:
[0049] 1 —fabric tent wall,
[0050] 2 —fabric door,
[0051] 3 —stiffening fabric at hinge line;
[0052] 4 —flexible bowing strip-opening frame;
[0053] 5 —tension hoop—opening frame;
[0054] 6 —stiffened edge—opening frame;
[0055] 7 —bowing strip retainer—opening frame (one at the top of the door and one at the bottom);
[0056] 8 —bowing strip hook and loop restraint—opening frame (one at the top of the door and one at the bottom);
[0057] 9 —flexible bowing strip—door frame;
[0058] 10 —tension hoop—door frame
[0059] 11 —stiffened edge—door frame;
[0060] 12 —bowing strip retainer—door frame top;
[0061] 13 —bowing strip retainer—door frame bottom;
[0062] 14 —hook and loop/magnetic closure;
[0063] 15 —ground spike loop—side wall;
[0064] 16 —handle;
[0065] 17 —ground spike loop—corner;
[0066] 18 —conventional tent;
[0067] 19 —fabric hinge centerline;
[0068] 20 —reinforcement pad.
[0069] The invention provides a door assembly and an opening assembly. A general arrangement of the two assemblies is shown in FIG. 1 .
[0070] The door assembly provides a straight segmented flexible bowing strip door frame 9 (constructed of metal, fiberglass or composites), which is inserted into a semi-circle-shaped door frame tension hoop 10 (constructed of fabric) attached to the fabric door 2 . The ends of the flexible bowing strip door frame 9 are positioned and restrained by the bowing strip retainers 12 and 13 (constructed of reinforced plastic or fabric) at the top and bottom of the door. Insertion of the bowing strip 9 into the semi-circle shaped tension hoop 10 and bowing strip restraint by the bowing strip retainers 12 and 13 causes the door fabric to be stretched tight and maintain the shape bowing strip 9 into the semi-circle-shaped door frame tension hoop 10 . A fabric handle 16 provides a convenient grasp for opening the door.
[0071] The opening assembly consists of a straight segmented flexible bowing strip opening frame 4 (constructed of metal, fiberglass or composites), which is inserted into a semi-circle-shaped opening frame tension hoop 5 (constructed of fabric) attached to the tent wall. The ends of the flexible bowing strip opening frame 4 are positioned and restrained by the bowing strip retainers 7 (constructed of reinforced plastic or fabric) and bowing strip hook and loop restraints 8 at the top and bottom of the door opening. Insertion of the straight bowing strip 4 into the semi-circle-shaped opening frame tension hoop 5 and bowing strip restraint by the bowing strip retainers 7 and bowing strip hook and loop restraints 8 causes the tent wall to be tight and the door opening to match the shape and size of the door. A reinforcement pad 20 provides additional strength to the fabric of the assembly.
[0072] The door assembly has a stiffened edge 11 which is a band of stiffer material fastened to the fabric extending around the semi-circle defined by the inside of the door frame tension hoop 10 which mates with a stiffened edge 6 on the outside of the opening frame tension hoop 5 . The purpose of the stiffened edge is to restrict mosquito and fly egress into the tent. At intervals along the stiffened edge, hook and loop/magnetic closures 14 provide attachment of the door assembly to the opening assembly in order to resist the wind from opening the door assembly. A stiffening fabric at the hinge line 3 allows the door to rotate about the plane of the tent wall. Side wall ground spike loop 15 allows attachments of the stiffening fabric to the ground to maintain the position of the door frame tension hoop 10 relative to the opening frame hoop 5 .
[0073] The embodiment herein has the following features:
[0074] In a camping, dining or screen tent, the use of a rigidly framed door assembly and rigidly framed opening assembly, the combination of which provides convenient hinged door access to and from the tent.
[0075] The rigidly framed door assembly comprising of a straight segmented flexible bowing strip door frame 9 , held in tension in a semi-circle shape by bowing strip retainers 12 and 13 .
[0076] The rigidly framed opening assembly comprising of a straight segmented flexible bowing strip opening frame 4 , held in tension in a semi-circle shape by bowing strip retainers 7 and bowing strip hook and loop restraints 8 .
[0077] The door frame tension hoop 10 and opening frame tension hoop 5 which give shape to the door and tent wall fabric.
[0078] The stiffened edges 6 and 11 to resist mosquitoes and flies from entering the tent.
[0079] The hook and loop/magnetic closures 14 to prevent the unintended opening of the door assembly.
[0080] The arrangement of FIGS. 8 to 12 is similar to that described above so that only the important differences will be described as follows.
[0081] The door assembly provides a straight segmented flexible bowing strip door frame 30 constructed of metal, fiberglass or composites similar to that previously described. This is inserted into an arc-shaped door frame tension hoop 31 constructed of fabric attached to the fabric door 2 . The top end of the flexible bowing strip door frame 30 is positioned and restrained by the bowing strip retainer at the top of the door as shown in the previous embodiment in FIG. 2 .
[0082] The bottom of the bowing strip 30 as shown in FIG. 10 is inserted into a cylindrical receptacle 33 in a bottom stiff retainer 32 constructed of reinforced plastic or metal at the bottom of the door. The door assembly also provides a straight segmented non-flexible or stiff door bottom brace 34 , constructed of tubular metal, fiberglass or composites so as to be resistant to flexing, which is received in a receptacle 35 in the retainer 32 . The retainer 32 is attached to the door 2 at the bottom corner by stitching or adhesive so as to provide a holder for the bowing strip and the brace. The retainer 32 is relatively stiff so as to prevent twisting at the bottom corner and to hold the brace and bowing strip connected at a fixed angle at the bottom corner allowing them to move together as the door is opened.
[0083] The brace 34 is inserted into a straight door frame tension hoop or sleeve 36 constructed of fabric and attached to the fabric door 2 along the bottom edge of the door. At the other end of the brace 34 , the brace is received in a receptacle 37 of a retainer 38 . The retainer 38 is stitched to the fabric of the tent at the hinge line so as to allow the end of the brace to pivot about the hinge line 19 .
[0084] The ends of the door bottom brace 34 are therefore positioned and restrained by the bowing strip retainers 32 and 38 at the bottom of the door. Insertion of the door bottom brace 34 into the straight tension hoop 36 causes the door fabric to stay flat upon the ground surface when in the closed position.
[0085] Insertion of the bowing strip 30 into the arc-shaped tension hoop 31 and bowing strip restraint by the bowing strip retainers 32 and 5 causes the door fabric to be stretched tight and maintain the shape of the door panel. A fabric handle 16 shown in FIG. 8 provides a convenient grasp for opening the door.
[0086] In this way the curved edge defined by the bowings strip at the edge of the door extends from a top end at the hinge line around to an opposite end at position defined by the retainer 32 at the floor of the fabric wall panel where the position defined by the retainer is spaced from the hinge line by the length of the brace.
[0087] The bowing strip is curved sufficiently that it meets the retainer 32 at an angel to the brace which is greater than 90 degrees. This provides a sufficient curvature on the bowing strip to hold the door tensioned and its fabric flat and to provide tension on the fabric attached to the brace. Also the retainer 32 is sufficiently rigid that it maintains the spatial relationship between the brace and the bowing strip, both in angle rotation and planar position. It effectively couples the brace to the bowing strip, so that the two in combination act much like the original sprung hoop. The brace is held in place in the retainers attached to the door panel fabric by the fact that its length is slightly greater than the distance between the retainers.
[0088] The opening in the tent 1 shown in FIGS. 8 and 11 is defined by an edge 40 of the fabric tent 2 which is shaped to match the door with a bottom edge 41 matching the length of the brace 34 and an arched top portion 42 extending from the bottom 41 upwardly and around to the hinge line 19 shown in FIG. 3 at the top. A second bowing strip 43 similar in construction to the first is inserted into an arc-shaped fabric hoop 44 at the edge 42 . The ends of the second flexible bowing strip 43 are positioned and restrained by the bowing strip retainers 45 at the bottom and 7 shown in FIG. 3 at the top.
[0089] The bowing strip 43 is also held in place by a hook and loop restraint 46 at the bottom and by a similar element 8 at the top. These are located adjacent the retainers and act to hold the bowing strip in place when inserted in the retainers. Other arrangements for holding the bowing strip in place can be provided. Bending of the straight bowing strip 43 into the arc-shaped opening frame tension hoop 44 and bowing strip restraint by the bowing strip retainers 45 and bowing strip hook and loop restraints 46 causes the tent wall to be tight and the door opening to match the shape and size of the door.
[0090] A reinforcement pad 47 at the bottom edge of the door opening on the side away from the hinge line 19 provides additional strength to the fabric of the assembly and carries the forces from the retainer 45 . A door sill strap 48 lays flat on the ground and connects the left side fabric tent wall 1 to the right side fabric tent wall 1 and provides integrity in the opening size and holds the tent wall 1 in a generally planar orientation. Thus the opening assembly and door assembly are held coplanar by ensuring alignment of and maintaining spacing between the bottom left and bottom right sides of the door opening. The ends of the strap 48 are held in place by ground spike loops 50 .
[0091] The door assembly has a stiffened edge 51 which is a band of stiffer material fastened to the fabric extending around the arc defined by the inside of the door frame tension hoop 31 which mates with a stiffened edge 53 on the outside of the opening frame tension hoop 44 . The purpose of the stiffened edge is to restrict mosquito and fly egress into the tent. At intervals along the stiffened edge, closures 14 shown on FIG. 7 provide attachment of the door assembly to the opening assembly in order to resist the wind from opening the door assembly. These can be of the hook and loop or magnetic type. A door sweep 52 constructed of reinforced fabric rests on the ground at the bottom strap 48 and helps to restrict mosquito and fly egress into the tent. A stiffening fabric at the hinge line 19 allows the door to rotate about the plane of the tent wall. The side wall ground spike loop 50 allows attachment of the stiffening fabric to the ground to maintain the position of the door frame tension hoop 31 relative to the opening frame hoop 44 .
[0092] The embodiment herein has the following features:
[0093] In a camping, dining or screen tent, the use of a rigidly framed door assembly and rigidly framed opening assembly, the combination of which provides convenient hinged door access to and from the tent.
[0094] The rigidly framed door assembly comprises a flexible bowing strip door frame, held in tension in an arc shape by bowing strip retainers in combination with a non-flexible door bottom brace, held in place by bowing strip retainer and door bottom brace retainer.
[0095] The rigidly framed opening assembly comprises a flexible bowing strip opening frame, held in tension in an arc shape by bowing strip retainers and bowing strip hook and loop restraints.
[0096] The door frame tension hoop, opening frame tension hoop, and door sill strap which give shape to the door and tent wall fabric.
[0097] The stiffened edges and door sweep to resist mosquitoes and flies from entering the tent.
[0098] The hook and loop/magnetic closures to prevent the unintended opening of the door assembly.
[0099] The fabric wall panel is arranged to have no sill portion thereof extending upwardly from the ground surface at the bottom edge at the opening.
[0100] The fabric wall panel is arranged to lie substantially flat against the ground surface at the bottom edge at the opening.
[0101] The fabric wall panel includes a strap lying substantially flat against the ground surface at the bottom edge at the opening.
[0102] Since various modifications can be made in my invention as herein above described, and many apparently widely different embodiments of same made within the spirit and scope of the Claims without department from such spirit and scope, it is intended that all matter contained in the accompanying specification shall be interpreted as illustrative only and not in a limiting sense.
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In a fabric enclosure such as a tent wall there is provided an opening in the fabric panel with a fabric closure panel for closing the opening having a hinge line along one side connecting the closure panel to the wall panel. The opening and the closure panel each define an edge thereof opposite to the hinge line which is curved from an end at the hinge line around to an opposite end separated from the hinge line by a non-flexible rod with the edge of the closure panel overlapping the edge of the opening for closure thereon and a flexible bowing strip attached to the edge of the closure panel which is forced into a bowed shape to apply tension to the closure panel tending to maintain the panel flat.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application Ser. No. 11/307,226, filed Jan. 27, 2006, which claims priority from U.S. Provisional Patent Application Ser. No. 60/648,133, filed Jan. 28, 2005.
FIELD OF THE INVENTION
[0002] This invention relates to stents provided with coatings for eluting medication to prevent or lessen the severity of restenosis.
PRIOR ART
[0003] In order to minimize the response of surrounding tissue to the trauma of stent insertion and expansion, stent coatings must be biocompatible. A further requirement is that a stent coating must adhere to a substrate undergoing plastic deformation. This occurs during insertion and expansion of the stent into the vasculature system. Plastic deformation involves grain rotation and elongation, and intersection of slip planes with the substrate surface. The result is that on a scale below the grain size of the substrate, deformation is highly non-uniform, with some areas undergoing little or no deformation and others extreme deformation with associated increase in surface roughness and irregularity. Therefore, coating adhesion must be preserved through the deformation process.
[0004] Conventional stent coatings can be classified as being either passive or active. Passive coatings rely on biocompatible materials to minimize the body's response to placement of the stent into the vasculature. Generally recognized “passive” coating materials include carbon, iridium oxide, titanium, and the like, as disclosed in U.S. Pat. No. 5,824,056 to Rosenberg. U.S. Pat. No. 5,649,951 to Davidson discloses coatings of zirconium oxide or zirconium nitride.
[0005] Drug eluting or “active” coatings have proven more effective for the prevention of restenosis. Such stents generally comprise a surface polymer containing a therapeutic drug for timed release. A second coating may be added to extend the period of effectiveness by limiting the rate of drug diffusion from the first, drug-containing coating. This second coating may be a polymer, or a sputtered coating as described in U.S. Pat. No. 6,716,444 to Castro et al.
[0006] However, polymeric drug eluting coatings suffer from a number of disadvantages. First, they can have poor adhesion to the stent, especially while undergoing plastic deformation during insertion and expansion of the stent into the vasculature. Secondly, due to biocompatiblity/hemocompatibility issues some polymers actually contribute to restenosis. Finally, that part of the coating facing the inside of the vasculature lumen loses its medication content to the bloodstream with little beneficial effect.
[0007] U.S. Pat. No. 6,805,898 to Wu et al. attempted to overcome adhesion problems by introducing roughness to the vasculature-facing portion of the stent while leaving the blood-facing side in a polished condition for better hemocompatibility. Surface roughness was increased by means of grit blasting, sputtering, and the like. Not only did augmenting surface roughness improve adhesion between the polymer and the stent, it also allowed for a thicker polymer coating to be applied. However, the final stent configuration still had eluting polymer in contact with body tissue, allowing biocompatibility issues to persist.
[0008] U.S. Pat. No. 5,607,463 to Schwartz et al. carried out experiments in which it was shown that tissue response to polymers could be reduced by means of a barrier layer of tantalum and niobium thin films on the exposed polymer surfaces. Specifically, in vivo tests showed an absence of thrombosis, inflammatory response, or neointimal proliferation when a thin tantalum or niobium barrier layer covered a polymer. However, in the case of a drug eluting polymer, these coatings detrimentally isolated the drug from the tissue as well.
[0009] U.S. Patent Application Pub. No. 2004/0172124 to Vallana et al. optimized the coating configuration by limiting the drug-eluting material to only that portion of the stent surface in contact with the vasculature. This was done by confining the drug eluting polymer to outward facing channels which were micro-machined into the stent mesh elements. All other stent surfaces were coated with hemocompatible carbon. Thus, the use of a biocompatible-problematic carrier polymer was minimized, but not eliminated.
[0010] In addition, U.S. Pat. No. 6,820,676 to Palmaz shows that, independent of the stent's surface composition, the surface texture of the stent or coating has an effect on the ability of proteins to adsorb into the stent surface, ultimately allowing thrombosis formation. It was shown that the surface texture can be controlled by grain size and other means to prevent protein adsorption and subsequent thrombosis.
[0011] Thus, even though much work has been done to develop stent systems comprising drug eluting polymers while minimizing, and even eliminating, thrombosis, inflammatory response and neointimal proliferation, further improvements are required to fully realize these goals. The present stent coating is believed to accomplish just that.
SUMMARY OF THE INVENTION
[0012] In the present invention, the drug-eluting outer layer of a stent consists of a porous sputtered metal or ceramic coating rather than a conventionally deposited polymer. This is done by placing the stent over a close-fitting mandrel and rotating the assembly in a sputter flux. The result is a coating that is evenly distributed over the outward-facing side of the stent's wire mesh while preventing the sputtered coating from reaching the inward facing side where a smooth hemocompatible surface is required. The stent is then removed from its mandrel, exposing all surfaces, and finally coated with a layer of carbon such as amorphous carbon or diamond-like carbon. The carbonaceous coating enhances biocompatibility without preventing elution of the therapeutic drug. The result is a stent that is adapted to both the hemodynamic and the immune response requirements of its vascular environment.
[0013] These and other objects and advantages of the present invention will become increasingly more apparent by a reading of the following description in conjunction with the appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a cross-sectional view of a stent 12 supporting a blood vessel 10 according to the present invention.
[0015] FIG. 2 is a cross-sectional view of a wire 14 comprising the stent 12 shown in FIG. 1 .
[0016] FIG. 2A is an enlarged cross-sectional view of the indicated portion of the stent wire 14 shown in FIG. 2 comprising a biocompatible porous columnar coating 16 supported on the stent wire 14 with a thin carbonaceous material 18 providing a cap on each of the columns as well as covering the inside-facing surface 14 B of the wire.
[0017] FIG. 3 is a cross-sectional view of the stent portion shown in FIG. 2A , but with the capillary spaces between the columnar coating 16 infused with a medication compound 20 .
[0018] FIG. 3A is an enlarged cross-sectional view of the indicated portion of FIG. 3 .
[0019] FIG. 4 is a cross-sectional view showing the interface between the stent and blood vessel 10 after deployment of the stent 12 .
[0020] FIG. 5 is an SEM photograph of a fracture cross-section of a porous columnar titanium nitride coating with porous carbon caps.
[0021] FIG. 6 is a SEM photograph showing sputtered columnar aluminum nitride adhering to a substrate that has been subjected to plastic deformation.
[0022] FIG. 7A is a schematic view of an unstrained stent wire 14 in a zero stress state.
[0023] FIG. 7B is a schematic view of the stent wire 14 shown in FIG. 7A having been strained within its elastic limit and depicting the resulting tension and compression stress forces therein.
[0024] FIG. 7C is a schematic view of the stent wire 14 shown in FIG. 7B being elastically strained and provided with a columnar coating 16 that is an unstrained state.
[0025] FIG. 7D is a schematic view of the stent wire 14 shown in FIG. 7C in a relaxed, unstrained state and depicting the resulting tension and compression stress forces in the columnar coating 16 .
[0026] FIG. 7E is a schematic view of the stent wire 14 shown in FIG. 7C having been expanded past its elastic limit and depicting the resulting tension and compression stress forces in both the wire and the columnar coating 16 .
[0027] FIG. 8A is a cross-sectional view of a polymer 26 used as a reinforcing material between individual columns 16 .
[0028] FIG. 8B is a cross-sectional view of the stent shown in FIG. 8A provided with a diffusion limiting polymeric coating 28 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] It has been found that coatings having a columnar structure can be made to adhere strongly to a substrate even while the substrate undergoes extensive plastic deformation. This is possible because the porous film consists of many strongly adhering individual columns rather than a single thin film coating. Furthermore, it has been shown that when thin columnar coatings are themselves coated with a biocompatible material such as carbon, the carbon continues the original columnar structure rather than disposing itself as a continuous non-porous barrier layer. This is described in U.S. Patent Application Pub. No. 2004/0176828 to O'Brien, which publication is assigned to the assignee of the present invention and incorporated herein by reference. These characteristics are put to use in the present invention as a medication-carrying structure on a stent for the purpose of eluting the medication into surrounding tissue to lessen or prevent restenosis.
[0030] Referring now to the drawings, FIG. 1 shows a cross-section of a blood vessel 10 with a stent 12 inserted and expanded therein. In the current invention, the medication eluting coating is limited to that portion of the stent in contact with tissue, which is exemplified by the blood vessel 10 .
[0031] The stent 12 is comprised of a plurality of wires 14 forming an elongated hollow tube and disposed so as to be capable of circumferential expansion. Commonly used stent materials include platinum, Nitinol, and even medical grade 316L stainless steel containing about 16% nickel. The wires 14 provide for an elongated, expandable hollow tube that can, in a preferred embodiment, increase in diameter when the ends of the hollow tube are moved closer relative to each other and decrease in diameter when the ends are moved apart. A design objective is to have as little length change as possible when the stent is expanded. Physicians have a hard enough time lining up a stent with a lesion without it acting like an accordion.
[0032] The stent 12 is positioned in the vasculature of a patient during or after a procedure, such as an angioplasty, atherectomy, or other interventional therapy, and then expanded to an appropriate size (i.e., approximately the same diameter as the vessel 10 in the region where placed), thus supporting that vascular region. When in its expanded configuration, the stent 12 provides support to the vascular walls thereby preventing constriction of the vascular region in which it is located and maintaining the vascular lumen open. This is often referred to as maintaining vascular patency.
[0033] FIG. 2 represents a cross-section of a wire 14 comprising the vascular stent 12 . The stent wire 14 has a roughly circular cross-section comprising an outside-facing surface 14 A and an inside-facing surface 14 B. The outside-facing surface 14 A of the stent wire faces the blood vessel wall and serves as a substrate provided with a coating 16 of columnar material to a thickness of about 0.1 μm to about 20 μm. Sputtering causes the columnar material to first be physically absorbed with some implantation into the wire material. This is due to the kinetic energy generated by the sputtering process prior to the column growing to its desired length.
[0034] While sputtering is a preferred method for depositing the columnar coating 16 , other suitable thin film deposition method can be used. These include chemical vapor deposition, pulsed laser deposition, evaporation including reactive evaporation, and thermal spray methods. Also, while the wire 14 is shown having a circular cross-section, that is not necessary. Other embodiments of the stent 12 comprise wires 14 having triangular, square, rectangular, hexagonal, and the like cross-sections.
[0035] As shown in FIGS. 3 and 3A , each column of the coating 16 comprises an intermediate portion 16 A extending to a base 16 B adhered to the inside-facing surface 14 B of the wire 14 and a tip 16 C. Each column is of a relatively consistent cross-section along its length extending to the base 16 B and tip 16 C. That way, the columns are discrete members that only adhere to the wire substrate at their base 16 B, but do not join to an immediately adjacent column. Titanium nitride is a preferred material for the columnar coating 16 , although other useful materials include, but are not limited to, boron, aluminum, calcium, gold, hafnium, iridium, molybdenum, niobium, platinum, rhenium, ruthenium, silicon, silver, tantalum, titanium, tungsten, yttrium, and zirconium, and carbides, oxides, nitrides, oxynitrides, carbonitrides thereof.
[0036] To further lessen the response of contacted tissue to the presence of the stent 12 , the inside-facing surface 14 B of the wire 14 as well as each columnar tip 16 C is coated with a carbonaceous material 18 , such as amorphous carbon or diamond-like carbon. During this operation, the carbon 18 assumes the morphology of a “cap” adhered to each tip 16 C of the porous columnar coating 16 supported on the outside-facing surface 14 A of the stent wire 14 . The carbon caps 18 , which are also preferably provided by a sputtering process, are at a thickness of about 0.05 μm to about 2.0 μm. That is, the porosity of the drug-eluting columnar coating 16 is maintained. This is because while the thickness of the carbon cap is sufficient to impart biocompatibility to the columnar tip 16 C, it is insufficient to form a continuous coating that could detrimentally isolate the drug eluting porosity inherent in the columnar structure. The carbon 18 that coats the bare metal inside-facing surface 148 of the stent wire 14 forms a smooth continuous pore-free layer suitable for contact with blood.
[0037] Finally, as shown in FIGS. 3 and 3A , the capillary spaces between the columns of the coating 16 and the carbon cap 18 are infused with medication 20 to inhibit restenosis. This can be done by various methods well known to those skilled in the art including spraying the stent with a medication solution, dipping the stent into a medication solution, immersing the stent in a medication solution under vacuum conditions and centrifuging the medication solution into the porosity.
[0038] FIG. 4 shows the interface between the treated stent wire 14 and the blood vessel 10 after deployment of the stent 12 therein. Medication 20 residing in the capillary spaces of the columnar coating 16 is directed into the vessel 10 supported by the stent with the vessel tissue only contacting the biocompatible carbonaceous caps 18 .
[0039] It is to be appreciated that the schematics of FIGS. 1 to 4 do not illustrate the extremely high surface area present in the inter-columnar capillaries. FIG. 5 is a SEM photograph of a fracture cross-section of a porous columnar coating illustrating, the volume of empty space therein and the internal surface roughness of the capillaries. In this case, the porous columnar coating consists of titanium nitride, which is widely used as a permanent implantable coating for bioelectrodes. Also visible in the photograph is the carbon cap on each individual titanium nitride column, comprising the outer 200 nm to 300 nm of the coating. Deposition of the carbon layer was done with the mandrel removed from the stent mesh. The mesh was fixtured to expose all surfaces of the stent to sputter flux. The stent was rotated in the sputter flux during deposition, which was done with DC sputtering of a carbon target in argon process gas. Typical conditions are 7 mTorr, 250 Watts, no bias. The result is a stent that presents a relatively thick, porous eluting layer containing therapeutic medication to the blood vessel wall, while presenting a smooth, hemocompatible face to the flowing blood.
[0040] FIG. 6 illustrates adhesion of a porous columnar coating of aluminum nitride even after extensive plastic deformation of the substrate. Reactive DC sputtering was used. The process gas was pure nitrogen at a pressure of about 5.3 mTorr. Power was set at 250 W on a 3 inch diameter planar target with no bias. Deposition time was 4 hours.
[0041] In that respect, a further aspect of the invention relates to controlling the stress state of each column comprising the coating 16 supported on the stent wires 14 . Fixturing the stent 12 on a mandrel (not shown) subjected to a sputter flux provides for coating the outside-facing surface 14 A thereof with the columnar coating 16 while protecting the inside-facing surface 14 B of the stent wire 14 . Increasing the degree of expansion over the mandrel to higher levels, within the elastic limit of the stent wire 14 , and sputtering in that expanded state, lessens the overall stress on the columnar coating 16 when the stent 12 is finally inserted and expanded in the blood vessel 10 . Then, when the stent is plastically deformed upon deployment into the vasculature, the individual columns are less likely to delaminate from the wire substrate as their connection to the substrate is in a relatively less stressed state. The associated carbon caps 16 experience the same compression and tension stress forces because they essentially “ride” on the tips 16 B of each column. This is illustrated in FIGS. 7A to 7E .
[0042] FIG. 7A shows an unstrained stent wire 14 . The wire has a generally elongate U-shape comprising spaced apart struts 14 C and 14 D joined together by a union portion 14 E. Datum points 22 and 24 are indicated adjacent to the terminus of the respective struts 14 C, 14 D. In actuality the struts comprise a continuous structure such as a mesh and have no “terminus”. When the stent is placed over a supporting mandrel (not shown), the distance between the datum points 22 , 24 is increased, as indicated by the opposing directions of the respective vector arrows 22 A and 24 A in FIG. 7B . The stresses set up in the union portion 14 E include both tension forces (+σe) and compression forces (−σe) within the elastic limits of the wire. The goal is to stress the union portion 14 E of the wire 14 within its elastic limits so that the tension and compression, strains create an opposite elastic pre-strain in the coating when the stent is removed from the mandrel. The struts 14 C, 14 D remain relatively unstressed.
[0043] FIG. 7C shows the stent wire 14 in the same stressed state illustrated in FIG. 7B , but after the sputtered columnar coating 16 is applied. The columnar coating 16 is in a zero stress state. Then, as shown in FIG. 7D , when the stent is removed from the mandrel, it elastically springs back with the distance between the datum points 22 , 24 being at or near to their original spacing shown in FIG. 7A . The columnar coating 16 is now in a stressed state opposite to that shown for the substrate in FIG. 7C . In that respect, the columnar coating 16 on the outside-facing surface 14 A is in a tension state within the elastic limits of the wire coating material (+σe) while the columnar coating on the inside-facing surface 14 B is in a compression state (−σe).
[0044] In FIG. 7E , the wire 14 undergoes plastic deformation during the stent's expansion and placement in the vasculature. This is depicted by the opposing directions of the respective vector arrows 22 A, 24 A. In this final state, the stress in the coating 16 is the stress due to deformation of the wire surface at the union portion 14 E minus the coating pre-stress, as shown in FIG. 7E . Therefore, the final tension (−σf) and compression (+σf) forces in the coating 16 are somewhat less than they would have been had the columnar coating been provided on the stent wire in a completely relaxed state in comparison to the actual stressed state the union portion 14 E was in during the deposition process. The difference is the amount of elastic deformation in the union portion 14 E of the stent wire 14 while the coating was being deposited ( FIG. 7C ).
[0045] The elastic limit of the stent wire 14 can be determined by placing the stent over increasingly larger diameter mandrels, until the spring back upon removal does not return the stent to its original dimension. Alternately, the film pre-stress can be achieved by using a nickel titanium shape memory alloy which can be made to assume the partially expanded configuration by heating in the sputter chamber.
[0046] Another aspect of the invention is shown in FIG. 8A . This embodiment relates to the use of a polymer 26 that is provided with a medication and infused into the porous columnar coating 16 to improve biocompatibility while increasing coating strength and adhesion. Suitable polymers include (but are not limited to) polyurethane, silicone, polyesters, polycarbonate, polyethylene, polyvinyl chloride, polypropylene methylacrylate, para-xylylene.
[0047] As shown in FIG. 8B , a polymer 28 can also be used to moderate and control the diffusion of the medication from the capillaries of the porous coating 16 into the surrounding tissue. In that case the polymeric coating 28 is added to the porous layer after it is infused with the therapeutic medication.
[0048] Because the process coats all surfaces of the stent, it allows selection from a wider range of substrate materials, including those which improved radiopacity characteristics. This is an important consideration for locating the stent correctly during placement in the vasculature.
[0049] It is appreciated that various modifications to the invention concepts described herein may be apparent to those of ordinary skill in the art without departing from the scope of the present invention as defined by the appended claims.
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A vascular stent comprising a drug-eluting outer layer of a porous sputtered columnar metal having each column capped with a biocompatible carbon-containing material is described. This is done by placing the stent over a close-fitting mandrel and rotating the assembly in a sputter flux. The result is a coating that is evenly distributed over the outward-facing side of the stent's wire mesh while preventing the sputtered columnar coating from reaching the inward facing side where a smooth hemocompatible surface is required. The stent is then removed from the mandrel, exposing all surfaces, and finally coated with a layer of carbon such as amorphous carbon or diamond-like carbon. The carbonaceous coating enhances biocompatibility without preventing elutriation of a therapeutic drug provided in the porosity formed between the columnar structures. The result is a stent that is adapted to both the hemodynamic and the immune response requirements of its vascular environment.
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This is a continuation-in-part application of Ser. No. 851,372 filed Nov. 14, 1977, now abandoned.
BACKGROUND OF THE INVENTION AND PRIOR ART
This invention relates to improved methods of utilizing solar radiation for heating purposes. Solar radiation is abundantly available on the earth's surface; however, its average intensity during high demand periods is usually minimal. This necessitates the need for very efficient, inexpensive solar energy collectors to make the whole concept economically practical and competitive with conventional fuels. Up until this time one had to compromise efficiency for low cost or vice versa. Maximum efficiency required the use of expensive materials and complicated production methods.
An object of this invention is to provide a method of getting maximum efficiency at a minimum cost in the field of high efficiency solar collectors through a novel means of combining inexpensive construction materials with a new concept in collector plate insulation technique. A further object of the present invention is to provide a solar collector that is basically simple in its design. The present invention eliminates the need for complicated gaskets to form hermetic seals which wear out because of constant thermal expansion and contraction and contact with harsh environmental factors such as high temperature and untraviolet light. Keeping in line with the concept of design simplicity this invention provides a way of eliminating complicated manifold systems which are both expensive and a major course of leaks.
SUMMARY OF THE INVENTION
This invention relates to a novel solar collector panel consisting of a solar radiation absorption plate insulated on the bottom and sides with conventional insulation materials such as styrofoam. In the preferred embodiment, the panel is insulated on the top initially by a dead air space and secondly, by a unique, transparent film envelope hermetically sealed and filled with a vapor phase insulating gas of low thermal conductivity. The absorption plate has channels which form a generally sinusoidal path on its underside. These channels are defined on the lower side and lateral sides by a plastic membrane hermetically sealed to the absorption plate. A heat transfer fluid is introduced through a conduit on one side of the collector plate and allowed to leave through a conduit on the opposite side after passing through the sinusoidal path of the channels. Each conduit is hermetically sealed to its respective entrance and exit end of the channels.
Solar radiation enters through the transparent film comprising the insulating envelope and the vapor phase gas that it contains, striking the solar radiation absorption plate and creating heat which is absorbed by a heat transfer fluid on the underside of the absorption plate which is fed by conduits by means of a circulating pump. The very high efficiency of this collector is derived from the vapor phase insulating gas of an extremely low thermal conductivity which is sealed in a unique, transparent plastic envelope and placed strategically over a dead air space above the solar radiation absorption plate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of a flat plate solar heating panel with parts broken away illustrating a preferred embodiment of the present invention;
FIG. 2 is a fragmentary elevational view taken in vertical cross section along line 2--2 of FIG. 1 showing the details of the panel construction;
FIG. 3 is an elevational view taken in vertical cross section of a thermal insulating envelope illustrated in FIG. 1;
FIG. 4 is an elevational view taken in vertical cross section similar to FIG. 2 but illustrating a modified form of thermal insulating envelope;
FIG. 5 is an elevational view taken in vertical cross section similar to FIG. 2 but illustrating a further embodiment of the present invention;
FIG. 6 is an elevational view taken in vertical cross section similar to FIG. 2 but illustrating yet another embodiment of the present invention; and
FIG. 7 is an elevational view taken in vertical cross section similar to FIG. 2 but illustrating an additional embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows an isometric view of a rectangular solar collector of the flat plate type, showing an inlet conduit 18 and an outlet conduit 20. The entire apparatus is supported on all four sides and on the top and bottom edges by sheath 19. FIG. 2 shows a cross sectional view of the panel in which solar energy enters the apparatus through sheets 4 and 5 and spaces 14 and 13 where the solar energy is absorbed by an absorption plate 9. As solar radiation is transformed into heat, heat transfer fluid traveling through chambers 10 is heated and returned to a storage facility or utilized immediately.
FIGS. 2 and 3 depict the preferred embodiment in more detail. Envelope 21 is formed by molding a flexible transparent film 5 into the desired shape and stretching taut flexible transparent film 4 on top of it forming a space or cavity 14. Films 4 and 5 are hermetically sealed at their peripheral edges 16 by joining the perimeter of film 4 to lip 23 of film 5. Preferably this is accomplished by a heat or dielectric sealing operation, although cementing or any other suitable hermetically sealing method will suffice. An insulating envelope indicated generally at 21 is formed between films 4 and 5 above the absorption plate 9 and adjacent sidewalls 25 of the panel. The envelope is kept taut either by mechanical restraints or cementing. Sidewalls 25 are preferably made from a rigid insulating material, such as styrofoam, according to conventional practices.
Envelope 21 thus has an inner space 14 in which is contained a vapor phase insulating gas of low thermal conductivity relative to air. The gas is inserted into envelope 21 by conventional means such as a needle valve and hermetically sealed thereafter. The gas within envelope 21 is allowed free thermal expansion and contraction caused by variations in the incident solar energy, because of the flexible nature of the envelope. Thus, the need for a pressure equalization membrane or valve is eliminated. Hermetic seal 16 is permanent and flexible and has a life expectancy equivalent to that of the plastic of films 4 and 5. The hermetic seal eliminates the possibility of leaks or contamination from the surrounding air which would dramatically reduce the efficiency of the collector. The use of this particular hermetic seal is an improvement over the prior art of sealing with gaskets or by cementing, in conjection with rigid or film glazings. The use of these gaskets resulted in the contamination or eventual loss of the vapor phase insulating gas. The gas within envelope 21 should be relatively clear, that is, one which allows a high percentage of solar energy transmittance, it must be stable and have excellent aging qualities especially in the continued presence of ultraviolet light. The gas must also be compatible with the plastic film which comprises the envelope, i.e., it must not cause cloudiness, crazing, cracking, brittleness, etc. The gas used in the preferred embodiment is a halocarbon or fluorocarbon noted for its excellent aging characteristics, low permeability and having a thermal conductivity of approximately 0.005 BTU/(hr) (ft) (°F.) about 33% that of air (0.15 BTU/(hr) (ft) (°F.) at 77° F. at 1 atm) making it a better insulating material than air by about 300%. The presence of flourine, bromine or other atoms from this family in the molecule give long lasting durability and stability to an organic molecule that has basically poor aging characteristics. Certain grades of polytetraflouroethylene are most suitable for the plastic film because of high transmitivity, excellent aging characteristics, compatibility with the vapor phase insulating gas, and low price. Film 4 of envelope 21 should be of a heavy enough grade (0.005 in. to 0.01 in. is sufficient) to withstand exposure to the environment. Although film 5 of envelope 21 may be of the same thickness as film 4, in an effort to cut cost, if may be of a thinner grade such as 0.001 inches. Polyester type films generally are not suitable for usage in solar applications because of ultraviolet degradation but may be used if the film has ultraviolet light absorbers or inhibitors or utilizes any method which inhibits or is resistant to the breakdown of the film by ultraviolet light. "LLumar" by Martin Processing is an example of this type of film.
Beneath absorption plate 9 are chambers 10 with their lower and lateral boundaries defined by plastic film 12 which may be of the same material as the insulating envelope. Plastic film 12 is hermetically sealed to the perimeter of the absorption plate 9, preferably folded over and sealed to the top and bottom. Alternatively, the absorption plate 9 may be folded over the marginal edges of envelope 21 and hermetically sealed thereto. Clamp 17, a mechanical restraint, extends throughout the entire perimeter, pinching both layers of the absorption plate 9 and the film 12 together and forming a stiff edge that can be mounted in a groove in side walls 25. Chambers 10 are formed by sealing flexible membrane 12 to the underside of absorption plate 9 in. long thin, spaced, parallel joints or seals stretching substantially end to end. Alternate ends of the joints or seals are spaced from the lateral edges to define openings which allow the heat transfer fluid passage from one chamber to the next until it travels beneath the entire lower surface 8 of the absorption plate 9. In this manner, a sinusoidal path is formed by the channels of film 12 which is selectively sealed to the underside of absorption plate 9. The heat transfer fluid is pumped against gravity, entering inlet conduit 18 and exiting through outlet conduit 20 which are substantially at the same elevation. By keeping the heat transfer fluid in chamber 10 directly in contact with the majority of surface 8 or absorption plate 9, heat will flow more rapidly from the absorption plate 9 to the heat transfer fluid, than would flow if small passageways separated from each other or tubing bonded to the absorption plate were used. The concept of faster, more uniform heat transference increases the overall efficiency of the collector by limiting the time of exposure to dead air space 13 and also limiting the rate of black body radiation by the absorption plate. The overall efficiency of the collector is also increased because absorption plate 9 is kept at a relatively uniform temperature, as opposed to having those areas farthest away from the heat transfer fluid, as in the case of tubing or narrow channels spaced a considerable distance apart, from building up higher temperatures resulting in a greater percentage of heat loss caused by conduction, convection and radiation. Absorption plate 9 is made of copper or some other material having a high rate of thermal conductivity to facilitate the rate of heat transfer.
Beneath membrane 12 is rigid insulating material 15, such as styrofoam, which insulates the collector on the bottom and gives rigidity to the entire system. Base 15 of the collector body is of the same material as walls 25 insulating the perimeter of the collector, giving the collector rigidity and providing a method of mounting the various components to the collector. Surrounding walls 25 is sheathing 19 which serves to hold the collector together and to define the outer lateral boundaries. Additional sheathing may be put on the bottom of base 15 to give additional strength.
FIGS. 5-7 illustrate various modifications which are capable of being employed with the basic structure illustrated in FIGS. 1 and 2. For example, the dead air space 13 of the collector panel 1 may be substantially eliminated and this is illustrated in FIG. 5. Thus, the envelope 21 may expand upwardly instead of downwardly in this embodiment. In each of FIGS. 5-7 only a single envelope 21 is illustrated, but it is to be understood that multiple envelopes may be used with or without dead air spaces.
FIG. 6 illustrates the use of a glass plate 26 atop absorption plate 9 while FIG. 7 shows the use of a similar glass plate 26 but in this form of the invention it is shown above the envelope 21. In FIG. 7 the glass plate is positioned sufficiently far above envelope 21 to leave a dead air space 29 above envelope 21. Other arrangements of the basic elements illustrated in FIGS. 1 and 2 may be employed.
It should be noted that this is the preferred embodiment of the invention and the scope of this invention is not limited to any one particular kind of film nor is the envelope limited to any particular size, shape, thickness or position relative to the absorption plate 9. The preferred embodiment uses a selective surface 11 of the upper surface of the absorption plate to inhibit infra-red radiation. A selective surface is defined as a high absorber of solar energy and a low emitter in the infra-red wavelengths and is formed in a manner familiar to those skilled in the art. However, this invention is not limited to the use of a selective surface to inhibit radiation from the absorption plate surface. Any suitable method of inhibiting radiation from the system, familiar to those skilled in the art, is acceptable. The use of certain types of glazings, such as glass, which are opaque to infra-red radiation may be used. They are placed in a position so as to keep radiation within the system, such as between absorption plate 9 and the insulating envelope 21, or even as an external coverplate on top of the insulating envelope 21. In some cases, where extremely high efficiency is not needed, it may not be desirable to insulate against radiation loss through the use of a selective surface or any other suitable means and the elimination of such inhibitors reduces the overall cost of the collector.
Between film 5 of envelope 21 and absorption plate 9 is a dead air space 13 which contributes to the overall insulating qualities of the collector. The width of space 13, although not limited to, should be one half inch when envelope 21 is in its average, operating expanded position. It has been found that a dead air space of one half inch above the absorption plate is the most desirable distance for keeping convective heat losses at a minimum. An absorption plate 9 is heated, convection currents will form; however, by keeping the vapor phase insulating gas contained in envelope 21, out of direct contact with the absorption plate 9, convective heat losses will be kept at a minimum. The gas contained in space 13 is preferably hermetically sealed and therefore subject to thermal expansion and contraction due to variations in the incident solar energy. However, no pressure equalization valve or membrane is needed because the flexible envelope 21 above it has sufficient flexibility to compensate for any variations in pressure.
It is considered within the scope of this invention to use more than one insulating envelope, either independently or in conjunction with each other. FIG. 4 is an example of two envelopes used in conjunction with each other. Chamber 28 is formed by hermetically sealing flexible transparent film 5 around their common perimeters and thus chambers 14 and 28 share a common wall 5. Chamber 28 may also be filled with a vapor phase insulating gas of low thermal conductivity, or may contain a dead air space, depending on the desired efficiency. These multiple chambered envelopes should be placed in a strategic position over the absorption plate 9 as in envelope 21 shown in FIG. 2. A strategic position is defined as that position relative to the absorption plate 9 that is most advantageous to the inhibition of conductive and convective heat losses. Chambers 14 or 28 may also hold a heavy or high density gas that has the ability to specifically inhibit convective heat losses.
While presently preferred embodiments of the invention have been illustrated and described, it will be recognized that the invention may be otherwise variously embodied and practiced within the scope of the claims which follow.
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A solar collector panel wherein a dead air space above an absorption plate is provided with a hermetically sealed vapor phase insulating gas within a plastic envelope. The flexible nature of the envelope permits expansion and contraction of the gas therewithin avoiding the necessity for a pressure equalization membrane or valve. A heat transfer fluid is circulated between channels along a sinusoidal path of a plastic member selectively sealed to the underside of the absorption plate.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a slide fastener stringer including a stringer tape and a series of fastener coupling elements sewn to the tape along one longitudinal edge thereof by utilizing multi-thread chain stitch or "double locked stitch".
2. Prior Art
In sewing a series of fastener coupling elements to a stringer tape for a slide fastener, one of the most widely used stitch types is multi-thread chain stitch or "double locked stitch", which is formed with two or more sewing threads, i.e. needle and looper threads. It has been customary to use a spun or multifilament yarn for either the needle thread or the looper thread, for such non-monofilament yarns are flexible and less stretchable and hence enable the fastener elements to be sewn to the tape tightly on a high-speed sewing machine without breakage of a sewing needle.
A common problem encountered with such prior art slide fastener stringer is that, because the material and fabric structure of modern stringer tapes are usually of the type having less frictional resistance, the sewing threads are liable to become loose from its cut end portions which have been cut as the fastener stringer of a continuous length has been severed into a slide fastener length. With this arrangement, when the opposed stringer tapes are laterally pulled at their one end in opposite directions during threading of a pair of the interengaged fastener stringers through a slider, the extreme one or two or even more of the fastener elements on each tape would be easily displaced. Consequently, it would be difficult or sometimes impossible to mount the slider onto the interengaged fastener stringer.
U.S. Pat. No. 3,783,476 discloses a slide fastener stringer having a row of fastener elements secured to a stringer tape by means of single-needle double locked stitch formed with needle and looper threads, of which only needle thread includes a monofilament yarn. The needle thread is disposed on the fastener-element side of the slide fastener stringer, and hence, the stitching must be done from that side. This requires a specially designed guide means to support the slide fastener stringer such that the surface of the stringer tape on which the fastener elements are to be attached faces upwardly during sewing operation. With this arrangement, sufficient degree of tightness of the stitching is difficult to achieve. Further, because the fastener elements are held, against the stringer tape, by the monofilamentary needle thread and both the fastener elements and the needle thread have less frictional resistance, the needle thread is liable to slip on the fastener elements and hence is not likely to keep the fastener elements stably in position on the tape. Moreover, the looper thread projects from the tape surface so that a slider is likely to wear out the looper thread.
U.S. Pat. No. 3,768,125 discloses another slide fastener stringer having a row of fastener elements secured to a stringer tape by means of single-needle double locked stitch formed with needle and looper threads. Such prior art slide fastener stringer has not sufficient degree of flexibility, which is one of the most important factors for slide fasteners, partly because monofilament yarns have rigidity by nature and partly because loops of the monofilamentary looper thread extend across and over the fastener elements. Further, because the fastener elements are held, against the stringer tape, by the monofilamentary looper thread and both the fastener elements and the monofilamentary looper thread have less frictional resistance, the needle thread is liable to slip on the fastener elements and hence is not likely to keep the fastener elements stably in position on the tape.
SUMMARY OF THE INVENTION
According to the present invention, sewing stitches securing a series of fastener elements to a stringer tape are formed with at least one needle thread and a looper thread. The needle thread consists of a thermoplastic monofilament yarn and has loops each passing through the tape from the underside thereof and extending through a space between adjacent two of the fastener elements. The looper thread consists of a spun or multifilament yarn and has loops extending across and over the fastener elements on the top side of the tape. The needle thread is interlaced and interlooped with the loops of the looper thread, and each of the needle thread loops has a constricted portion engaging with adjacent two of the looper thread loops. After stitching of the fastener elements to the tape, the thermoplastic monofilamentary needle thread has been heat-set to become dimensionally stable. Such constricted portions of the needle thread loops serve to keep the looper thread from becoming loose even at their cut end portions. This prevents the fastener elements from being displaced on the tape at the end of the element row from which a slider is threaded or mounted.
Further, top surfaces of the needle thread loops are disposed above or flush with those of the looper thread loops so that the looper thread can be kept nicely from being worn out due to frictional engagement with a slider.
It is therefore an object of the present invention to provide a slide fastener stringer which enables smooth threading of a slider.
Another object of the invention is to provide a slide fastener stringer which has a row of fastener elements kept stably in position on a stringer tape and hence is free from accidentally splitting apart from a companion stringer when the coupled stringers are bent in either direction.
Still another object of the invention is to provide a slide fastener stringer which can be manufactured less costly.
Many other advantages, features and additional objects of the present invention will become manifest to those versed in the art upon making reference to the detailed description and the accompanying drawings in which preferred structural embodiments incorporating the principles of the present invention are shown by way of example.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary top plan view of a pair of interengaged slide fastener stringers each embodying the present invention;
FIG. 2 is an end elevation of the slide fastener stringers of FIG. 1;
FIG. 3 is a fragmentary cross-sectional view taken along line III--III of FIG. 1;
FIG. 4 is a fragmentary cross-sectional view taken along line IV--IV of FIG. 1;
FIG. 5 is a fragmentary perspective view of sewing stitches of FIGS. 1-4, showing the formation of needle and looper threads;
FIG. 6 is a side elevational view of a loop of the needle thread;
FIG. 7 is a top plan view of the needle thread loop of FIG. 6;
FIGS. 8 and 9 illustrate the manner in which the pair of interengaged slide fastener stringers of FIG. 1 is threaded through a slider;
FIG. 10 is a transverse cross-sectional view of a slide fastener stringer according to a second embodiment;
FIG. 11 is a longitudinal cross-sectional view of the slide fastener stringer of FIG. 10;
FIG. 12 is a cross-sectional view similar to FIG. 10 but showing a slide fastener stringer according to a third embodiment;
FIG. 13 is a fragmentary plan view of a slide fastener stringer according to a fourth embodiment;
FIG. 14 illustrates various examples of cross-sectional shape of the needle thread; and
FIGS. 15 and 16 are comparative cross-sectional views illustrating looper thread under varying tension.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The principles of the present invention are particularly useful when embodied in a slide fastener assembly (hereinafter referred to as "slide fastener") such as shown in FIGS. 1-4, generally indicated by the numeral 21.
The slide fastener 21 comprises a pair of fastener stringers 22, 23 including a pair of stringer tapes 24, 25, respectively, each supporting on and along one longitudinal edge thereof a series of fastener elements 26 in the form of a continuous filamentary coil made of a thermoplastic synthetic resin. Each series of fastener elements 26 is secured to one of the tapes 24, 25 by means of sewing stitches. The type of the sewing stitches is multi-thread chain stitch or "double locked stitch", which is formed with a needle thread 27 and a looper thread 28. Each of the fastener elements 26 has a pair of spaced upper and lower legs 29, 30, and a coupling head 31 extending therebetween. The lower leg 30 of each fastener element lies on the top surface 33 (FIGS. 2 and 3) of the stringer tape 24, 25 and is connected to the upper leg 29 of a preceding or succeeding one of the fastener elements 26 by a connecting portion 32, the upper element leg 29 being spaced away from the same tape surface 33. A core 34 in the form of a textile cord extends longitudinally through the series of fastener elements 26 and is held by the needle thread 27 against the connecting portions 32 in the interior of the fastener elements 26.
The needle thread 27 consists of a monofilament yarn made of a thermoplastic synthetic resin such as nylon. The looper thread 28 consists of a non-monofilament yarn, i.e. a multifilament or spun yarn, which is made of a synthetic resin such as polyester.
As shown in FIG. 3, the needle thread 27 has loops 35 each passing through the tape 24, 25 from the underside thereof and extending through a space between adjacent two of the fastener elements 26, each of the needle thread loops 35 having a constricted portion 35a (FIGS. 5 and 6). The loops 35 of the needle thread 27 are interlaced and interlooped with the looper thread 28 such that those interlacings and interloopings 37 are located between adjacent element legs 29. One (36) of adjacent two loops 36, 36b of the looper thread 28 extends across and over the upper element leg 29 adjacent thereto and around the constricted portion 35a of the needle thread loop 35. The other looper thread loop 36a is interlaced with that needle thread loop 35 so as to be disposed above said one looper thread loop 36. One end of the loop 36 is blended into one end of a preceding loop 36a through a connecting portion 36b, and the other end of the loop 36 is blended into the other end of a succeeding loop 36a through a connecting portion 36b. The connecting portion 36b extends through the corresponding one of the needle thread loops 35 so as to be disposed therein in intimate contact with the looper thread loop 36a. As shown in FIGS. 3 and 4, the looper thread loop 36, which extends around the constricted portion 35a, is interposed between the looper thread loop 36a and the core 34. Thus, the constricted portion 35a serves to keep the looper thread loop 36 from becoming loose. The looper thread loop 36a and the connecting portion 36b extend so as to be disposed closely in the needle thread loop 35 so that the loop 36a also is not likely to become loose. Further, the individual needle thread loops 35 extend upwardly beyond the topmost surfaces 36a (FIG. 4) of the looper thread 28 by a predetermined distance l (FIG. 4) so that a slider 44 (FIG. 2) is not likely to wear out the looper thread 28. The distance l is equal to the diameter of the needle thread 27 at the maximum. And the minimum value for the distance l may be nil; that is, the topmost surfaces 35b of the needle thread loops 35 may be flush with those of the looper thread 28.
These structural features can be effected by selecting a particular degree of tension F of the looper thread 28 and a particular degree of tension f of the needle thread 27 in stitching. As is well known in the art, if the looper thread 28 is tensioned less strongly (under the tension F') while the needle thread 27 is tensioned strongly (under the tension f'), such that looper thread portions 28a, 28b, 28c on the upper element leg 29 are arranged in the fashion illustrated in FIG. 15, the interlacings and interloopings 37 are retracted toward the tape 24, 25, causing the surfaces 35b of the needle thread loops 35 to be lowered below the surfaces 36c of the looper thread 28. Conversely, if the looper thread 28 is tensioned strongly (under the tension F") while the needle thread 27 is tensioned less strongly (under the tension f"), such that the looper thread portions 28a, 28b, 28c are now arranged in the fashion illustrated in FIG. 16, the interlacings and interloopings 37 and hence the surfaces 35b of the needle thread loops 35 are raised above the surfaces 36c of the looper thread 28. And, such required degrees of tension F, f for the looper thread 28 and the needle thread 27 are defined by the following inequalities:
F">F>F'
f'>f>f"
As shown in FIG. 7, the individual needle thread loop 35 has a widened portion 35c.
After stitching of the fastener elements 26 to the stringer tape 24, 25 as described above, the needle thread 27, which consists of a thermoplastic monofilament yarn, has been heat-set by applying a heated medium, for instance, during a dyeing process. As a result, the needle thread 27 has become dimensionally stable; that is, the bent configurations 35a,38,39 (FIGS. 3 and 4) of the needle thread 27 are maintained against further dimensional change, thereby preventing the needle thread 27 as well as the looper thread 28 from becoming loose at the cut end portions 40,41 of the slide fastener stringers 22,23, respectively.
More specifically, in case the needle thread 27 has been cut such that its cut end 42 point upwardly (FIG. 4), the needle thread 27 is not likely to become loose because the bent configuration 38 of the needle thread 27 is kept in stable. In case the needle thread 17 has been cut such that its cut end 43 point downwardly (FIG. 3), the looper thread 28 is held at its cut end portion by the extreme needle thread loop 35 of which bent configuration 35a,39 would not change. Accordingly, the extreme one or two of the fastener elements 26 can be prevented nicely from being separated apart from the tape 24,25, no matter where the cut end of the stringer 22,23 is located.
The interengaged slide fastener stringers 22,23 thus constructed can be threaded through the slider 44 (FIGS. 8 and 9) from its rear end mouth 45 with maximum ease. In such threading, the interengaged slide fastener stringer 22,23 are inserted into the slider from the rear end mouth 45 thereof until the leading end of the interengaged rows of fastener elements 26 reaches just in front of a slider neck 46, as shown in FIG. 8. At that time, the opposed stringer tapes 24,25 are gripped at their respective leading ends by the fingers. Then, the opposed stringer tapes 24,25 are pulled in the directions indicated by arrows 47,48 (FIG. 8), respectively, to disengage the mating of the opposed rows of fastener elements 16 at their leading end portions, as shown in FIG. 9. Subsequently, the opposed stringer tapes 24,25 are pulled beyond the front end 51 of the slider 44 in the directions of arrows 49,50, respectively. Thus, the mounting of the slider 44 onto the interengaged slide fastener stringers 22,23. During this threading operation, the extreme one or two of the fastener elements 26 on each tape 24,25 are kept stable in position even when relatively great pulls (47,48) act on the opposed stringer tapes 24,25.
According to an embodiment of FIGS. 10 and 11, each fastener element 26 has a groove 52 extending across its upper leg 29, and the looper thread portions 28a,28b, 28c are received in the groove 52 and is kept in stable. According to an embodiment of FIG. 12, the upper leg 29 of each fastener element 26 has corrugations 53 for receiving the looper thread portions 28a,28b,28c, one in each corrugation. Given such groove 52 or corrugations 53, it is possible to minimize the thickness H (FIG. 11) of the slide fastener stringer 22,23.
According to an embodiment of FIG. 13, the lockstitching is formed with two needle threads 54,55 and one looper thread 28.
To obtain an increased degree of frictional resistance, the needle thread 27 may be of a noncircular cross section, such as ellipse (a), triangle (b), square (c) or rectangle (d) (FIG. 14).
In any one of the embodiments described above, the needle thread 27 is disposed on the tape side of the slide fastener stringer 22,23, while the looper thread 28 is on the fastener-element side. With such arrangement, the slide fastener stringer can be guided in such a manner that the surface 33 of the stringer tape 24,25 on which the fastener elements 26 are to be attached faces downwardly during stitching. This requires no specially designed guide means and hence no expensive and complicated sewing machine.
Although various minor modifications may be suggested by those versed in the art, it should be understood that I wish to embody within the scope of the patent warranted hereon, all such embodiments as reasonably and properly come within the scope of my contribution to the art.
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A slide fastener stringer includes a stringer tape and a series of fastener elements sewn to the stringer tape on one of the opposite surfaces thereof along its one longitudinal edge by means of double locked stitches composed of at least one needle thread and a looper thread. The needle thread includes a thermoplastic monofilament yarn, and the looper thread includes a spun or multifilament yarn. The stitching has been done from the tape side of the slide fastener stringer. Loops of the looper thread project hardly from the topmost surface of the needle thread loops so that a slider is not likely to wear it out. Each of the needle thread has a constricted portion which serves to keep the looper thread loops from becoming loose. After stitching of the fastener elements to the tape, the thermoplastic monofilamentary needle thread has been heatset to suitably shrink and then become dimensionally stable.
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This divisional application claims priority from U.S. patent application Ser. No. 10/749,716 filed Dec. 31, 2003 now U.S. Pat. No. 7,007,561, which claims priority from U.S. Provisional Application Ser. No. 60/437,467 filed Dec. 31, 2002.
BACKGROUND
This disclosure relates to improvements in measurement and calibration of apparatus used for testing the track strength of railroad track, tie and fastener conditions using a loaded gauge axle assembly which imparts a calibrated downward force and a calibrated outward force on the rails, and measures the load applied to the rails to determine the strength of the rails, ties and fasteners.
By way of background but not limitation, various types of measurement and calibration devices are utilized by the industry for testing strength of railroad tracks, ties and fasteners including a “Gauge Restraint Measurement System (GRMS)” from the U.S. Department of Transportation also described in an article entitled “AAR's Track Loading Vehicle” and U.S. Pat. No. 5,756,903 issued May 26, 1998. The teachings of said U.S. Pat. No. 5,756,903 are incorporated by reference as if fully set forth herein.
The track strength testing vehicle of U.S. Pat. No. 5,756,903 measures changes in hydraulic fluid pressure to determine both changes in load due to track strength changes and to control the load applied.
This system introduces potential error in the measurements because of factors such as time lag between changes at the wheel and measurement of pressure, errors-introduced by pressure changes made to preserve load at the wheel, and the number of components, instruments and calculations involved. This system does not account for frictional forces within the split-axle assembly and cannot be used as a true rail/wheel force through direct transducer measurement.
While the track strength testing taught in U.S. Pat. No. 5,756,903 is believed to be reliable and cost effective, its measurement system is believed to be somewhat over-inclusive, in that the statistical variations result in indications of track failure, when in fact the track is within specifications. Improved accuracy, therefore, can be expected to have economic and time saving benefits in minimizing unnecessary repairs, and operational benefits in the ability to reliably and rapidly locate those areas in need of repair.
The testing apparatus of U.S. Pat. No. 5,756,903 is a significant improvement over the very large sized competitive track testing machines in that the load gauge axle assembly can be comparatively easily removed and replaced, both for maintenance, and also for calibration. Under the arrangement of U.S. Pat. No. 5,756,903 complete calibration is accomplished by removal of the axle assembly and testing in a laboratory or shop. Field calibration can only be accomplished on certain components and systems. Rail car mounted testing apparatus, or track maintenance apparatus the size and mass of rail cars are even more difficult to calibrate, as the size of the vehicle and its components essentially requires removal from service and return to a shop.
In view of the above, it should be appreciated that there is a need for a device that accurately measures track strength and permits expedient calibration of the measurement device. The present disclosure satisfies these and other needs and provides further related advantages.
SUMMARY
The disclosure comprises a direct measuring loaded gauge axle assembly that measures track strength by directly measuring loads on split axles as vertical loads are imposed by hydraulic rams. Horizontal loads are supplied by a horizontal ram through split axles and flanged steel wheels to the rail head of the railroad tracks, enabling improved calibration to measure track strength and electronic data recording and comparison.
Other features and advantages of the disclosure will be set forth in part in the description which follows and the accompanying drawings, wherein the embodiments of the disclosure are described and shown, and in part will become apparent upon examination of the following detailed description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The above mentioned and other features of this disclosure and the manner of obtaining them will become more apparent and the disclosure will be best understood by reference to the following description of embodiments of the disclosure taken in conjunction with the accompanying drawings in which:
FIG. 1 is a side elevational view of the motor vehicle and loaded gauge axle track strength apparatus on a railroad track;
FIG. 2 is a top plan view of the motor vehicle body and loaded gauge axle track strength apparatus with the body portion in section to show the arrangements;
FIG. 3 is a front elevational view of the loaded gauge axle track strength apparatus with the calibration assembly with the calibration subsystem;
FIG. 4 is a left side elevational view of the loaded gauge axle track strength apparatus with the calibration subsystem;
FIG. 5 is a top plan view of a first side of the prior art loaded gauge axle track strength with the load cell sensor embodiment;
FIG. 6 is a front sectional view of a first side of the prior art loaded gauge axle track strength apparatus with the load cell sensor embodiment;
FIG. 7 is a top plan view of a second side of the loaded gauge axle track strength apparatus;
FIG. 8 is a front sectional view of a second side of the loaded gauge axle track strength apparatus;
FIG. 9 is a display of the data collected by the loaded gauge axle track strength apparatus;
FIG. 10 is a plot of results from the prior art load loaded gauge axle track strength apparatus;
FIG. 11 is a plot of results from the improved loaded gauge axle track strength apparatus;
FIG. 12 is a flow chart of the load axle calibration subsystem; and
FIG. 13 is an exploded view of the loaded gauge axle track strength apparatus.
DETAILED DESCRIPTION
While the present disclosure will be described fully hereinafter with reference to the accompanying drawings, in which a particular embodiment is shown, it is to be understood at the outset that persons skilled in the art may modify the disclosure herein described while still achieving the desired result. Accordingly, the description that follows is to be understood as a broad informative disclosure directed to persons skilled in the appropriate art and not as limitations on the present disclosure.
As illustrated in the drawings, the truck vehicle 10 has road wheels 12 and high rail wheels 14 . This arrangement enables operation of the vehicle on ordinary roads, driving to railroad tracks 16 and straddling them, then actuating the retractable high rail wheels 14 to partially lift the truck off the rails 17 . Motive drive is nevertheless still provided with the road wheels through the rubber tires 18 . Gauge axle assembly 20 is located between the truck wheels 12 .
The high rail units 14 are preferably forward of the front end 22 and rearward of the rear end 24 of the vehicle, forward of the front end 22 on a front frame extension 26 and rearward of the rear end 24 on a frame extension 28 , as shown in FIG. 1 .
The gauge axle assembly 20 is used to apply a calibrated side load on the tracks 16 . Variation in track side load is measured by the gauge axle assembly 20 and the measurements taken are analyzed to determine the strength of the track 16 by measuring variations in hydraulic pressure as load is also placed on the gauge axle. Split axle assembly 30 made up left and right generally square sectioned shafts 32 , 34 each having a spindle 36 , 38 on its outboard end 40 , 42 , as generally discussed in U.S. Pat. No. 5,756,903 and as shown in FIGS. 6 and 8 .
Spindles 36 , 38 and bearings 44 have wheels 46 . Wheels 46 have surfaces 48 that diverge toward flange 50 . Bearing races 49 and 51 in the wheel 46 and on the spindles 36 , 38 have thrust and support surfaces.
At the inboard ends 52 , 54 a hydraulic ram 56 is attached to clevis and pin fittings 58 , 60 . Ram 56 provides the outward force necessary for the flange 50 of the wheel 46 to maintain contact with the head 19 of the tracks 16 . Shafts 32 , 34 are carried on ultra high molecular weight (UHMW) plastic slides 62 , 64 in housing 66 .
An improvement in this application, compared to U.S. Pat. No. 5,756,903 is in major measurement improvements enabled by new split axle shafts 232 , 234 , or 332 , 334 that incorporate force sensors positioned on the shafts.
As described in the aforementioned patent, distortion or variation in hydraulic pressure is directly measured by a linear transducer on the hydraulic line pressurizing ram 56 . Track strength is then calculated by comparing the measured pressure under a constant lateral load to an unloaded gauge measurement and a delta gauge or a rail movement is computed. Because this system measures fluid pressure, there is a slight time lag in obtaining reading, rendering it difficult to accurate log measurements. Certain inaccuracies in the system occur due to physical properties of hydraulic fluid and friction in the hydraulic system, which results in a greater deviation in the numbers calculated than desired.
In order to have a substantially constant load applied to the wheels 46 in the prior art systems, hydraulic pressure in the hydraulic ram 56 needs to be constantly adjusted. When a track weakness, caused by rail, tie or fastener failure, permits the wheels 46 to move, movement of the hydraulic piston in the hydraulic ram 56 causes the volume in the hydraulic system to increase, decreasing fluid pressure in the system. To compensate for movement of the piston of the hydraulic ram 56 , system hydraulic pressure is increased by the controls.
When the track returns to a gauge closer to the desired mean gauge in the specification, there is a consequent decrease in volume in the cylinder of the hydraulic ram 56 , increasing fluid pressure in the system. To compensate for movement of the piston of the hydraulic ram 56 , system pressure is reduced by the controls. Compensation in the system for fluxation in pressure creates a large disparity in the resultant measurements.
Because of the great deviation, caused by the fluxation in cylinder volume, railroads unnecessarily stop and physically inspect track that in fact is within specification, which reduces the efficiency of maintenance operations and increases maintenance costs. These plots of the open loop hydraulic system utilizing force measurements taken off of the hydraulic system are shown in FIG. 10 . The more accurate results of the improvement, described below, are shown in FIG. 11 .
The present disclosure addresses these undesirable traits by using direct mechanical measurement of changes in load or strain in split axle shafts 232 , 332 as shown in FIGS. 5-8 . The axle assembly measures changes in load or strain in each of the split axle shafts 232 , 332 . The axle assembly 20 applies a lateral load by use of hydraulic ram 56 and applies a vertical load with use of hydraulic cylinders 82 . The axle assembly 20 will be described regarding one side of the loaded gauge axle assembly 20 , it being understood the other side is a mirror image. Shaft 232 , of the first embodiment of the present disclosure, uses load cells 256 , 258 while shaft 332 , of the second embodiment of the present disclosure, uses strain sensors 356 , 358 . Either the strain sensors 356 , 358 or the load cells 256 , 258 provide essentially instantaneous measurement of changes in load on the split axle shafts 232 , 332 . The installation of force transducers, such as the load cells 256 , 258 in the cantilevered section of the split axle shafts 232 or 332 outside of the frictional elements of the axle assembly 20 subjects the load cells 256 , 258 to rail/wheel forces and not frictional forces created by the hydraulic ram 56 . The avoidance of frictional forces at the measurement point permits a more accurate detection of lateral weakness in the analyzed track.
Vertical and lateral forces placed upon the track are separately and independently, measured by the load cells 256 , 258 . The direct force vertical and lateral measurement in the non-rotating split axle shafts 232 is continuous along the running track. The orientation of the load cells 256 , 258 within each of the split axle shafts 232 determines whether the analog output load cells 256 will be lateral load output or vertical load output. The load cells 256 , 258 are designed so that the orientation of the load cell within an opening determines whether the forces measured are lateral or vertical. The load cells include alignment markings wherein the orientation of the markings dictates the type of force measured. Positioning the alignment markings in a vertical orientation allows the load cells to measure lateral force and positioning the alignment markings of the load cells forty five degrees from vertical permits the load cells to measure vertical force. While orienting load cells within the split axle shafts 232 in the described configuration is the preferred method of measuring forces in the split axle shafts 232 , other configurations of the load cells for measuring lateral and vertical forces may also be used to achieve the same result. Further, other possible force measuring devices that may be used to measure vertical and lateral forces within the split axle shafts 232 .
Split axle shaft 232 includes a spindle 36 at the outboard end 240 as shown in FIG. 8 . The spindle is adapted to accept bearings 44 and wheel 46 . Wheel 46 includes surfaces 37 that diverge toward a flange 50 . The wheel 46 and flange 50 are positioned on the head 19 of the rail 16 . Bearing races 49 and 51 in the wheel 46 and on the spindles 36 , 38 have thrust and support surfaces to prevent lateral and vertical play between the wheel 46 and the split axle shaft 232 . The use of bearings 44 permits the wheel 46 to rotate along the track while the split axle shaft 232 remains stationary. This is necessary so that the orientation of the load cells 256 , 258 remain constant.
At the inboard end 252 of each of the split axle shafts 232 the hydraulic ram 56 is attached by clevis and pin fittings 58 , 60 . The hydraulic ram 56 is expanded and contracted by varying pressure on both ends of the cylinder within the hydraulic ram 56 in response to signals from the load cells 256 , 258 . The hydraulic ram 56 is designed to pull and push the split axle shafts 232 so that a constant force is applied to the tracks. Using a closed loop system, as described below, a substantially constant lateral force and a substantially constant vertical force in an allowable range set by the FRA for GRMS measurement is applied to the tested track.
The split axle shafts 232 are located at opposite ends of the hydraulic ram 56 and are slidably disposed within a housing 66 , as shown in FIG. 13 . One skilled in the art will recognize that FIG. 13 is merely a clarification of the axle assembly 20 of FIGS. 3-8 . The housing 66 includes inner support channels 67 , wherein the inner support channels 67 slide with respect to the housing 66 . The inner support channels 67 are secured to the split axle shafts 232 . To permit movement of the inner support channels 67 with respect to the housing, ultra high molecular weight (UHMW) plastic slides 62 , 64 are used.
Spaced in from end 240 of the split axle shaft 232 is a load sensing region 242 , as shown in FIGS. 7 and 8 . In the first embodiment, utilizing load cells 256 , 258 , load sensing region 242 is machined or formed to define two opposed recesses 244 , 246 in side surfaces 247 of the split axle shafts 232 . The recesses 244 , 246 are vertically formed, so that the full height of split axle shaft 232 is intact, but the width is reduced by about sixty percent, each recess having a depth of about 30 percent, with the remaining solid portion forming a web 250 comprising about 40 percent of the width of split axle shaft 232 .
The web 250 , positioned between the recesses 244 , 246 , is itself bored to provide two apertures 252 , 254 to receive load cells 256 , 258 , for which the leads 260 are lead away from the apertures in groove 262 to protect the wiring for the load cells 256 , 258 as shown in FIG. 7 . During the application of lateral and vertical forces by hydraulic ram 56 and cylinders 82 , the apertures 252 , 254 slightly deform, exerting pressure on the load cells 256 , 258 . The force exerted on the load cells 256 , 258 is translated into analog signals that are transmitted to a signal conditioning amplifier.
The load cells 256 , 258 are tubular members that are adapted to measure force applied to their structure. The load cells 256 , 258 are designed so that their orientation within the apertures 252 , 254 determine whether the output for a given cell relates to vertical or lateral load. To measure lateral force on the split axle shaft 232 , the alignment markings of the load cell 256 are positioned in a vertical orientation within the aperture 252 . To measure vertical force on the split axle shaft 232 , the alignment markings of the load cell 258 are positioned forty five degrees from vertical. The load cells 256 , 258 continuously measure lateral and vertical force applied to the rails, the values of which are recorded. While orienting load cells within the split axle shafts 232 in the described orientation is the preferred method of measuring forces in the split axle shafts 232 , other configurations of the load cells for measuring lateral and vertical forces may also be used to achieve the same result.
In the second embodiment, using strain sensors 356 , 358 , shaft 332 includes a spindle 36 at the outboard end 340 of the split axle shaft 332 . At the inboard ends 352 the hydraulic ram 56 attaches to clevis and pin fittings 359 . Spaced in from end 340 is a load/strain region 342 . The load/strain region 342 is created by creating opposing recesses 343 within the split axle shaft 332 . Between the recesses 343 is a central web 345 . It is preferable that the central web portion 345 be approximately ½″ in thickness. In the second embodiment, the central web portion 345 of the load/strain region 342 is surface fitted with strain sensors 356 , 358 , which transmit strain information to the control system. The strain sensors 356 , 358 can be attached to the surface of the central web portion 345 with adhesive, fasteners or welding. The compression or shear deformation of the central web portion 345 is measured by the strain sensors, creating an analog signal sent to the signal conditioning amplifier. The strain information detected by the strain sensors 356 , 358 , permits the control system to monitor load force on the split axle shafts 332 and vary hydraulic pressure within the hydraulic ram 56 to compensate for movement in the track.
Due to the unique advantages of the non-rotating split axle embodiment taught herein and in U.S. Pat. No. 5,756,903, either load sensors 256 , 258 or strain sensors 356 , 358 can be used to directly measure load/strain on the axle, in a selected direction. Competitive track strength testing vehicles with rotating axles cannot be easily adapted to use of load/strain measurements because of the difficulty of identifying the direction of load/strain as the axle rotates. The direct force measurement in the non-rotating axle shaft 332 is continuous along the running rail.
The lateral and vertical force control of the gauge restraint measurement system is a closed-loop control system that is capable of making continuous changes in force exerted by the hydraulic ram 56 in response to force readings provided by the load cells 256 , 258 . This arrangement ensures that a constant force is continuously applied to the track as the gauge restraint measurement system is rolling down the railway at speeds varying from 5 mph to 35 mph. It is essential to apply a constant lateral and vertical force upon the tracks even while the tracks are moving in response to the force so that an accurate and consistent measurement of variations in gauge, hence lateral strength of the track can be measured to show the extent of lateral weakness of the track. As the test vehicle encounters a laterally weak section in the track, the track moves in response to the forces, decreasing the load on the load cells. In response to the decrease in force, the hydraulic ram 56 expands increasing the force on the track until the desired force is achieved. Without the increase in force, accurate track gauge measurements could not be made.
The closed loop hydraulic control system is designed to maintain a constant rail/wheel lateral force. This is accomplished by use of a hydraulic servo-valve controlled by force feedback provided by force transducers, load cells 256 , 258 , in the extremity of the split axle shaft 232 , closest to the wheel. Using the closed loop system, pressure on the rail does not drop with movement of the track. To maintain constant pressure on the tracks, the hydraulic servo-valve is used to rapidly increase pressure on either side of the hydraulic ram 56 . In the preferred embodiment a Moog 72 - 102 servo valve is used to supply pressurized fluid to either end of the hydraulic ram 56 . The servo-valve includes a first hydraulic line that connects to a first end of the hydraulic ram 56 , and when pressurized, causes the ends of the hydraulic ram 56 to move outward exerting additional pressure on the split axle shafts 232 . Pressurizing the first hydraulic line, causes the extension of the hydraulic ram 56 and the extension of the overall length of the axle assembly 20 , which compensates for outward movement of the track. The servo-valve also includes a second hydraulic line that connects to a second end of the hydraulic ram 56 , and when pressurized, causes the ends of the hydraulic ram 56 to pull inward, decreasing pressure on the split axle shafts 232 . Pressurizing the second hydraulic line causes the retraction of the hydraulic ram 56 and an overall decrease in the length of the axle assembly 20 to compensate for lack of track movement, i.e. standard track gauge within specifications.
The servo-valve is controlled by the system computer in response to signals received from the load cells 256 , 258 . If the load cells 256 , 258 send a signal showing a drop in force on the track, due to track lateral weakness, the computer sends an analog signal to the servo-valve to increase hydraulic pressure in the first end of the hydraulic ram 56 , maintaining constant force on the split axle shafts 232 and expansion of the overall length of the axle assembly 20 . If the load cells 256 , 258 send a signal showing an increase in force on the track, due to the transitioning from a weak section of track to a strong section of track, the computer sends an analog signal to the servo-valve to increase hydraulic pressure in the second end of the hydraulic ram 56 , maintaining a constant force on the split axle shafts 232 , reducing the overall length of the axle assembly 20 . The closed loop force control system has a fast response time that effectively reacts to changes in track conditions. The closed loop system pushes the split axle shafts 232 outward and pulls the split axle shafts 232 inward to create a uniform load on the track. This arrangement creates a highly constant force on the track, permitting highly accurate track strength measurements.
To measure physical changes in distances between the rails of the track being tested in the preferred embodiment, a laser measurement system is used. While a laser measurement system is utilized, other means for measuring may also be incorporated such as mechanical means. The front of the track strength testing vehicle is equipped with an inspection camera and laser measurement device to measure unloaded gauge. The laser measurement device at the front of the vehicle takes a pre-force distance measurement of the track in an unstressed state. The measurement data is sent to and recorded by the system computer. A second inspection camera and laser measurement device is mounted under the vehicle adjacent to the load axle 20 , and is adapted to measure the distance between the rails of the track being tested under load. The values collected by the second laser measurement device are recorded by the system computer. The computer compares the differences between the first and second measurements and records the difference. The difference in the track gauge between a loaded and unloaded state in combination with the associated forces is used to determine whether a section of track is in need of repair.
The direct measurement of load/strain on the split axle shafts 232 themselves enables the track strength testing vehicle to acquire and store load axle force data and provide a graphical display that is used for the evaluation of the gauge restraint measurement system GRMS load axle performance during revenue service. In addition to the features described in U.S. Pat. No. 5,756,903 and the improvements described above, this improvement utilizes a computer used for the load cell calculations, including signal amplification and A/D cards.
Lateral and vertical load values are calculated by the load cell computer from input from the load cells 256 , 258 . The load cell computer used for the load cell calculations uses converter boards to convert amplified and conditioned analog signals developed by the load cell circuitry to digital values (A/D converter boards). The signal conditioner boosts the analog signal from the load cells 256 , 258 . The A/D boards covert the amplified analog signal to a digital signal. The A/D converter board values can be used for force calculation purposes. The calculated lateral and vertical load values are used as digital inputs to the program.
The three cameras used in the system have one camera positioned to send video of the track directly ahead of the track strength testing vehicle. This video is used to correlate track conditions with graphical results produced by the program. The video also allows for custom graph production during playback mode. The two other cameras used in the system send video that allows monitoring load axle wheel performance in a loaded and unloaded state and the lateral and vertical position of the load axle with respect to the vehicle. An illustration of the display 400 , is shown in FIG. 9 .
Camera graphics show the left wheel, 402 , right wheel 404 and outside environment 406 . Data plots on the left, drivers side, 408 and right side 410 show the progression of data collection and plot points in a ‘scatter plot’ form relative to statistical envelopes 412 , 414 . Corresponding histograms 416 , 418 provide a different statistical view of the data points. Finally, in the preferred embodiment, an array 420 of computer control ‘buttons’ is in the lower center of the display 400 .
Typical computer controls will be used to operate the system, including start, reset, pause and resume functions, in addition to various data field entry. The controls are used for such functions as skipping curves, switches, frogs, constructing custom graphs to show tangent behavior only or curve behavior only.
A primary function of the system is that of graph-building and retaining accumulated graphed data, correlated to the odometer and track location video. The graphs plot data points for left and right rails, displaying the data points as accumulated plots with applied vertical force on the “y” axis and applied horizontal force on the “x” axis. Also displayed are the limits of permissible deviation of the “x” and “y” values from an ‘envelope’ of acceptable force. The general display is shown in FIG. 9 , while a comparison of data plots in the prior art loaded gauge axle track strength apparatus compared to the improvement, both using the computer monitoring system described above, are shown in FIG. 10 and FIG. 11 , respectively.
The system allows the operator to view a two-dimensional graph of lateral and vertical forces displayed on a computer monitor. A two-dimensional scatter-graph is displayed for each wheel showing a dot for each foot of travel along the running rail. Dots are positioned on the graph with later position relative to the horizontal scale and vertical position relative to the vertical scale calibrated in kips (thousands of pounds). A third dimension is added by color graduation of the scatter-graph according to frequency of occurrence. Thus, the graphical display showing a degree of force control effectiveness is made available to the operator (and customer). The resulting display is not unlike a weather-radar image that illustrates different colors for variations in rain density/intensity. Graphical force distribution information is made available to the operator so that he can monitor control system performance. By visually monitoring the force distribution scatter-graph, the operator can detect control system degradation over time and take corrective action. Pattern recognition enables an operator to identify a developing problem at the component level, which greatly enhancing the maintainability of the system and the availability of the system to produce revenue, resulting in significant economic benefit for the operator and better service to the customer.
Experimentation has shown the interrelation between the load/strain sensor arrangement and the plots described above. With the prior art hydraulic pressure sensing surrogate for the mechanical properties, points were more frequently outside the permissible ‘envelope’ as shown in FIG. 10 . This plot is created using an open loop force control apparatus, and it is for this reason it is designated as “Prior Art.” In fact, however, the display apparatus is that of the improvement as to display and calculations discussed herein. Using the closed loop control system, greater precision and fewer false indications of inadequate strength are received. This is shown in FIG. 11 . It will be observed that the data points plotted 422 using the open loop system covers a much larger area of the graph than plot 424 , using the closed loop system.
The track strength measurement system can be quickly calibrated without the need to send the system to an independent laboratory that could take a measurement vehicle offline for several weeks, causing loss in revenue. Accordingly, an additional feature of the track strength measurement system is the Load Axle Calibration Subsystem, hereafter sometimes abbreviated “LACS”.
The purpose of the LACS application is to automatically increment vertical and lateral hydraulic pressures in a planned sequence while simultaneously acquiring load axle load cell force data and comparing to permanently installed NIST traceable transfer standard load cells 460 , 462 , hereinafter referred to as transfer standard cells, in order to generate correction constants for the load cell correction application as a field calibration procedure, as shown in FIGS. 3 and 4 . This self-contained system directly compares the transfer standard cells 460 , 462 with the force measurement signals generated by the internal load-axle load cells and establishes a linear mathematical relationship that is stored in the measurement system computer. The system utilizes the transfer standard cells 460 , 462 that independently measure the force applied to the wheels 46 by the hydraulic cylinders 82 . The transfer standard cells 460 , 462 can be removed from the vehicle and sent to a testing center to ensure their accuracy. A spare set of transfer standard cells 460 , 462 can be retained so that the vehicle is not out of service. Typically the transfer standard cells 460 , 462 need to be calibrated once a year to ensure accuracy.
The entire calibration procedure of the load axle 20 takes approximately 10-15 minutes. The application automatically installs calibration constants for the load cell correction application and prints a calibration report for distribution to the customer.
The LACS system utilizes vertical polyester web straps 450 , 452 to support wheels 46 and a lateral polyester web strap 454 to restrict lateral movement of the wheels 46 as shown in FIGS. 3 and 4 . While polyester web straps are preferred, other types of material and harnesses may be used to restrict vertical and lateral movement. A centering device is incorporated on top of the load axle 20 during calibration to center the axle ensuring vertical loading. Vertical loads are sensed by transfer standard cells 460 , 462 and lateral loads are sensed by transfer standard cell 464 . The vertical load cells 256 are tested by use of transfer standard cells 460 , 462 . The calibration procedure can be performed in a hotel parking lot prior to starting the track testing work day.
To calibrate the system, the operator places the vertical polyester web straps 450 , 452 over the wheels 46 and connects the ends of the polyester web straps 450 , 452 to a transfer standard cell support bracket 463 . A separate support bracket 456 is directly connected to a first end of each of the transfer standard cells 460 , 462 . The transfer standard cells 460 , 462 are connected to the vehicle at a second end. Once the polyester web straps 450 , 452 are in position around the wheels 46 , the hydraulic cylinders 82 are expanded incrementally to test vertical load cells 256 . The hydraulic cylinders 82 are moved downward with ten increments of increasing force. The test begins with a load of 2,000 lbs vertical force applied to the split axle shafts 232 and moves upward in ten equal increments until 15,000 lbs of vertical force is achieved. The vertical force values detected by the transfer standard cells 460 , 462 are compared to the vertical force values detected by the load cells 256 . If the vertical force measured from the load cells 256 varies from the vertical force measured by the transfer standard cells 460 , 462 , the load cells 256 are recalibrated to match the values of the transfer standard cells 460 , 462 .
To calibrate lateral load force, a polyester web strap 454 is attached to the wheels 46 by use of brackets to restrict lateral movement of the wheels. The transfer standard cell 464 is fitted to the lateral polyester web strap 454 so that an independent lateral load can be detected. Once the lateral polyester web strap 454 and transfer standard cell 464 are in position, the hydraulic ram 56 is expanded in 10 equal increments from 2,000 lbs to 9,000 lbs so that test values can be gathered. The lateral force values measured by the transfer standard cell 464 are compared to the lateral force values measured by the load cells 258 . The analog signal from the load cells 258 are assigned a numerical force value, which is compared to the output reading of the transfer standard cell 454 . If the lateral force value gathered from the load cells 258 varies from the lateral force output reading of the transfer standard cell 454 , the values assigned to the output of the load cells 258 are recalibrated to match the load values of the lateral strains sensor 454 . The NIST transfer standard cells 460 , 462 , 464 are calibrated annually to maintain traceability for GRMS system calibration and performance.
Calibration files are retained and used to maintain a historical statistical quality assurance graph for the detection of gradual or abrupt system changes. The statistical quality assurance graph is used as a maintenance and monitoring tool by both field crew and engineering staff as a maintenance and design decision making tool.
In the preferred embodiment, the calibration subsystem uses a cPCI QNX processor and cPCI analog/digital A/D converter in 3U Eurocard chassis. This will be operatively connected to a server used for the host program including A/D cards and D/A cards. Measurements are provided by transfer standard cells from Sensotec model AL416EL or similar from Omega Engineering.
The LACS hardware 500 to support the transfer standard cells 460 , 462 , 464 will be mounted beneath the truck body above the load axle wheels as shown in FIGS. 3 and 4 . Signal conditioning will be used for the three tertiary standard load transducers to amplify the analog signals from the load transducers.
Lateral 502 , and vertical force values 504 , 506 , from transfer standard cells 460 , 462 , 464 are fed from the three signal conditioner amplifiers 508 , 510 and 512 into three available channels of the LC computer A/D card as shown in FIG. 12 . The cPCI computer 514 used for the load cell calculations uses an A/D converter to convert analog signals developed by the axle load cell circuitry to digital values that can be used for force calculation purposes. These raw lateral and vertical force values are fed through the signal conditioner 516 and then directly through the load cell computer 514 as uncorrected values and used as digital inputs to the calibration program running on the host computer.
As the calibration operation is performed, progress of the test procedure, verification of performance within specifications or failure, and documentation of identification, time, specification and reporting of same will be displayed and provided.
Various features of the disclosure have been shown and described in connection with the illustrated embodiment, however, it is understood that these arrangements merely illustrate, and that the disclosure is to be given its fullest interpretation.
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A direct measuring loaded gage axle assembly that measures track strength by directly measuring constant load on split axles as vertical loads are imposed by a hydraulic ram, and horizontal loads being supplied by horizontal rams through split axles and steel wheels to the railroad tracks enabling improved calibration to measure changes in track gauge indicating track strength condition and further including electronic data recording and comparison.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a divisional application of U.S. patent application Ser. No. 14/731,616 filed on Jun. 5, 2015 (which application claims the priority, under 35 U.S.C. .sctn.119, of U.S. Provisional Patent Application Ser. No. 62/008,260 filed on Jun. 5, 2014), the entire disclosures of which are hereby incorporated herein by reference in their entirety.
BACKGROUND
Firearm silencers are well known in the art of weaponry, and a variety of construction methods and materials have been proposed for minimizing the noise associated with expanding gases created or produced from the firing of a weapon. Sound energy is produced when the propellant in a cartridge (or shell) is ignited to force the bullet or shotgun projectile down the muzzle of a firearm. Silencers (also known as suppressors) for firearms operate on the principles of converting a portion of this sound energy into heat energy by diverting or trapping the pressurized gas in chambers within the silencer body. The pressurized gas is forced to expand into the spaces within the silencer, thereby decreasing the pressure, velocity and temperature of the gases prior to their release into the atmosphere or external environment.
A major advantage of using a silencer is hearing protection for the firearm user and bystanders. This is especially important in a home defense situation where the confined walls reflect sounds and resulting hearing damage can be more pronounced. In addition, the use of a silencer helps to conceal the location of a firearm, which may be useful in military, police, and sporting, hunting, and/or other shooting situations. The delayed-release of the propellant gases may also reduce the recoil of the firearm and even increase the precision of a rifle by the redirection of the exhaust gases to offset muzzle flip.
The result is that a firearm silencer can absorb and reduce the audible frequencies, vibrations, and contain or reduce muzzle flash resulting from the rapid expansion of gases leaving a firearm muzzle as a projectile exits the gun bore. However, for silencers to effectively contain and subsequently divert expanding gases and other combustion by-products emitted from the muzzle of a firearm, the silencer (suppressor) may require excessively large (volume) and cumbersome cylinders or tubes, especially with higher caliber firearms.
Therefore, in order to effectively suppress the sound of a firearm, a silencer (or suppressor) must have an internal volume large enough to capture gases emitted from the firearm before releasing the cooled gases to the atmosphere. The larger the internal volume of the silencer, the greater amount of sound can be suppressed, and so it is desirable to increase the size of the silencer for effective sound suppression. However, to achieve this, with conventional concentric, cylindrical suppressors having a desired internal volume, the outer diameter of the suppressor becomes too large and the suppressor can interfere with sight lines of the firearm. Additionally, with conventional concentric, cylindrical suppressors having a smaller outer diameter tube would then result in a longer silencer which impacts the overall length of the firearm.
Current gun silencers use a fixed length chamber to suppress the sound of a projectile as said projectile exits a gun barrel. The elements in the chamber are stationary and function to channel, absorb, or delay sound waves through the fixed chamber; hence the overall length of the silencer is fixed and can be too long, thereby impacting the overall length of the firearm. In view of the preceding, there is a need for a firearm silencer or sound suppressor having an effective internal volume that does not burden the firearm by adding unnecessary length to the barrel of the gun.
Therefore, a need exists to overcome the problems with the prior art as discussed above.
SUMMARY OF THE INVENTION
The present invention is a silencer (or suppressor) for a firearm which is intended for reducing the sound and flash signature of the host firearm. The invention overcomes the above-noted and other deficiencies of the prior art by providing a firearm silencer and methods for manufacturing and fastening a silencer onto a firearm that has a very compact reduced form factor (or length) which has significant benefit to the operability and maneuverability of the firearm.
This silencer (or suppressor) can be mass-produced and, therefore, lowers costs dramatically while still providing a design which is compact space-saving and achieves a level of sound suppression comparable to prior art larger silencers.
The invention creates the novel silencer with a minimum of three parts or chambers longitudinal to the firearm through which a projectile travels in a concentric manner through the silencer along a center line bore. The first chamber comprises a cylindrical housing, a mount, with means for attachment of a firearm barrel to the proximal end of the cylindrical housing, the silencer being mounted (or securely affixed) to the barrel of the firearm. This attachment to the barrel can be done with a standard screw mount or a quick detach method (such as a three lug twist connect method) which would maintain the alignment of the bore of the firearm to the through hole passage of the silencer.
This first chamber has an inner tube along a centerline bore through which the projectile passes through to the second chamber, the distal end of first chamber has a boundary surface which has holes for gases from the second chamber to be vented rearward back through the first chamber. The first chamber has a baffle chamber that can be filled with gas porting baffles or sound absorbing materials.
The proximal end of the second chamber is connected to the distal end of the first chamber with a boundary that has holes for venting gases from the barrel of the firearm rearward through the first chamber. The second chamber houses a third chamber which is partially (or fully) retracted into the second chamber by a concentric spring.
The third chamber is a cylindrical housing concentric and smaller in diameter to the second chamber thereby allowing the third chamber to expand or retract back into the second chamber in a piston action. The third chamber is partially or can be fully held in a retracted position inside the second chamber by a spring in a concentric shape between the boundary of the second and third chamber. The third chamber has an inner tube which is in line with the barrel of the firearm and acts as a through bore for the projectile to pass from the firearm barrel through the second and third chamber and is also in line with the through bore of the first chamber. The third chamber inner tube is perforated or has vent holes to allow gases to vent from the inner tube to the outer chamber.
When a projectile (such as a bullet or shotgun shell) is fired from a gun, the projectile exits the barrel of the firearm and enters the proximal end of first chamber. Since the first chamber inner tube has no perforations or vent holes, the projectile and the gases pass through and exit the distal end of the first chamber and into the proximal end of the second chamber. The projectile passes through the second and third chamber along the third chamber inner tube and exits the silencer at the distal end of the third chamber. Moreover, when the gases following the projectile enter the second chamber along the inner tube of the third chamber, the gases quickly vent out through the holes of the inner tube the large cavity of the second and third chamber. The pressure of these gases then expand and causes the third chamber to expand distally outward like a piston from the second chamber and in line with the projectile, greatly increasing the volume to contain the exhausted gases and maintaining control of the timing, flow, and direction of these gases on how then vent to the outside.
The expanding gas then pushes the retracted third chamber longitudinally outward, distally away from the barrel of the firearm like a piston, thereby expanding the combined volume of the combine second and third chambers. Then the portion of emitted gas caught in the expanded second and third chamber is re-directed to flows rearwards (proximally to the barrel) towards the first chamber. The first chamber is proximal to the second and third chamber with through-hole openings formed in the end cap between the two chambers. This gas flow pathway traveling rearward (proximally to the barrel) of the claimed silencer device allows the gases discharged from the barrel of the firearm to exit into the atmosphere in a controlled manner which reduces heat, sound, and flash of the projectile. As the gases are vented backward, the third chamber begins to retract back into the second chamber by the compression spring.
This piston action by the silencer allows the device to maintain a very compact form factor (length) on the firearm for the vast majority of the time. When a projectile is fired, the silencer momentarily expands the third chamber to accommodate the gases in a controlled manner, and then retract back to a compact length. This allows the silencer to be manufactured and mounted onto a firearm in an extremely compact form factor and still performs the sound suppression function similar to that of a much larger comparable device.
These, and possibly other defects of the previously known silencers, are remedied by the present silencer, which is characterized by three or more separate chambers being formed longitudinally in the silencer, the silencer being mounted (or securely affixed) to the barrel of the firearm.
Although the invention is illustrated and described herein as embodied in a firearm silencer and methods for manufacturing and fastening a silencer onto a firearm, it is, however, not intended to be limited to the details shown because various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims. Additionally, well-known elements of exemplary embodiments of the invention will not be described in detail or will be omitted so as not to obscure the relevant details of the invention.
Other features that are considered as characteristic for the invention are set forth in the appended claims. As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one of ordinary skill in the art to variously employ the present invention in virtually any appropriately detailed structure. Further, the terms and phrases used herein are not intended to be limiting; but rather, to provide an understandable description of the invention. While the specification concludes with claims defining the features of the invention that are regarded as novel, it is believed that the invention will be better understood from a consideration of the following description in conjunction with the drawing figures, in which like reference numerals are carried forward. The figures of the drawings are not drawn to scale. Further, it is noted that the figures have been created using a computer-aided design computer program. This program at times removes certain structural lines and/or surfaces when switching from a shaded or colored view to a wireframe view. Accordingly, the drawings should be treated as approximations and be used as illustrative of the features of the present invention.
Before the present invention is disclosed and described, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. The terms “a” or “an”, as used herein, are defined as one or more than one. The term “plurality,” as used herein, is defined as two or more than two. The term “another,” as used herein, is defined as at least a second or more. The terms “including” and/or “having,” as used herein, are defined as comprising (i.e., open language). The term “coupled,” as used herein, is defined as connected, although not necessarily directly, and not necessarily mechanically. As used herein, the term “about” or “approximately” applies to all numeric values, whether or not explicitly indicated. These terms generally refer to a range of numbers that one of skill in the art would consider equivalent to the recited values (i.e., having the same function or result). In many instances these terms may include numbers that are rounded to the nearest significant figure.
In this document, the term “longitudinal” should be understood to mean in a direction corresponding to an elongated direction of the silencer or firearm. The term “distal” end should be understood to mean the section farthest from the barrel of the firearm. The term “proximal” end should be understood to mean the section closest to the barrel of the firearm.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying figures, where like reference numerals refer to identical or functionally similar elements throughout the separate views, which are not true to scale, and which, together with the detailed description below, are incorporated in and form part of the specification, serve to further illustrate various embodiments and to explain various principles and advantages all in accordance with the present invention.
FIG. 1 shows block diagrams illustrating the major functional blocks and their relative position of a firearm and the Silencer (Suppressor) Apparatus.
FIG. 2 shows block diagrams illustrating the major functional blocks of the Compact Space-saving Silencer (Suppressor) in the retracted compact position.
FIG. 3 shows block diagrams illustrating the major functional blocks of the Compact Space-saving Silencer (Suppressor) in the extended position.
FIG. 4 shows block diagrams illustrating the major functional blocks of the Compact Space-saving Silencer (Suppressor) in an alternate embodiment with the first chamber along-side chamber 2 in the extended position.
DETAILED DESCRIPTION
Herein various embodiment of the present invention are described. In many of the different embodiments, features are similar. Therefore, to avoid redundancy, repetitive description of these similar features may not be made in some circumstances. Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention. It shall be understood, however, that description of a first-appearing feature applies to the later described similar feature and each respective description, therefore, is to be incorporated therein without such repetition.
A silencer or noise suppressor for a firearm utilizing concepts of the invention is illustrated in FIG. 1 . The silencer ( 102 ) can include a cylindrical body having a cylindrical bore proximally attached to the barrel ( 103 ) of a firearm ( 101 ) axially extending to the distal end of the silencer where a projectile ( 104 ) would exit the silencer. The silencer ( 102 ) bore is sized to allow connection to a firearm and to permit passage of a projectile. The silencer ( 102 ) can be threaded for at least a portion of its length and can be attachable with a standard threaded screw mount or a quick detach method (such as a three lug twist connect method) or other commonly used mechanical attachment methods which maintain the common bore line ( 105 ) [or center line] of the barrel ( 103 ) to the silencer assembly, thereby rendering the silencer ( 102 ) selectively installable and removable from the weapon or firearm. A firearm barrel ( 103 ) is the portion of a firearm or weapon that directs a fired projectile and the muzzle is the end portion of the barrel. The terms weapon, gun, shotgun, and firearm will be used interchangeably herein.
The silencer ( 102 ) according to the present invention is preferably made of aluminum; however other suitable material such as titanium, other metal or alloy, synthetic material etc. can be used for the manufacture of this silencer. Sound absorbing materials can include aluminum chips, steel mesh or steel wool, or other suitable silencing material. Baffles can include one or more metal or plastic or composite baffles having conical sections and ports and other structures designed to direct and/or port gases, by-products of combustion and sound energy in such a fashion as to reduce the sound energy and muzzle flash emitted from the silencer in conjunction with the firing of a projectile.
More specifically, FIG. 2 is a sectional view of one embodiment of the gun silencer ( 205 ) in a retracted state. The silencer (suppressor) is made of at least three chambers including a first chamber ( 210 ), a second chamber ( 220 ), and a third chamber ( 230 ) partially retracted into the second chamber ( 220 ).
In one embodiment, the cylindrical shaped first chamber ( 210 ) includes a threaded end cap ( 211 ) configured to be secured to threads ( 212 ) on a barrel of a firearm ( 240 ). The threaded end cap ( 211 ) is one embodiment that may be employed for the securement of silencer apparatus to the barrel of the firearm, other methods may include quick disconnect methods such as a three lug mount or any other known method that would maintain the alignment and bore of the firearm to the silencer and maintain a straight through hole path for the projectile. As shown, the threaded end cap ( 211 ) has an annular aperture ( 218 ) that allows a projectile to freely pass through the first chamber. The first end cap ( 211 ) is proximal to the barrel and the second end cap ( 214 ) is distal to the barrel. The first chamber has a solid inner tube ( 217 ) with openings ( 218 ) on the distal and proximal ends of the first chamber at endcaps ( 211 & 214 ). The projectile and the gases are flowed outward from the barrel ( 240 ) though the first chamber ( 210 ) and into the second chamber ( 220 ) and third chamber ( 230 ). The size of the aperture opening ( 218 ) is configured with a diameter that is the same or greater than the diameter of a projectile and would allow for unrestricted passage and exit from the barrel of the firearm through the claimed silencer apparatus. Accordingly, the threaded end cap ( 211 ) is configured to securely attach to the barrel of the firearm ( 240 ) and sized to receive a projectile exiting the barrel.
Several features have been designed into the first chamber to reduce the noise of a firearm discharge. The discharging firearm with projectile and expanding gases are passed from the first chamber ( 210 ) into the second chamber ( 220 ) and through the third chamber ( 230 ) to the distal end of the silencer ( 205 ) along the bore line.
When a projectile (such as a bullet or shotgun shell) is fired from a gun, the projectile exits the barrel of the firearm ( 240 ) and enters the proximal end of first chamber through the first end cap ( 211 ). Since the first chamber inner tube ( 217 ) has no perforations or vent holes, the projectile and the gases pass through and exit the distal end of the first chamber through second end cap ( 214 ) and into the proximal end of the second chamber ( 220 ). The projectile passes through the second and third chamber along the third chamber inner tube ( 235 ) and exits the silencer at the distal end of the third chamber through third end cap ( 233 ). Moreover, when the gases following the projectile enter the second chamber along the inner tube of the third chamber ( 235 ) which is perforated with vent holes, the gases quickly vent out into the large cavity of the second and third chamber. The pressure of these gases then expand and causes the third chamber ( 230 ) to expand distally outward like a piston from the second chamber ( 220 ) and in line with the projectile, greatly increasing the volume which functions to contain the exhausted gases and maintaining control of the timing, flow, and direction of these gases on how they vent to the outside.
One element of sound reduction in the first chamber ( 210 ) is that the expanding gases captured by the second chamber ( 220 ) and third chamber ( 230 ) are redirected rearward to the first chamber ( 210 ) through vents ( 215 ) in the second end cap ( 214 ). This redirection more effectively utilizes the noise suppressor's internal volume of the first chamber ( 210 ) thereby providing more time for the gases to cool. Another element of sound reduction for the first chamber is that the internal volume of the first chamber ( 213 ) can be empty or filled with sound absorbing materials or sound baffles. Turbulence is created by this venting of gases through the first chamber (with either empty, sound absorbing materials or baffles), allowing the associated gases more time to cool and expand thereby reducing the sound and flash signature of the host firearm. Another element of sound reduction is the gases can be vented in multiple directions such as through vent holes ( 216 ) at the first end cap ( 211 ) or can be upward or downward through side vent holes ( 219 ). The choice of selecting an upward venting of gas can be used to offset muzzle flip of the barrel as the projectile is fired. A downward direction of the gases could be used to better conceal the sound and location of the firearm.
The second chamber ( 220 ) has a cylindrical shape of same diameter to the first chamber ( 210 ) and is connected to the end cap ( 214 ) on the proximal end and has an opening on the distal end flanges ( 222 ) or ridge edge concentric to accommodate the third chamber ( 230 ) which can expand or contract longitudinally into the second chamber ( 220 ). The second cylinder has a concentric spring ( 224 ) which compresses the third chamber ( 230 ) into the second chamber ( 220 ). The spring ( 224 ) concentric with the second chamber ( 220 ) and third chamber ( 230 ) utilizes the end flanges of the second chamber ( 222 ) and end flanges or ridges of the third chamber ( 231 ) to hold the chambers in a normally retracted position. The second chamber ( 220 ) has a concentric alignment guide ring ( 221 ) mounted on the end cap ( 214 ) with the bore which will be further discussed for the functions involving the third chamber ( 230 ).
The third chamber ( 230 ) has a cylindrical shape concentric to the second chamber ( 220 ) and smaller in diameter such that the third chamber ( 230 ) can retract partially or wholly into the second chamber ( 220 ). The proximal end of the third chamber ( 230 ) contains an end flange or ridge ( 231 ) which extends radially outward from the cylinder body ( 232 ) and fits into the inside diameter of the second chamber ( 220 ), this end flange or ridge contacts the concentric spring ( 224 ). The distal end of the third chamber ( 230 ) has a third end cap ( 233 ) which has an opening ( 234 ) concentric with the bore and is large enough to allow the passage of the projectile from the firearm to pass through. The third chamber ( 235 ) has an inner tube ( 235 ) concentric with the bore and wide enough to allow the passage of a projectile to pass through freely. The inner tube ( 235 ) can be partially or fully vented with holes ( 236 ) extending radially away from the bore and allows gases to vent from the inner tube ( 235 ) to the outer section of the third chamber ( 230 ). The internal volume of the third chamber ( 237 ) can be empty or filled with sound absorbing materials or sound baffles. Turbulence is created by this venting of gases through sound absorbing materials or baffles, allowing the associated gases more time to cool and expand thereby reducing the sound and flash signature of the host firearm.
The second chamber ( 220 ) with a distal second end cap ( 214 ) has an alignment guide ring ( 221 ) which holds the third chamber inner tube ( 235 ) in line with the bore in the retracted position. This allows for an accurate alignment of the various elements of the silencer to the bore line and ensures the projectile will pass through these elements freely.
Regarding FIG. 2 , if in the retracted state, the third chamber ( 230 ) can be designed to be fully retracted into the second chamber ( 220 ). Then the length (L 3 ) of the third chamber is smaller than the length of the second chamber (L 2 ) and hence the extension length (L 5 ) would be zero.
If in the retracted state, the third chamber ( 230 ) is designed not to fully retract into the second chamber ( 220 ), then the length (L 3 ) of the third chamber is larger than the length of the second chamber (L 2 ) and the extension length (L 5 ) would be the amount that the third chamber ( 230 ) extends beyond the second chamber ( 220 ).
Regarding FIG. 3 , illustrates the novel silencer as shown in FIG. 2 in an expanded state. The expanding gases and projectile from the firearm causes the third chamber ( 330 ) to extend distally outward longitudinally along the bore axis. This extension allows the silencer ( 305 ) to accommodate the expanding gases in a controlled manner through the actions of the second chamber ( 320 ) and third chamber ( 330 ) and redirect these gases rearward back towards the first chamber ( 310 ). In the extended state, the third chamber ( 330 ) can be extended from the second chamber ( 320 ). The length (L 3 ) is the length of the third chamber and (L 4 ) is the length of the third chamber recessed inside the second chamber ( 320 ) and (L 5 ) is the length of the third chamber ( 330 ) extended beyond the second chamber ( 320 ). The concentric spring ( 324 ) is shown in the compressed state and would apply pressure to retract the third chamber ( 330 ) as the gases pass rearward through to the first chamber ( 310 ). The gases trapped in the third chamber then can flow rearward through the distal end cap ( 314 ) with ports ( 315 ) radially along the end cap, then passes though the first chamber ( 310 ) and exits to the atmosphere through ports ( 316 ) on the distal end cap ( 311 ) or out the sides through holes ( 319 ).
The amount of volume expansion possible from the expanding third chamber relative to the second chamber in the case of a cylinder shape can be expressed approximately by the following formulas
Volume of the Second Chamber [ VS 1]=(3.14)×(Radius of Second Chamber^2)× L 2
Volume of Third Chamber extending outward [ VT 1]=(3.14)×(Radius of Third Chamber^2)×[ L 5 in FIG. 3]
One Ratio of expansion can be expressed as [ VS 1+ VT 1]/[ VS 1]
There are other factors such as the area of the compression spring ( 324 ) and area of the materials from the second inner tube ( 335 ) that may be subtracted for a more exact ratio, but the benefits can be generally derived with the formula above.
Empirical data shows that meaningful expansion benefits can occur at ratios of 130% with greater benefit occurring at 150%-175%, up to a theoretical limit approaching 200%. This novel invention structure indicates that the greater the volume expansion, the better the sound suppression with having a retractable chamber for space-saving benefits.
In the preferred embodiment, the elements of the silencer ( 305 ) are designed with inner tube elements ( 317 ), ( 321 ), and ( 335 ) with openings that are slightly larger than the projectile width. This allows the projectile to pass untouched as it travels from the barrel of the gun ( 340 ) through the silencer ( 305 ).
If a tighter aperture is desired to seal as much of the gases into the silencer, a washer-like “wipers” which have a central hole for passage of the projectile that has a slightly smaller diameter than the actual diameter of the projectile can be used at the last proximal point of the silencer on the third end cap location hole ( 334 ). This arrangement provides momentary gas sealing during the passage of the projectile through the series of wipers and chambers. The wipers are typically made of softer materials such as rubber so after several rounds are fired through the wipers; the hole is resized to barely touch the projectile but provide for a closer fit that can be achieved safely from a metal aperture.
In a second embodiment, the silencer ( 305 ) can be used to silence or suppress a shotgun that uses a cup and wad assembly for the shotgun shell. If a shotgun utilizes such a wad and cup ammunition, the silencer ( 305 ) apparatus can be used to silence or suppress the sound of the projectile. The overall structure as detailed for the silencer ( 305 ) in the first embodiment is used along with the following changes. The inside diameter of the first chamber end cap opening ( 318 ), inner tube ( 317 ), alignment guide ring ( 321 ) and third chamber inner tube ( 335 ) and hole ( 334 ) has substantially and very closely manufactured to be the same inside diameter as the barrel ( 340 ) of the shotgun. This would allow an uninterrupted path of uniform diameter for the shotgun shell with the wad, cup, and shot configuration to pass through the barrel of the gun ( 340 ) and the silencer ( 305 ) freely. The uninterrupted and uniform diameter of the barrel with the silencer allows the shotgun shell to maintain its flight [and pellet] configuration until it exits the silencer ( 305 ).
Regarding FIG. 4 , in a third embodiment, the overall structure as detailed for the silencer ( 305 ) in the first embodiment is used along with the following changes for the third embodiment. The second chamber ( 420 ) is of cylindrical shape includes a threaded end cap ( 411 ) configured to be secured to threads ( 412 ) of a barrel of a firearm ( 440 ). The threaded end cap ( 411 ) may be employed for the securement of silencer apparatus to the barrel of the firearm, other methods may include quick disconnect methods such as a three lug mount or any other known method that would maintain the alignment and bore of the firearm to the silencer and maintain a straight through hole path for the projectile. As shown, the threaded end cap ( 411 ) has an annular aperture ( 418 ) which then connects to a second end cap ( 414 ). The second end cap ( 414 ) has a concentric alignment guide ring ( 421 ) which aligns the third chamber inner tube ( 435 ) with the bore line in the retracted position.
The second chamber ( 420 ) has an opening with a flange or ridge ( 422 ) on the distal end concentric to the bore line to accommodate the third chamber ( 430 ), which can expand or contract longitudinally into the second chamber ( 420 ). The second cylinder has a concentric spring ( 424 ) which compresses the third chamber ( 430 ) into the second chamber ( 420 ). The spring ( 424 ) concentric with the second chamber ( 420 ) and third chamber ( 430 ) utilizes the flanges or ridges of the second chamber ( 422 ) and flanges or ridges of the third chamber ( 431 ) to hold the chambers in a normally retracted position.
The first chamber ( 410 ) can be of cylindrical or square or oval shape attached along-side the second chamber ( 420 ) and with openings ( 415 ) along-side the walls of the second chamber ( 420 ) into the first chamber ( 410 ), whereby the gases are flowed through the second chamber ( 420 ) and third chamber ( 430 ) and downward to the first chamber ( 410 ). In this embodiment, the projectile does not pass through the first chamber ( 410 ); the first chamber is attached to the side of the second chamber ( 420 ) and is used to port the gases. The first chamber ( 410 ) has vent holes ( 416 ) that can be placed on the ends caps or sides to allow the gases to exit in one of multiple directions.
The elements of the silencer ( 405 ) such as the aperture opening ( 418 ), alignment guide ring ( 421 ), third chamber inner tube ( 435 ), and end cap opening ( 434 ) are designed with openings that are slightly larger than the projectile width. This allows the projectile to pass untouched as it travels from the barrel of the gun ( 440 ) through the silencer ( 405 ).
In a fourth embodiment, the silencer ( 405 ) can be used to silence or suppress a shotgun that uses a cup and wad assembly for the shotgun shell. The elements as discussed in FIG. 4 and the third embodiment above are applicable as a base for the fourth embodiment along with the following differences. If a shotgun firearm utilizes shotgun shell ammunition with a wad and cup configuration, the silencer ( 405 ) apparatus can be used to silence or suppress the sound of the projectile. The changes from the third embodiment discussed above are, the inside diameter of the end cap opening ( 418 ), alignment cup ( 421 ) and third chamber inner tube ( 435 ) has substantially and very closely manufactured to be the same inside diameter as the barrel ( 440 ) of the shotgun. This would allow an uninterrupted path of uniform diameter for the shotgun shell in the wad and cup to pass through the barrel of the gun ( 440 ) and the silencer ( 405 ) through key elements such as end cap ( 411 ), ring ( 421 ), inner tube ( 435 ) and end cap opening ( 434 ) freely. The uninterrupted and uniform diameter of the barrel with the silencer allows the shotgun shell to maintain its flight [and pellet] configuration until it exits the silencer ( 305 ).
In order to address various issues and advance the art, the entirety of this application for COMPACT SPACE-SAVING GUN SILENCER (including the Cover Page, Title, Headings, Field, Background, Summary, Brief Description of the Drawings, Detailed Description, Claims, Abstract, Figures, Appendices, and otherwise) shows, by way of illustration, various embodiments in which the claimed innovations may be practiced. The advantages and features of the application are of a representative sample of embodiments only, and are not exhaustive and/or exclusive. They are presented only to assist in understanding and teach the claimed principles. It should be understood that they are not representative of all claimed innovations. As such, certain aspects of the disclosure have not been discussed herein. That alternate embodiments may not have been presented for a specific portion of the innovations or that further undescribed alternate embodiments may be available for a portion is not to be considered a disclaimer of those alternate embodiments. It will be appreciated that many of those undescribed embodiments incorporate the same principles of the innovations and others are equivalent. Thus, it is to be understood that other embodiments may be utilized and functional, logical, operational, organizational, structural and/or topological modifications may be made without departing from the scope and/or spirit of the disclosure. As such, all examples and/or embodiments are deemed to be non-limiting throughout this disclosure. Also, no inference should be drawn regarding those embodiments discussed herein relative to those not discussed herein other than it is as such for purposes of reducing space and repetition. For instance, it is to be understood that the logical and/or topological structure of any combination of any mechanical components (a component collection), other components and/or any present feature sets as described in the figures and/or throughout are not limited to a fixed operating order and/or arrangement, but rather, any disclosed order is exemplary and all equivalents, regardless of order, are contemplated by the disclosure. Furthermore, it is to be understood that such features are not limited to serial execution, but rather, any number of mechanical conditions such as projectile and gases processing, may execute processes asynchronously, concurrently, in parallel, simultaneously, synchronously, and/or the like are contemplated by the disclosure. As such, some of these features may be mutually contradictory, in that they cannot be simultaneously present in a single embodiment. Similarly, some features are applicable to one aspect of the innovations, and inapplicable to others. In addition, the disclosure includes other innovations not presently claimed. Applicant reserves all rights in those presently unclaimed innovations including the right to claim such innovations, file additional applications, continuations, continuations in part, divisions, and/or the like thereof. As such, it should be understood that advantages, embodiments, examples, functional, features, logical, operational, organizational, structural, topological, and/or other aspects of the disclosure are not to be considered limitations on the disclosure as defined by the claims or limitations on equivalents to the claims. It is to be understood that, depending on the particular needs and/or characteristics of a COMPACT SPACE-SAVING GUN SILENCER, various embodiments of the said invention, may be implemented that enable a great deal of flexibility and customization. For example, aspects of the COMPACT SPACE-SAVING GUN may be adapted for a Pistol firearm. While various embodiments and discussions of the silencer have included rifles and shotguns, however, it is to be understood that the embodiments described herein may be readily configured and/or customized for a wide variety of other applications and/or implementations.
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A compact silencer device for a firearm comprising of multiple chambers which trap the gases from a projectile exiting the barrel of a gun to slow down the gases and reduce the temperature, sound, and flash associated with the projectile. In one embodiment, the first chamber which attaches to the barrel of the firearm comprises of sound baffling materials or gas porting baffles which vent gases from the second chamber passing rearward. The second chamber comprises of a chamber which can accommodate a retractable third chamber of the device, the second and third chamber of the device can have sound baffles to slow down the gases from the projectile.
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TECHNICAL FIELD
This invention relates to a steam generator for a pressurized water-cooled nuclear reactor comprising first means for the supply of hot primary water from the reactor to the generator, second means for return of hot water to the reactor, third means for the supply of secondary or feed water to the generator and fourth means for the removal of steam created by the feed water in the generator.
DISCUSSION OF PRIOR ART
For a pressurized water reactor of the so-called PIUS type, described, inter alia, in U.S. Pat. No. 4,526,742 (Hannerz), a steam generator is suitably used for once-through flow of the feed water on the secondary side, a so-called once-through steam generator (OTSG), which directly produces a somewhat superheated, dry steam in the fourth means.
For several reasons it is desirable to use an embodiment of steam generator in a water-cooled nuclear reactor in which the steam is generated inside heat-exchange tubes which are surrounded by the hot radioactive primary cooling water. In particular, if the steam generator is situated inside the same concrete pressure vessel as the reactor core, a riser tube for coolant leaving the core and the so-called density locks, it is desirable for all the heat-exchange tubes to be easily accessible for inspection and repair from above, since tube attachments to a tube plate near the bottom of a steam generator are of necessity very difficult to reach.
In an embodiment of steam generator in which steam generation occurs inside heat-exchange tubes, service operations, such as non-destructive inspection and plugging of defective tubes, is suitably carried out in direct contact with the secondary side, which has not been contaminated with--or has only insignificantly been contaminated with--radioactivity. In order to avoid that such servicing operations have to be preceded by extensive dismantling work, it is convenient to gain entry access to the heat-exchange tubes via an outgoing steam conduit (i.e. the fourth means), which typically has a diameter of 700-800 mm. Since the incoming feed water pipe (i.e. the third means) normally has much too small a diameter to permit entry by maintenance personnel, it should also be possible to provide access to the weld joint between the inlet or feed water end of each heat-exchange tube and the tube plate via the steam conduit. One object of this invention is to provide a steam generator which permits this while at the same time allowing at least substantially the entire length of each heat-exchange tube to be used for heat transfer. Thus the invention can provide a steam generator for a water-cooled nuclear reactor which is available for non-destructive testing and repair without encroaching on the primary or radioactive side of the reactor cooling system.
SUMMARY OF THE INVENTION
The afore-stated object of the invention is achieved by a construction in which a horizontal tube plate is provided in the steam generator, the upper surface of which tube plate is contacted by the secondary water but not by the primary water and in which at least one vertically disposed U-shaped bundle of heat-exchange tubes is used, each tube in the bundle being welded to the tube plate at its two upper ends, the fourth means being adapted to allow service access to all tube/tube plate welds.
Suitably the tube plate is of annular form and the primary water flows upwardly through the center of the tube plate in a riser tube forming part of the first means. Above the tube plate the riser tube can feed the hot primary water to an annular duct forming part of the second means and through which the third and fourth means pass, water in this annular duct flowing below the tube plate to surround and contact the tubes of the at least one bundle and exchange thermal energy with the feed water/steam flowing in the heat-exchange tubes.
Conveniently there are four bundles of U-shaped tubes, the inlet end of each tube in each bundle being in communication with the third means and the outlet end of each tube in each bundle being in communication with the fourth means. To allow access to the inlet ends of the tubes from the steam outlet, the inlet ends can be contained in an openable (or removable) water box. The flow of primary water back to the reactor core can be via radial gaps left between the tube bundles.
BRIEF DESCRIPTION OF THE DRAWINGS
One embodiment of steam generator in accordance with the invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a sectional view of the steam generator taken on the line A--A in FIG. 2;
FIG. 2 is a sectional view on the line B--B in FIG. 1;
FIG. 3 is a sectional view on the line E--E in FIG. 4, and
FIG. 4 is a sectional view on the line C--C in FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The drawings show a steam generator for a water-cooled nuclear reactor which ducts primary reactor cooling water past an array of heat-exchange tubes through which secondary, or feed, water is converted into steam.
The heat-exchange tubes 1 have a U-shape and are attached, at both upper ends, to one and the same horizontal tube plate 2. The hot water from the primary system of the reactor flows upwardly in a riser tube 8 and is then supplied from above to an annular chamber 3, the outer wall 4 of which constitutes the upper outer boundary of the steam generator. The inner wall 12 of the steam generator, at two portions 5 located opposite to each other (each of which comprises about 20% of the circumference of the inner wall 12), is perforated by a large number of small holes through which the hot primary water flows inwardly below the tube plate 2 to contact the hot end of each heat-exchange tube located behind the inner wall. The steam generated in the tubes 1 passes out through the tube plate 2 into a steam chamber above this inlet portion.
The flow of secondary water inside and primary water outside the tubes thus takes place in counter flow, while steam generation takes place inside and cooling of the primary water takes place outside the tubes.
When the primary water has passed along the entire length of each U-tube and has reached the underside of that area on the tube plate 2 where the feed water inlet end of the U-tubes is welded, the primary water loses contact with the tube bundle and passes via a perforated plate out into a respective one of four radially disposed vertical gaps 6, each of which separates a region where the primary water flows upwards from a region where it flows downwards. The primary water then flows downwards along these gaps 6 to their lower ends where the gaps connect with an annular space 7 having an outer diameter approximately equal to the above-mentioned outer diameter of the outer wall 4. From the space 7 the primary water flows in a further annular duct 7a back to the reactor.
A plurality of U-shaped tube bundles, preferably four, depend from the one tube plate 2, this being given an annular shape by virtue of the centrally located riser tube 8. Suitably, as shown, the steam generator is provided with two output steam conduits 9 and two feed water pipes 10. The riser tube 8 and chamber 3 constitute the aforementioned first means, the space 7 and duct 7a the second means, the pipes 10 the third means and the conduits 9 the fourth means.
The inlets to the U-shaped tubes, where the feed water flows in, are separated from the steam space by means of a removable water box 11 which can be removed if any tube is to be plugged. The tubes 1 throughout their length may be reached for non-destructive testing, for example with an eddy current probe from the outlet end opening which is accessible from the steam space. In an alternative embodiment, which is shown in FIG. 1 of the drawings, each feed water box 11 is located somewhat above the tube plate 2 and is connected thereto by means of extensions 1a of the heat-exchange tubes 1.
A U-tube arrangement with downward flow on the secondary side presupposes that the mass flow there is relatively large in order to obtain a stable flow. However, for a reactor of the PIUS type it is desirable, in the case of partial power output, to operate with an approximately constant outlet temperature from the reactor core, whereas the primary mass flow is approximately constant when the inlet temperature on the primary side rises with decreasing power. To reduce the thermal stresses in the tube plate, the feed water can be preheated with fresh steam in a situation of partial power output.
The feed water flow, on the other hand, can be made to be approximately proportional to the power output of the reactor. For this reason, in a steam generator provided with U-tubes, the feed water can be completely evaporated even before it reaches the 360° turn at the lower end, and under these circumstances there is a risk that the flow conditions on the secondary side become unstable. This can be avoided, for example, by arranging for the number of U-tubes which are being used for feed water flow to be adjusted to the volume of feed water flow. In practical terms this can be achieved by locating the inlet ends of the heat-exchange tubes in a plurality of mutually separable spaces. Under full power operating conditions, all these spaces are used and are connected to each other and to the feed water pipes 10. When the power and the steam production of the reactor are reduced, some of the heat-exchange tubes are successively shut off from the supply of feed water, whereas the remaining tubes still receive a supply of feed water close to the normal supply volume, whereby the flow therein remains stable. In this way, a stable flow on the secondary side can be ensured over the entire power range.
The primary cooling water, which does not come into contact with heat-exchange tubes which are supplied with feed water on the secondary side, will not, under these circumstances, be cooled in the steam generator. However, after leaving the steam generator, the primary cooling water will be mixed with fully cooled water which has been contacting water-filled heat-exchange tubes, and the resultant mixture has the same temperature as if the same amount of feed water had been supplied to all the tubes. Since the cooling of the primary coolant in a steam generator typically only amounts to about 30° C., thermal stresses in the equipment, caused by the sectioning, can be prevented from reaching impermissible values.
Various modifications can be made to the design shown in the drawings and all such modifications falling within the scope of the following claims should be understood to be part of this invention.
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Steam generators are used in pressurized water-cooled nuclear reactors for generating steam which issues from the generator through a large bore steam outlet. Heat-exchange tubes through which feed water flows are surrounded by hot cooling water from the reactor. The tubes must be capable of being inspected and repaired. To simplify inspection and repair, the tubes are U-shaped and each end of each tube is connected upwardly to a tube plate in the steam generator, whereby each end of each tube can be reached in a simple manner through an outgoing steam outlet.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to semiconductor fabrication and more particularly to an integrated circuit which employs local interconnect for reducing cross coupled noise within conductors arranged above the local interconnect. The local interconnect is advantageously connected to a power supply for sinking transient noise spikes from the overlying conductors.
2. Description of the Relevant Art
An integrated circuit includes numerous conductors extending across the topography of a monolithic substrate. A set of interconnect lines (or conductors) which serve to electrically connect two or more components within a system is generally referred to as a "bus". A collection of voltage levels are forwarded across the conductors to allow proper operation of the components. For example, a microprocessor is connected to memories and input/output devices by certain bus structures. There are numerous types of busses which are classified according to their operation. Examples of well-known types of busses include address busses, data busses and control busses.
Conductors within a bus generally extend partially parallel to each other across the semiconductor topography. The conductors are isolated from each other and from underlying conductive elements by a dielectric, a suitable dielectric being, for example, silicon dioxide ("oxide"). Conductors are thereby lithography patterned across the semiconductor topography, wherein the topography comprises a substrate with a dielectric placed thereon. The topography can also include one or more layers of conductors which are covered by a dielectric material. The layers of conductors overlaid with a dielectric present a topography upon which a subsequent layer of conductors can be patterned.
Conductors are made from an electrically conductive material, a suitable material being a metal or metal silicide. Substrate includes any type of material which can retain dopant ions and the isolated conductivity regions brought about by those ions. Typically, substrate is a silicon-based material which receives p-type or n-type ions.
In order to complete the fabrication of an integrated circuit, isolated regions within the substrate and conductors spaced above the substrate must be interconnected. Wherever a connection is needed between a substrate and conductor, or between conductors on separate levels, an opening in the dielectric must be provided to allow such context to occur. Formation of openings and fabrication of ohmic materials in those openings is generally referred to as contact technology. Depending upon what is being contacted, contact technology varies. For example, contact of a polysilicon conductor to an isolated silicon region differs substantially from contact of a metal conductor to a polysilicon conductor or metal to silicon. Typically, the design rule spacing requirements are dissimilar depending upon the features being contacted.
Contact of a polysilicon conductor to underlying silicon substrate is performed simply by forming an opening in the interposed dielectric. When the polysilicon is subsequently deposited, the polysilicon forms an electrical contact with the silicon in the opening but is isolated everywhere else. The aforementioned contact structure is typically referred to as a "buried contact" because a metal conductor can cross over a dielectric-covered buried contact without making an electrical connection to it. The use of buried contacts provides an important benefit in that it makes available an additional level of interconnect on an integrated circuit.
A polysilicon conductor, as part of a buried contact, is not as universal as a metal conductor for two reasons. First, a polysilicon conductor cannot cross over regions where a transistor gate exists without making a contact to the gate. Second, polysilicon resistivity is substantially higher than that of aluminum (Al). Since metal conductors can extend in an unrestricted fashion across a semiconductor topography, metal conductors are generally referred to as global interconnects, to distinguish them from the routing-restricted interconnect of polysilicon. Thus, polysilicon conductors are distinguished from metal conductors, and are often termed "local interconnect".
There are many types of materials used to establish local interconnects. For example, local interconnects can be formed in numerous ways, some of which are (i) a refractory metal silicide upon polysilicon, (ii) a single or double-doped polysilicon, (iii) multi-layered refractory metal partially converted to silicide, and (iv) refractory metal deposited by physical vapor deposition (PVD) or chemical vapor deposition (CVD).
Local interconnects and associate buried contacts serve an important function. Primarily, local interconnects make available an additional level of interconnect on the integrated circuit. Local interconnects, when covered with a dielectric, allow global interconnect such as metal conductors to extend over the local interconnect and buried contacts. Thus, local interconnects afford an additional interconnect level provided the added resistance of a local interconnect would not deleteriously affect circuit performance. For this reason, local interconnects are generally used for short interconnect runs relative to much longer metal conductors. Local interconnects are used primarily to interconnect gates and drains in MOS circuits, and are prevalent in, for example, high density VLSI logic and SRAMs. An SRAM cell layout can be substantially reduced when a local interconnect level and associated buried contacts are used.
Referring now to FIG. 1, an exemplary SRAM cell of conventional design is shown. SRAM cell 10 includes a pair of cross-coupled transistors 12 and a pair of access transistors 14. Application of a word bit (W0 and W1) will force the output from transistors 12 to undergo a change in state when a sufficient voltage magnitude and duration of bit input (B0 or B1) exists.
A chief disadvantage of an SRAM cell is that it consists of several devices (four are shown), as compared to only two devices needed for a dynamic memory cell. Thus, even when the same set of design rules is used, an SRAM die cannot be built with as many cells as a DRAM die. As SRAMs have evolved, they have undergone an increase in density. Most of this has been due to the use of smaller line widths. However, density improvements occur when using, for example, buried contacts, local interconnects, and poly load resistors 16 in lieu of devices.
FIG. 1 illustrates an SRAM cell having four devices and two poly load resistors 16, instead of a cell having six devices. In a four-transistor cell having two poly load resistors 16, there are no P-channel devices, so no N-channel-to-P-channel isolation is needed. Furthermore, the poly load resistors 16 simply require buried contacts rather than metal contacts needed to connect N-channel and P-channel devices. Buried contacts, by definition, take less space than metal contacts.
The smaller geometry afforded by poly load resistors is principally achieved by using not only buried contacts, but associated local interconnect as well. Typically, a high density SRAM cell employs two polysilicon local interconnect levels. A first level of local interconnect is typically a metal polycide structure formed upon polysilicon, and is generally used for the VSS power line as well as the gates of MOS transistors 12. The local interconnect level is also a polycide conductor for both the high-valued load resistors 16 and the low-resistance VDD lines. From the above, it is recognized that local interconnect is advantageously used in SRAMs or in any VLSI device when short interconnect runs are needed, or where buried contact sizings prove advantageous. Conventionally, however, local interconnects are therefore used not only to connect to VSS or VDD, but when applied in an SRAM environment are also used as gate-to-drain interconnect structures. If local interconnect is coupled as a gate structure it, by definition, must take on differing operational voltage values ranging between VDD and VSS or alternating between VDD and VSS (depending upon the voltage value of B0 or B1). In the cross-coupled example, the voltage value on one local interconnect gate structure will be opposite that of the other local interconnect gate structure. In conventional applications, therefore, local interconnects must take on non-fixed operational voltage values of the functional circuit.
It would be desirable to employ local interconnect not simply as short routing runs of a multi-layered structure. An improvement might exist whereby the local interconnect is used to remove cross-coupling noise of adjacent conductors. To remove the operational noise of the conductor, an improvement is needed whereby the local interconnect is coupled to a fixed power supply voltage, and is not afforded the opportunity to transition from the power supply or between power supplies as in conventional designs. The improved design must thereby use a local interconnect for reasons dissimilar from conventional local interconnects.
SUMMARY OF THE INVENTION
Broadly speaking, the present invention contemplates an integrated circuit which employs a power-coupled local interconnect to reduce cross-coupling noise within the integrated circuit. More specifically, a local interconnect is used to sink noise from an overlying conductor through the local interconnect and into a power supply connected to the local interconnect. The improved architecture thereby employs local interconnect outside the integrated circuit operational routing--i.e., not within the normal interconnect structure of an integrated circuit. The local interconnect is directly coupled to a power supply (VDD or VSS) and is distanced from the conductors which carry operational current or voltage of an integrated circuit. Defined herein, VDD refers to a power supply above or below ground (preferably above ground at or approximately equal to 1.5 volts to 5.0 volts above ground). VSS is defined as ground voltage (e.g., 0.0 volts).
The integrated circuit thereby comprises an interconnect structure which includes a local interconnect patterned upon a semiconductor topography, or a local interconnect inlaid into a dielectric. Placed upon the local interconnect is a dielectric, and placed upon the dielectric is a metal conductor. The local interconnect is connected directly to a power supply which serves to capacitive couple any transient noise within the metal conductor through the dielectric and to power supply via the local interconnect.
The local interconnect is typically made from a conductive material having higher resistivity than aluminum, and certainly higher resistivity than the metal conductor. The local interconnect comprises either polysilicon, doped polysilicon, refractory metal/silicide, or appropriate combinations of each. The local interconnect preferably occupies a local, relatively small area of semiconductor topography generally larger in lateral dimension then the overlying metal conductor. According to an alternative embodiment, the local interconnect extends along an axis parallel to the longitudinal axis associated with the metal conductor. In the latter instance, the local interconnect extends a substantial distance along and below the metal conductor and is somewhat smaller in overall lateral area than the overlying conductor provided, however, that the local interconnect reserves an area outside the lateral area occupied by the conductor. The reserved area of local interconnect is that which extend laterally from the overlying metal conductor for receiving a contact and overlying power-coupled conductor. In either embodiment, the local interconnect is arranged directly below the longitudinal run of the metal conductor, except for the contact area occupied by the power-coupled conductor.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects and advantages of the invention will become apparent upon reading the following detailed description and upon reference to the accompanying drawings in which:
FIG. 1 is a circuit diagram of a static random access memory (SRAM) cell employing local interconnect according to a conventional design;
FIG. 2 is a partial, top plan view of a set of global interconnect (metal conductors) spaced over power-coupled local interconnect;
FIG. 3 is a processing step shown along plane A of FIG. 2, wherein a single-doped or dual-doped polysilicon local interconnect is formed according to one exemplary embodiment;
FIG. 4a is a processing step shown along plane A of FIG. 2, wherein a dual layer of refractory metal is formed according to another exemplary embodiment;
FIG. 4b is a processing step subsequent to that shown in FIG. 4a, wherein an upper layer of the dual layer is selectively removed and a temperature cycle is applied to the remaining layers;
FIG. 4c is a processing step subsequent to that shown in FIG. 4b, wherein the layers unaffected by the temperature cycle are removed to form a refractory metal silicide local interconnect;
FIG. 5 is a processing step shown along plane A of FIG. 2, wherein dual layer of refractory metal local interconnect is formed according to yet another exemplary embodiment;
FIG. 6a is a processing step shown along plane A of FIG. 2, wherein a single layer of refractory metal is formed according to still another exemplary embodiment;
FIG. 6b is a processing step subsequent to that shown in FIG. 6a, wherein the single layer of refractory metal is selectively removed;
FIG. 6c is a processing step subsequent to that shown in FIG. 6b, wherein an upper portion of the single layer of refractory metal is converted to a nitride and a lower portion of the single layer of refractory metal is converted to a silicide to form a barrier-enhanced, refractory metal local interconnect;
FIG. 7 is a processing step subsequent to either FIGS. 3, 4c, 5 or 6c , wherein a dielectric is deposited upon the local interconnect; and
FIG. 8 is a processing step subsequent to FIG. 7, wherein a global interconnect (metal conductor) is patterned directly above at least a portion of the dielectric-covered local interconnect.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
Turning now to drawings, FIG. 2 illustrates a partial, top plan view of an integrated circuit 20. Integrated circuit 20 includes a set of global interconnect, metal conductors 22, spaced over power-coupled local interconnect 24. Local interconnect 24 is defined herein above as being routing restrictive to areas outside of polysilicon gate areas or polysilicon within active areas (i.e., areas where active transistors are formed), and are of higher resistivity than conductors 24. Conductors 24 are defined as conductors made of aluminum, or aluminum silicide. Local interconnect 24 is made of any conductive material less than the conductivity of aluminum, and preferably includes polysilicon, doped polysilicon, refractory metal, refractory metal silicide, and/or a combination of multi-layer refractory metal nitrides and silicides.
FIG. 2 illustrates integrated circuit 20 as having a plurality of metal conductors 22, wherein selected conductors 22 reside a dielectric-spaced distance above local interconnect 24. FIG. 2 also illustrates the varying size of local interconnect 24. Illustrated by reference numerals 24a and 24b, local interconnect 24a is shown as being wider than overlying conductor 22, and extends along the entire longitudinal axis of conductor 22. Conversely, local interconnect 24b is shown of lesser width than conductor 22. Regardless of its configuration, local interconnect 24 preferably extends a substantial length of conductor 22, and protrudes laterally from underneath conductor 22 to a contact region 26. Contact region 26 is defined as a region exclusive of conductor 22. Region 26 is sized so as to receive a contact 28 and an overlying power-coupled conductor 30. Conductors 30, 22, region 26 and contact 28 obey minimum spacing rules applicable to MOS circuit implementations.
FIG. 2 further depicts a conductor 32 having no associated local interconnect 24. Local interconnect 24 is thereby used only below "critical" conductors 22. Critical conductors 22 are defined as those which require transient noise spike suppression afforded by a closely spaced, powered local interconnect. Integrated circuit 20 further includes active and field regions 34 and 36, respectively. Regions 34 and 36 reside a dielectric spaced distance below the conductors as well as below local interconnect 24. Active regions 34 serve to receive devices, and field regions 36 serve to isolate devices.
Referring to FIGS. 3-6, various embodiments are shown by which local interconnect 24 are formed. FIGS. 3-6 are shown along plane A of FIG. 2, in accordance with a processing sequence necessary to form various types of local interconnect structures.
FIG. 3 depicts polysilicon 40 deposited across semiconductor topography 42. Polysilicon layer 40 is thereafter selectively removed using lithography techniques. The removed regions are shown by dashed lines, and are designated as reference numeral 44. Regions between removed areas 44, or retained polysilicon, are designated as local interconnect 24c. Local interconnect 24c, as shown according to one embodiment, has a polysilicon layer previously implanted with either a single or dual set of dopants. For example, polysilicon 40 can be deposited with an n-type ion (for an NMOS process) or both n-type and p-type ions (for a CMOS process). The dopant ions are directed in accordance with arrows 48.
FIG. 4a illustrates, according to an alternative embodiment, a layer of refractory metal 50, such as titanium (Ti) is deposited upon topography 42, followed by deposition of amorphous silicon 52. FIG. 4b illustrates, in a subsequent processing step, selective removal of amorphous silicon 52. The etch material is chosen to remove silicon, but is not sensitive to removal of underlying refractory metal. The thickness of refractory metal and amorphous silicon is chosen such that the amorphous silicon will react fully with the underlying refractory metal during a subsequent processing step in which a thermal cycle 56 is applied. Thermal cycle 56 causes the retained silicon to react with underlying refractory metal, to form local interconnect 24d. The unreacted refractory metal 58 is thereafter removed, as shown by FIG. 4c. Removal of the unreacted refractory metal is carried forth using a wet etch solution comprising, for example, H 2 SO 4 and H 2 O 2 . A final, higher temperature anneal cycle is then applied, as shown by reference numeral 60. The higher temperature anneal is used to reduce the resistivity of the ensuing refractory metal silicide of local interconnect 24d.
FIG. 5 illustrates an alternative formation of local interconnect. According to this embodiment, local interconnect 24e is formed by depositing two separate levels of refractory metal, suitable refractory metal includes titanium followed by tungsten (W). Alternatively, titanium and tungsten can be simultaneously deposited from a single sputter target. The titanium and tungsten layer is then selectively removed, and in regions where the layer is retained, a local interconnect 24e is formed.
FIGS. 6a-6c depict another alternative formation of local interconnect. Specifically, FIG. 6a illustrates deposition of refractory metal nitride, or deposition of metal followed by a nitride anneal. In either instance, an ensuing refractory metal nitride 62 is formed. Refractory metal nitride 62 preferably comprises titanium which is selectively patterned and removed, as shown in FIG. 6b. FIG. 6b depicts removal 64 and retainage 66 of layer 62. Removal and retainage of layer 62 is performed using conventional lithography techniques. FIG. 6c illustrates application of a thermal cycle 68 to the retained metal nitride material, causing a film of metal nitride 70 at the upper portion and metal silicide 72 at the lower portion. According to another embodiment, material 72 is polysilicon, and a metal silicide 70 is formed upon polysilicon 72. A metal oxide or nitride can be formed upon the metal silicide or metal nitride material 70. By varying the temperature and ambient gas during the anneal cycle, it is possible to obtain various metal nitride and metal silicide thickness combinations. Unmasked metal nitride is removed, as shown in FIG. 6b, preferably using a fluorine-based dry etch sequence. FIG. 6c depicts a finalized local interconnect 24f. It is understood that, contrary to photolithography patterning, material 66 can be formed through a damascene process. According to a damascene process, material 66 is inlaid into a trench within a dielectric. Thereafter, material is removed from the upper surface of the dielectric leaving only material within the trench. Removal is carried forth by either an etchback step or a chemical-mechanical polish (CMP) step.
Given the various composition and processing sequences used to produce local interconnect 24 (shown in FIGS. 3-6c) a local interconnect is formed which, according to FIG. 2, is connected via contact 28 to VDD or VSS. A powered local interconnect 24 is shown in FIG. 7 along plane A of FIG. 2. Deposited upon local interconnect 24 is a dielectric 80. Dielectric 80 is preferably deposited using physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), or spin-on deposition techniques. In the former instance, a silane or TEOS source is used to produce dielectric 80 as it is being deposited upon and between local interconnect 24. In a latter instance, a liquid material of silicon (i.e., silicates, siloxanes, or silsesquioxanes) or TEOS is spin-on deposited and subsequently cured. In either instance, dielectric 80 contains sufficient insulative characteristics to isolate non-noise (steady state) signals from local interconnect 24. However, if sufficiently high transients occur; then capacitive coupling within dielectric 80 sinks the noise spikes of the signal to local interconnect 24.
FIG. 8 illustrates a processing step subsequent to FIG. 7, wherein a metal conductor 22 is formed by selectively removing a conductive layer of metal 82. Conductive metal 82 comprises aluminum or other metals, and metal conductor 22 is formed using well-known lithography techniques. The thickness of dielectric 80 between conductor 22 and local interconnect 24 is sufficient to allow coupling of noise spikes but disallow coupling of non-noise signals.
It would be appreciated to those skilled in the art having the benefit of this disclosure that this invention is capable of applications with numerous types of MOS-processed circuits. Furthermore, it is to be understood that form of the invention shown and described is to be taken as presently preferred embodiments. Various modifications and changes may be made to each and every processing step as will be obvious to a person skilled in the art having the benefit of this disclosure. It is intended that the following claims be interpreted to embrace all such modifications and changes and, accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense.
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An integrated circuit is provided having an improved interconnect structure. The interconnect structure includes a power-coupled local interconnect which is always retained at VDD or VSS (i.e., ground) level. The local interconnect resides a dielectric-spaced distance below critical runs of overlying interconnect. The powered local interconnect serves to sink noise transients from the critical conductors to ensure that circuits connected to the conductors do not inoperably function. Accordingly, the local interconnect extends along a substantial portion of the conductor length, and is either wider or narrower than the conductor under which it extends. The local interconnect can either be polysilicon, doped polysilicon, polycide, refractory metal silicide, or multi-level refractory metal.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to U.S. Provisional Application No. 60/261,654, filed Jan. 13, 2001, the disclosure of which is incorporated herein by reference in its entirety.
STATEMENT OF GOVERNMENT SUPPORT
[0002] This invention was made with government support under grant number K08 AI01728-01 and U0I-A133383 from the National Institutes of Health. The United States government may have certain rights in this invention.
FIELD OF THE INVENTION
[0003] This invention relates to the treatment of bovine viral diarrhea virus (BVDV) and hepatitis C virus (HCV) infections.
BACKGROUND OF THE INVENTION
[0004] Bovine viral diarrhea virus (BVDV) is an enveloped, single-stranded, positive sense RNA virus in the genus Pestivirus and the family Flaviviridae. Based on the presence or absence of visible cytopathic effect when susceptible cell monolayers are infected, two pathogenic biotypes of BVDV, referred to as cytopathic and noncytopathic, have been identified. Perdrizet J A in B. P. Smith (ed), Large Animal Internal Medicine, First Edition (Mosby Press, St Louis, 731-737 (1990)). A differentiation is also made between biotypes of BVDV (referred to as biotypes I and II) based on certain viral RNA sequences in the 5′ untranslated region of the genome. Pellerin C, et al., Virology 203, 260-268 (1994); J. F. Ridpath et al., Virology 205, 66-74 (1994).
[0005] BVDV may cause acute infection in cattle, resulting in bovine respiratory disease, diarrhea and severe reproductive losses. Clinical symptoms of acute BVDV infection may range from the almost undetectable to the severe. Infection of pregnant cows and heifers may result in breeding problems (e.g., irregular heats), abortion, premature births or the birth of weak or stunted calves. In some cases, temporary damage to an animal's immune system may occur even when the clinical symptoms are not apparent. In addition to the illness caused by the virus itself, infected animals are more susceptible and are more likely to suffer from other diseases, such as pneumonia.
[0006] In addition to causing acute disease, BVDV may also establish persistent infections. Potgieter, Vet. Clin. North Am. Food Anim. Pract 11, 501-520 (1995). Persistent BVDV infections are generally established via in utero infection of a developing fetus with a noncytopathic BVDV. The resulting animals are born immunotolerant of the particular BVDV by which they are infected, and may continually shed virus throughout their life span. While some persistently infected animals exhibit congenital malformations due to BVDV infection, many animals persistently infected with BVDV appear clinically normal. Baker, Rev. Sci. Tech 9, 25-41 (1990); Bielefeldt-Ohmann, Vet. Clin. North Am. Food Anim. Pract 11, 447-476 (1995). Persistently infected animals are thought to be the major disseminators of BVDV in the cattle population.
[0007] There are more than 140 vaccines against BVDV commercially available in the United States. Bolin, Am J. Vet Res. 46, 2476-2470 (1995). Unfortunately, vaccination does not provide complete protection against BVDV infection, as some vaccinated cattle still become infected with the virus. At present, there is no known cure for BVDV infection. Accordingly, a need exists for an effective treatment for BVDV infection.
[0008] In vitro production of embryos has become a useful therapy for increasing reproductive performance of animals and for treating infertility of both, animals and humans. In vitro production of bovine embryos could permit the humane, world-wide transfer of genetic material among cattle while limiting the transmission of many pathogens. However, in vitro-produced bovine embryos are potential vectors for transmission of BVDV. B. Avery et al., Vet Rec 132, 660 (1993); A. Bielanski et al., Theriogenology 46, 1467-1476 (1996); T. Tsuboi et al., Vet Microbiol 49, 127-134 (1996); O. Zurovac et al., Theriogenology 41, 841-853 (1994). BVDV can be introduced into the embryo production system in association with gametes, serum, somatic cells, cumulus oocyte complexes (COCs), and result in contaminated in vitro fertilized (IVF) embryos or cell lines. K. V. Brock et al., J Vet Diagn Invest 3, 99-100 (1991); C. R. Rossi et al., Am J Vet Res 41, 1680-1681 (1980); P. J. Booth et al., J Reprod Fert Abstr Ser Suppl 9, 28 (1992); M. D. Fray et al., Vet Pathol 35, 253-259 (1998); R. Harasawa et al., Microbiol Immunol 39, 979-985 (1995); T. Shin et al., Theriogenology 53, 243 (2000). Association of noncytopathic BVDV with transferred IVF embryos may cause infection of embryo recipients, early embryonic death, abortion or birth of persistently infected offspring.
[0009] An analogous hazard exists in human in vitro embryo production. Viral transmission to human embryos and embryo recipients by means of contaminated embryo culture media has been reported. Addition of an anti-viral agent to the culture medium surrounding in vitro-produced embryos could prevent or reduce transmission of virus to the embryo or embryo recipient. P. M. Grosheide et al., Vaccine 9, 682-687 (1991); W. G. Quint et al., J Clin Microbiol 32, 1099-1100 (1994); H. C. van Os et al., Am J Obstet Gynecol 165, 152-159 (1991). Accordingly, an antiviral agent that could be added to both animal and human in vitro embryo production systems may have important applications.
[0010] The organization of the portion of the BVDV genome that encodes the proteins used in viral replication is very similar to that of human hepatitis C virus (HCV), another flavivirus. S. W. Behrens et al., J Virol 72, 2364-2372 (1998). It is believed that more than 80% of the individuals infected with HCV will eventually develop a chronic form of the disease. As the disease develops, the liver of the infected subject is progressively damaged, with the symptoms generally being commensurate with cirrhosis and liver failure (e.g., jaundice, abdominal swelling, and finally, coma). The cycle of disease from infection to significant liver damage can take 20 years or more. Liver failure due to HCV is the presently the leading cause of liver transplants in the United States. It is suspected that there are, at present, more than 5 million people in the United States that are infected with HCV, and perhaps as many as 200 million around the world, making HCV infection a significant public health threat.
[0011] The development of a vaccine for HCV infection is uncertain, due in part to the high mutation rate of the virus. Recombinant interferon alpha-2b (INTRON A®/Schering) has proved effective in some cases of chronic hepatitis C. However, it has been reported that relapse occurs in at least half the responders after the interferon alpha-2b treatment is discontinued. Additionally, interferon alpha-2b may exacerbate hepatocyte injury caused by autoimmune chronic active hepatitis. J. Y. N. Lau et al., Br Med J. 306, 469-470 (1993). The nucleotide analog ribavirin (VIRAZOLE®/ICN Pharmaceuticals) has been shown to reduce concentrations of hepatitis C viral RNA in an infected subject, although at a slower rate than interferon alpha-2b. As with BVDV infection, a need exists for an effective treatment for HCV infection.
SUMMARY OF THE INVENTION
[0012] In view of the foregoing, one aspect of the invention relates to novel compounds that are useful in treating members of the Flaviviridae family of viruses, such as bovine viral diarrhea virus (BVDV) infection and hepatitis C virus (HCV) infection. Compounds of the present invention will have a structure according to Formulas (I)-(VI), as follows:
[0013] wherein:
[0014] X 1 and X 3 are each independently selected from the group consisting of O, S and NR 9 , wherein R 9 is H or alkyl;
[0015] X 2 and X 4 are each independently CH or N;
[0016] A is selected from the group consisting of H, alkyl, aryl,
[0017] R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of H, alkyl, alkoxy, amidine, halide, alkylhalide, nitro and amino groups;
[0018] R 6 is H, alkyl or aryl; and
[0019] R 7 and R 8 are each independently selected from the group consisting of H and alkyl.
[0020] Additional aspects of the invention include pharmaceutical compositions comprising a compound having a structure according to Formulas (I)-(VI), or a pharmaceutical salt thereof (i.e., an “active compound”), in a pharmaceutically-acceptable carrier. Pharmaceutical compositions of the present invention are useful in the treatment of bovine viral disease virus (BVDV) infection and hepatitis C virus (HCV) infection.
[0021] Certain aspects of the invention relate to methods of treating bovine viral disease virus (BVDV) infection in a subject in need of such treatment. The method comprises administering to the subject a compound according to Formulas (I) through (VI), or a pharmaceutically acceptable salt thereof, in an amount effective to treat bovine viral disease virus (BVDV) infection.
[0022] Other aspects of the invention relate to methods of treating hepatitis C virus (HCV) infection in a subject in need of such treatment. The method comprises administering to the subject a compound according to Formulas (I) through (VI), or a pharmaceutically acceptable salt thereof, in an amount effective to treat hepatitis C virus (HCV) infection.
[0023] A further aspect of the present invention is the use of the active compounds described herein for the manufacture of a medicament for the treatment of bovine viral disease virus (BVDV) infection in a subject in need of such treatment.
[0024] Still another aspect of the present invention is the use of the active compounds described herein for the manufacture of a medicament for the treatment of treating hepatitis C virus (HCV) infection in a subject in need of such treatment.
[0025] The foregoing and other aspects of the present invention are explained in detail in the specification set forth below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 illustrates four chemical schemes useful in the synthesis of compounds of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The present invention now will be described more fully hereinafter with reference to the accompanying specification and drawings, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set-forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0028] The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.
[0030] With respect to the compounds of the Formulas (I) through (VI), as used herein, the term “alkyl” refers to C1-10 inclusive, linear, branched, or cyclic, saturated or unsaturated (i.e., alkenyl and alkynyl) hydrocarbon chains, including for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, and allenyl groups. The term “alkyl” specifically includes cycloakyl hydrocarbon chains, which as used herein refers to C3 to C6 cyclic alkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. In the present invention, preferred alkyls are the lower alkyls. The term “lower alkyl” refers to C1 to C4 linear or branched alkyl, such as methyl, ethyl, propyl, butyl, isopropyl, sec-butyl, and tert-butyl.
[0031] The term “alkyl” also encompasses substituted alkyls, which include aminoalkyls, hydroalkyls, oxygen-substituted alkyls (i.e., alkoxy groups), and halogen-substituted alkyls (i.e., alkyl halides, polyhaloalkyls). The term “aminoalkyl,” as used herein, refers to C1 to C4 linear or branched amino-substituted alkyl, wherein the term “amino” refers to the group NR′R″, and wherein R′ and R″ are independently selected from H or lower alkyl as defined above, i.e., —NH 2 , —NHCH 3 , —N(CH 3 )2, etc. The term “hydroxyalkyl” as used herein refers to C1 to C4 linear or branched hydroxy-substituted alkyl, i.e., —CH 2 OH, —(CH 2 ) 2 OH, etc. The term “alkoxy” as used herein refers to C1 to C4 oxygen-substituted alkyl, i.e., —OCH 3 . The term “loweralkoxy,” as used herein, refers to C1 to C4 linear or branched alkoxy, such as methoxy, ethoxy, propyloxy, butyloxy, isopropyloxy, and t-butyloxy.
[0032] The terms “halo” and “halide” have their conventional meaning and refer to fluoro, chloro, bromo, and iodo groups. Preferred halo groups include chloro groups, and preferred alkyl halides of the present invention include CF 3 . “Nitro” groups; as used herein, have the structure —NO 2 .
[0033] The term “aryl” as used herein refers to C3 to C10 cyclic aromatic groups such as phenyl, naphthyl, and the like, and specifically includes substituted aryl groups including but not limited to tolyl, substituted phenyl, and substituted naphthyl. Aryl groups may be substituted with halo, amino, nitro, and the like. Heterocyclic aromatic rings and polycyclic aromatic groups are also included in this definition of “aryl.” Specific examples of aryl groups encompassed by the present invention include but are not limited to cyclopentadienyl, phenyl, furan, thiophene, pyrrole, pyran, pyridine, imidazole, isothiazole, isoxazole, pyrazole, pyrazine, pyrimidine, and the like.
[0034] The compounds of the present invention are also useful in the form of their pharmaceutically acceptable salt forms. Such salts may include, but are not limited to, the gluconate, lactate, acetate, tartarate, citrate, phosphate, borate, nitrate, sulfate, hydrobromide and hydrochloric salts of the compounds. Compounds of Formulas (I)-(VI) and their pharmaceutically acceptable salts are referred to herein as “active compounds” or “active agents.”
[0035] The compounds represented by the Formulas (I) through (VI) may be formed by synthesis procedures that are described in the Examples below, as well as by certain methods known in the art. Some of these known methods are set forth below in the Examples by description or by reference (the disclosures of which are all incorporated herein by reference in their entirety).
[0036] Examples of compounds useful in the present invention are set forth in Table 1, below. In Table 1, the A groups are as follows:
TABLE 1 Selected Compounds Of The Present Invention Compound Name Formula A X1 X2 X3 X4 R1 R2 R3 R4 R6 R7 R8 DB 456 I A3 O C NH N NH2 H H H — H H DB 457 I A3 O C NH N NO2 H H H — H H DB 458 I A1 O C NH N NO2 H H H alkyl — — DB 459 I A1 O C NH N NH2 H H H alkyl — — DB 606 V A3 O C — — OCH3 H H H H H H DB 619 VI A1 NH C — — H H H — H — — DB 673 VI A2 O C — — H H H — H — — DB 680 VI A2 O C — — CH 3 H CH 3 — H — — DB 686 VI A2 S C — — H H H — H — — DB 687 VI A2 S N — — H H H — H — — DB 700 VI A2 O C — — H H H — H — — DB 701 VI A2 O C — — CF3 H CF3 — H — — DB 705 VI A2 O C — — H H H — H — — DB 708 VI A2 O C — — Cl H Cl — H — — DB 711 VI A2 O C — — OCH 3 H OCH 3 — H — — DB 752 VI A2 S C — — CH 3 H CH 3 — H — — DB 771 II A2 O C NH N H H H — H — — DB 772 II A3 O C NH N H H H — — H H
[0037] Formulas of the compounds set forth above are as follows:
[0038] As noted above, the compounds, methods and compositions of the present invention are useful for treating bovine viral diarrhea virus (BVDV) infections and hepatitis C virus (HCV) infections. The term bovine viral diarrhea virus infection means any infection (e.g., acute, latent or persistent) caused by a virus classified as a bovine viral disease virus (BVDV). As set forth above, BVDV is an enveloped, single-stranded, positive sense RNA virus in the genus Pestivirus and the family Flaviviridae. The term bovine viral disease virus (BVDV), as used herein, encompasses all BVDV strains and all serotypes and variants thereof, including live, attenuated, killed or otherwise inactivated forms. The term BVDV specifically includes cytopathic and noncytopathic strains, and strains of both biotype I and biotype II. The term “hepatitis C virus (HCV) infection” includes any infections caused by the hepatitis C virus (HCV), which includes all strains, serotypes and variants of HCV.
[0039] In one embodiment of the invention, a subject is administered a therapeutically-effective amount of the compound of formulas (I) through (VI), or a pharmaceutically acceptable salt thereof. A “therapeutically-effective” amount as used herein is an amount of a compound of formulas (I) through (VI) that is sufficient to alleviate (e.g., mitigate, decrease, reduce) at least one of the symptoms associated with BVDV or HCV infection. It is not necessary that the administration of the compound eliminate the symptoms of BVDV or HCV, as long as the benefits of administration of compound outweigh the detriments. Likewise, the terms “treat” and “treating” in reference to BVDV or HCV, as used herein, are not intended to mean that the avian subject is necessarily cured of BVDV or HCV; or that all clinical signs thereof are eliminated, only that some alleviation or improvement in the condition of the subject is effected by administration of the compound of Formulas (I) through (VI).
[0040] Suitable subjects of the present invention include humans and animals. When the subject is an animal, mammals are preferred, with livestock (e.g., cattle, pigs, sheep, horses) and primates (e.g., monkeys, apes) being particularly preferred. In embodiments of the present invention where BVD are treated, bovine subjects (e.g., cows, bulls, calves) are preferred. In embodiments of the present invention where HCV infections are treated, humans are the preferred subjects. Subjects may be adult, adolescent, juvenile, infant, or neonatal. In one embodiment of the invention, the subject is a live embryo, and may be in utero or in vitro (in the case of an embryo being maintained for in vitro fertilization).
[0041] Subjects may be administered the compounds and compositions of the present invention by any suitable means. Exemplary means are oral administration (e.g., in the form of a liquid or solid), intramuscular injection, subcutaneous injection, and intravenous injection. Pharmaceutical formulations of the present invention comprise active compounds of the invention in a pharmaceutically acceptable carrier. Suitable pharmaceutical formulations include those suitable for inhalation, oral, rectal, topical, (including buccal, sublingual, dermal, vaginal and intraocular), parenteral (including subcutaneous, intradermal, intramuscular, intravenous and intraarticular) and transdermal administration. The most suitable route of administration in any given case may depend upon the anatomic location of the condition being treated in the subject, the nature and severity of the condition being treated, and the particular active compound which is being used. The formulations may conveniently be presented in unit dosage form and may be prepared by any of the methods well known in the art.
[0042] In methods of the present invention where treatment is carried out during an in vitro fertilization (IVF) procedure, the compounds may be administered to the embryo by adding the active compound, in a suitable concentration, to the medium in which the embryo is being obtained.
[0043] In the manufacture of a medicament according to the invention (the “formulation”), active compounds or the pharmaceutically acceptable salts thereof (the “active compounds”) are typically admixed with, inter alia, an acceptable carrier. The carrier must, of course, be acceptable in the sense of being compatible with any other ingredients in the formulation and must not be deleterious to the patient. The carrier may be a solid or a liquid, or both, and is preferably formulated with the compound as a unit-dose formulation, for example, a tablet, which may contain from 0.5% to 99% by weight of the active compound. One or more active compounds may be incorporated in the formulations of the invention, which formulations may be prepared by any of the well known techniques of pharmacy consisting essentially of admixing the components, optionally including one or more accessory therapeutic ingredients.
[0044] Formulations suitable for oral administration may be presented in discrete units, such as capsules, cachets, lozenges, or tablets, each containing a predetermined amount of the active compound; as a powder or granules; as a solution or a suspension in an aqueous or non-aqueous liquid; or as an oil-in-water or water-in-oil emulsion. Such formulations may be prepared by any suitable method of pharmacy which includes the step of bringing into association the active compound and a suitable carrier (which may contain one or more accessory ingredients as noted above). In general, the formulations of the invention are prepared by uniformly and intimately admixing the active compound with a liquid or finely divided solid carrier, or both, and then, if necessary, shaping the resulting mixture. For example, a tablet may be prepared by compressing or molding a powder or granules containing the active compound, optionally with one or more accessory ingredients. Compressed tablets may be prepared by compressing, in a suitable machine, the compound in a free-flowing form, such as a powder or granules optionally mixed with a binder, lubricant, inert diluent, and/or surface active/dispersing agent(s). Molded tablets may be made by molding, in a suitable machine, the powdered compound moistened with an inert liquid binder. Formulations for oral administration may optionally include enteric coatings known in the art to prevent degradation of the formulation in the stomach and provide release of the drug in the small intestine.
[0045] Formulations of the present invention suitable for parenteral administration comprise sterile aqueous and non-aqueous injection solutions of the active compound, which preparations are preferably isotonic with the blood of the intended recipient. These preparations may contain anti-oxidants, buffers, bacteriostats and solutes which render the formulation isotonic with the blood of the intended recipient. Aqueous and non-aqueous sterile suspensions may-include suspending agents and thickening agents. The formulations may be presented in unit\dose or multi-dose containers, for example sealed ampoules and vials, and may be stored in a freeze-dried (lyophilized) condition requiring only the addition of the sterile liquid carrier, for example, saline or water-for-injection immediately prior to use. Extemporaneous injection solutions and suspensions may be prepared from sterile powders, granules and tablets of the kind previously described. For example, in one aspect of the present invention, there is provided an injectable, stable, sterile composition comprising a compound of Formula (I)-Formula (VI), or a salt thereof, in a unit dosage form in a sealed container. The compound or salt is provided in the form of a lyophilizate which is capable of being reconstituted with a suitable pharmaceutically acceptable carrier to form a liquid composition suitable for injection thereof into a subject. The unit dosage form typically comprises from about 10 mg to about 10 grams of the compound or salt. When the compound or salt is substantially water-insoluble, a sufficient amount of emulsifying agent which is physiologically acceptable may be employed in sufficient quantity to emulsify the compound or salt in an aqueous carrier.
[0046] Further, the present invention provides liposomal formulations of the compounds disclosed herein and salts thereof. The technology for forming liposomal suspensions is well known in the art. When the compound or salt thereof is an aqueous-soluble salt, using conventional liposome technology, the same may be incorporated into lipid vesicles. In such an instance, due to the water solubility of the compound or salt, the compound or salt will be substantially entrained within the hydrophilic center or core of the liposomes. The lipid layer employed may be of any conventional composition and may either contain cholesterol or may be cholesterol-free. When the compound or salt of interest is water-insoluble, again employing conventional liposome formation technology, the salt may be substantially entrained within the hydrophobic lipid bilayer which forms the structure of the liposome. In either instance, the liposomes which are produced may be reduced in size, as through the use of standard sonication and homogenization techniques.
[0047] Of course, the liposomal formulations containing the pharmaceutically active compounds identified with the methods described herein may be lyophilized to produce a lyophilizate which may be reconstituted with a pharmaceutically acceptable carrier, such as water, to regenerate a liposomal suspension.
[0048] In addition to the active compounds, the pharmaceutical formulations may contain other additives, such as pH-adjusting additives. In particular, useful pH-adjusting agents include acids, such as hydrochloric acid, bases or buffers, such as sodium lactate, sodium acetate, sodium phosphate, sodium citrate, sodium borate, or sodium gluconate. Further, the compositions may contain microbial preservatives. Useful microbial preservatives include methylparaben, propylparaben, and benzyl alcohol. The microbial preservative is typically employed when the formulation is placed in a vial designed for multidose use. Of course, as indicated, the pharmaceutical formulations of the present invention may be lyophilized using techniques well known in the art.
[0049] Pharmaceutical formulations of the present invention may comprise compounds of the present invention in lyophilized form. Alternatively, pharmaceutical formulations of the present invention may comprise compounds of the present invention in a pharmaceutically acceptable carrier. Such pharmaceutical formulations are generally made by admixing the compounds described herein with a pharmaceutically acceptable carrier. Pharmaceutically acceptable carriers are preferably liquid, particularly aqueous, carriers, the selection of which are known in the art. For the purpose of preparing such formulations, the compound may be mixed in a buffered saline (e.g., pH 6 to 8) or conventional culture media. The formulation may be stored in a sterile glass container sealed with a rubber stopper through which liquids may be injected and formulation withdrawn by syringe.
[0050] With respect to all the methods described herein, a therapeutically effective dosage of any specific compound the use of which is in the scope of present invention, may vary somewhat from compound to compound and subject to subject, and will depend upon the condition of the subject and the route of delivery. A dosage from about 1 mg/kg to about 15 mg/kg of subject body weight, or about 20 mg/kg of subject body weight, or even about 25 mg/kg of subject body weight may be employed for intravenous injection or oral administration.
[0051] The concentration of the compound of the present invention or a pharmaceutically acceptable salt thereof in a formulation of the present invention may be determined by the skilled artisan and will vary according to certain conditions, including the characteristics of subject being treated (e.g., species, age, weight), the severity and type of the infecting virus or the strain that the subject is being vaccinated against, the dosage form being used, and the like.
[0052] The compounds of the present invention may be administered in conjunction with other antiviral compounds, as may be determined by the skilled artisan.
[0053] The present invention is explained in greater detail in the Examples which follow. These examples are intended as illustrative of the invention, and are not to be taken as limiting thereof.
EXAMPLES 1-12
Synthesis of Inventive Compounds
[0054] In the following Examples, compound numbers (compounds 2, 5, 5a, etc.) refer to compounds with structures that are set forth in FIG. 1 .
EXAMPLE 1
[0055] General Methodology: Chemical Synthesis and Analysis
[0056] Melting points were determined with a MEL-TEMP® 3.0 capillary melting point apparatus and are uncorrected. 1 H nuclear magnetic resonance spectra were recorded on a Varian Unity+300 or a Varian VRX 400 instrument, with peak assignments relative to residual DMSO (2.49 ppm) or CHCl 3 (7.24 ppm). Mass spectra were recorded on a VG Instruments 70-SE spectrometer at the Georgia Institute of Technology, Atlanta, Ga. Elemental analyses were performed by Atlantic Microlab, Norcross, Ga. All final compounds were dried in vacuo (oil pump) at 50-60° C. for at least 36 hours before elemental analysis. Unless otherwise stated, all reagent chemicals and solvents (including anhydrous solvents) were purchased from Aldrich Chemical Co., Fisher Scientific, or Lancaster Synthesis and used as received. Acetonitrile (CaH 2 ), triethylamine (CaH 2 ), and ethanol (Mg/I 2 ) were distilled from the indicated drying agent. 2,6-Dimethyl-4-nitrobromobenzene and S-(2-Naphthylmethyl)thioacetimidate were prepared according to the literature. See B. M. Wepster, Rec. Trav. Chim. 73, 809-818 (1954), D. N. Kravtsov, J. Organometal. Chem. 36, 227-237 (1972); B. G. Shearer et al., Tetrahedron Lett. 38, 179-182 (1997).
EXAMPLE 2
Preparation of 2,5-bis(4-nitrophenyl)furans
[0057] The following representative procedures are variations of a general procedure previously described in A. Kumar et al., Heterocyclic Comm. 5, 301-304 (1999).
[0058] 2,5-Bis(2-methyl-4-nitrophenyl)furan (Compound 2b). To a solution of 2-bromo-5-nitrotoluene (4.32 g, 20 mmol) and tetrakis(triphenylphospine)palladium (0) (0.40 g) in anhydrous 1,4-dioxane (50 ml) was added 2,5-bis(tri-n-butylstannyl)furan (6.46 g, 10 mmol) and the mixture was heated overnight under nitrogen at 95-100° C. The resulting orange suspension was diluted with hexanes (15 ml), cooled to room-temperature, and filtered to give, after rinsing with hexanes, an orange solid (3.10 g), mp 241-243° C. The product was recrystallized from DMF (100 ml) to give a bright orange fluffy solid (2.87 g, 85%), mp 242-243° C. 1 H NMR (DMSO-d 6 ): 2.69 (s, 6H), 7.31 (s, 2H), 8.12 (m, 4H), 8.23 (s, 2H). Anal. Calcd. for C 18 H 14 N 2 O 5 (338.31): C, H, N.
[0059] 2,5-Bis(4-nitrophenyl)furan (Compound 2a). Yield: 88%; orange fluffy solid; mp 269-270° C. (not recrystallized), lit. mp 270-272° C., Ling, C. et al., J. Am. Chem. Soc. 1994, 116, 8784-8792.
[0060] 2,5-Bis(2-methoxy-4-nitrophenyl)furan (Compound 2c). Yield: 77%; bright orange granular solid; mp 308-310° C. (DMF). 1 H NMR (DMSO-d 6 ): 4.10 (s, 6H), 7.37 (s, 2H), 7.90 (s, 2H), 7.94 (d, 2H), 8.22 (d, 2H). Anal. Calcd. for C 18 H 14 N 2 O 7 .0.1 H 2 O (372.11) C, H, N.
[0061] 2,5-Bis(2-chloro-4-nitrophenyl)furan (Compound 2d). Yield: 71%; fluffy orange solid; mp 247-247.5° C. (DMF/MeOH). 1 H NMR (DMSO-d 6 ): 7.70 (s, 2H), 8.29 (dd, J=8.8, 2.2 Hz, 2H), 8.36 (d, J=8.8 Hz, 2H), 8.43 (d, J=2.2 Hz, 2H). Anal. Calcd. for C 16 H 8 Cl 2 N 2 O 5 (379.15): C, H, N.
[0062] 2,5-Bis(4-nitro-2-trifluoromethylphenyl)furan (Compound 2e). Yield: 74%; fluffy golden needles; mp 158.5-159° C. (EtOH). 1 H NMR (DMSO-d 6 ): 7.38 (s, 2H), 8.24 (d, J=8.7 Hz, 2H), 8.57 (d, J=2.4 Hz, 2H), 8.62 (dd, J=8.6, 2.4 Hz, 2H). Anal. Calcd. for C 18 H 8 F 6 N 2 O 5 (446.26): C, H, N.
[0063] 2,5-Bis(2,6-dimethyl-4-nitrophenyl)furan (Compound 2f). Yield: 65%; yellow needles; mp 156.5-157.5° C. (DMF/EtOH/H 2 O). 1 H NMR (DMSO-d 6 ): 2.34 (s, 12H), 6.85 (s, 2H), 8.04 (s, 4H). Anal. Calcd. for C 20 H 18 N 2 O 5 (366.36): C, H, N.
EXAMPLE 3
Preparation of 2,5-bis(4-aminophenyl)furans
[0064] The following procedures are representative.
[0065] 2,5-Bis(4-amino-2-methylphenyl)furan (Compound 3b). To a suspension of the bis-nitro derivative 2b (2.87 g) in EtOAc (90 ml) and dry EtOH (10 ml) was added Pd/C (10%) (0.40 g) and the mixture was hydrogenated on a Parr apparatus at an initial pressure of ˜50 psi. After the uptake of hydrogen subsided (generally 3-6 hours), the resulting solution was filtered over Celite and the pale yellow to colorless filtrate was concentrated in vacuo to near dryness to give, after dilution with hexanes, the pure diamine as a pale yellow/green solid (2.17 g, 91%), mp 174-176° C., which required no purification. 1 H NMR (DMSO-d 6 ): 2.33 (s, 6H), 5.15 (br s, 4H), 6.42 (s, 2H), 6.46 (m, 4H), 7.35 (d, 2H). MS (EI): m/z 278 (M + ).
[0066] 2,5-Bis(4-aminophenyl)furan (Compound 3a). Yield: 94%; pale green/tan solid; mp 218-221° C., lit 46 mp 213-216° C. MS (EI): m/z 250 (M + ).
[0067] 2,5-Bis(4-amino-2-methoxyphenyl)furan (Compound 3c). The original oil was reconcentrated with benzene to give a yellow/tan solid which was triturated with ether. Yield: 79%; mp 201-202.5° C. 1 H NMR (DMSO-d 6 ): 3.80 (s, 6H), 5.25 (br s, 4H), 6.24 (dd, J=8.3, 2.0 Hz, 2H), 6.30 (d, J=1.9 Hz 2H), 6.56 (s, 2H), 7.48 (d, J=8.4 Hz, 2H). MS (EI): m/z310 (M + ).
[0068] 2,5-Bis(4-amino-2-trifluoromethylphenyl)furan, (Compound 3e). Original red oil crystallized from EtOAc/hexanes in two crops as a red/orange solid. Combined yield: 81%; mp (first/major crop) 89.5-91° C.; mp (second crop) 91.5-92° C. 1 H NMR (DMSO-d 6 ): 5.79 (br s, 4H), 6.52 (s, 2H), 6.82 (dd, J=8.4, 2.4 Hz, 2H), 6.98 (d, J=2.2 Hz, 2H), 7.43 (d, J=8.4 Hz, 2H). MS (EI): m/z 386 (M + );
[0069] 2,5-Bis(4-amino-2,6-dimethylphenyl)furan (Compound 3f). Yield: 99%; white fluffy solid; mp 144.5-146° C. 1 H NMR (DMSO-d 6 ): 2.01 (s, 6H), 5.06 (br s, 4H), 6.24 (s, 2H), 6.29 (s, 4H). MS (EI): m/z 306 (M + ).
[0070] 2,5-Bis(4-amino-2-chlorophenyl)furan (Compound 3d). To a suspension of the corresponding bis-nitro derivative 2d (1.22 g, 3.2 mmol) in dry EtOH (100 ml) and DMSO (20 ml) was added SnCl 2 .2H 2 O (5.80 g, 25.7 mmol) and the mixture was heated under nitrogen at 80° C. After 4-5 hours, TLC showed that starting material had been consumed, and thus the mixture was cooled, neutralized with NaOH (aq), and extracted with EtOAc. The extract was washed with water, brine, then dried (Na 2 SO 4 ) and concentrated. The resulting oil was crystallized from benzene/hexane with partial concentration to give a light brown solid (0.74 g, 71%), mp 191.5-193° C. Catalytic hydrogenation was not explored. 1 H NMR (DMSO-d 6 ): 5.60 (br s, 4H), 6.61 (dd, J=8.6, 2.2 Hz, 2H), 6.68 (d, J=2.2 Hz 2H), 6.82 (s, 2H), 7.56 (d, J=8.6 Hz, 2H). MS (EI): m/z 318 (M + ).
EXAMPLE 4
Preparation of 2,5-bis(4-N,N′-di-BOC-guanidinophenyl)furan derivatives
[0071] The following procedures are representative.
[0072] 2,5-Bis(4-N,N′-di-BOC guanidinophenyl)furan (Compound 4a). To a room-temperature solution of 2,5-bis(4-aminophenl)furan (0.626 g, 2.5 mmol) and 1,3-bis(tert-butoxycarbonyl)-2-methyl-2-thiopseudourea (1.56 g, 5.3 mmol) in anhydrous DMF was added triethylamine (1.59 g, 15.7 mmol) followed by mercury(II) chloride (1.57 g, 5.8 mmol) and the resulting suspension was stirred at room-temperature for 22 hours. After diluting with CH 2 Cl 2 and sodium carbonate solution, the suspension was filtered over Celite and the filtrate was washed well with water (3×) and finally with brine. After drying (Na 2 SO 4 ), the solvent was removed in vacuo and the residue was diluted with MeOH to give the BOC-protected bis-guanidine as a pale yellow solid. The collected product was purified by reprecipitation from CH 2 Cl 2 /MeOH to give a fluffy yellow solid (1.25 g, 68%), mp>400° C. dec. 1 H NMR (CDCl 3 ): 1.50 and 1.53 (2s, 36H), 6.65 (s, 2H), 7.66 (s, 8H) 10.38 (br s, 2H), 11.61 (br s, 2H).
[0073] 2,5-Bis(2-methyl-4-N,N′-di-BOCguanidinophenyl)furan (Compound 4b). Yellow solid, mp>250° C. dec. Yield: 62%. 1 H NMR (CDCl 3 ): 1.51 and 1.52 (2 s, 36H), 2.53 (s, 6H), 6.60 (s, 2H), 7.40 (s, 2H), 7.62 (d, 2H), 7.74 (d, 2H), 10.34 (s, 2H), 11.62 (br s, 2H).
[0074] 2,5-Bis(2-methoxy-4-N,N′-di-BOCguanidinophenyl)furan (Compound 4c). Yellow solid, mp>300° C. dec. Yield: 79%. 1 H NMR (CDCl 3 ): 1.50 and 1.53 (2 s, 36H), 3.95 (s, 6H), 6.95 (s, 2H), 7.13 (d, 2H), 7.59 (s, 2H), 7.86 (d, 2H), 10.36 (s, 2H), 11.55 (br s, 2H).
[0075] 2,5-Bis(2-chloro-4-N,N′-di-BOCguanidinophenyl)furan (Compound 4d). Pale yellow/tan solid, mp>400° C. dec. Yield: 63%. 1 H NMR (CDCl 3 ): 1.52 (s, 36H), 7.17 (s, 2H), 7.63 (dd, 2H), 7.79 (d, 2H), 7.88 (d, 2H), 10.43 (s, 2H), 11.59 (br s, 2H).
[0076] 2,5-Bis(2-trifluoromethyl-4-N,N′-di-BOC guanidinophenyl)furan (Compound 4e). Bright orange solid. Yield: 88%. 1 H NMR (CDCl 3 ): 1.51 and 1.53 (2s, 36H), 6.77 (s, 2H), 7.82 (d, 2H), 7.94 (s, 2H), 8.00 (d, 2H), 10.52 (s, 2H), 11.59 (br s, 2H).
[0077] 2,5-Bis(2,6-dimethyl-4-N,N′-di-BOC guanidinophenyl)furan (Compound 4f). Pale yellow/off-white solid, mp>300° C. dec. Yield: 89%. 1 H NMR (CDCl 3 ): 1.51 and 1.53 (2s, 36H), 2.23 (s, 12H), 6.31 (s, 2H), 7.33 (s, 4H), 10.27 (s, 2H), 11.63 (br s, 2H).
EXAMPLE 5
Deprotection of N,N′-di-BOC guanidines
[0078] The following procedures are representative, and are further illustrated in FIG. 1 .
[0079] 2,5-Bis(4-guanidinophenyl)furan dihydrochloride (Compound 5a). A solution of the corresponding N,N′-di-BOCguanidine (1.19 g, 1.62 mmol) in CH 2 Cl 2 (15 ml) was diluted with dry EtOH (10 ml) and saturated at ice-water bath temperature with anhydrous HCl. The solution was then stirred at room-temperature, for 2-3 days (drying tube), with the product slowly precipitating (shorter reaction times generally gave incomplete deprotection). The resulting suspension was concentrated to near dryness, with the solid then taken up in hot EtOH. After filtering to clarify, the solution was concentrated to near dryness to give a suspension, which was diluted with ether and collected to yield, after drying in vacuo at 50-60° C. for 2 days, the bis-guanidine dihydrochloride as an off-white/tan solid (0.66 g, quantitative), mp>300° C. dec. 1 H NMR (DMSO-d 6 ): 7.12 (s, 2H), 7.31 (d, 4H), 7.58 (br s, 8H), 7.86 (d, 4H), 10.09 (br s, 2H). MS (FAB, thioglycerol): m/z 335.3 (MH + , 100). Anal. Calcd. for C 18 H 18 N 6 O.2HCl.0.25EtOH (407.30): C, H, N.
[0080] 2,5-Bis(4-guanidino-2-methylphenyl)furan dihydrochloride (Compound 5b). Tan solid, mp 265-271° C. dec. 1 H NMR (DMSO-d 6 ): 2.53 (s, 6H), 6.93 (s, 2H), 7.17 (m, 4H), 7.56 (br s, 8H), 7.82 (d, 2H), 10.06 (br s, 2H). MS (FAB, thioglycerol): m/z 363.3 (MH + , 100). Anal. Calcd. for C 20 H 22 N 6 O.2HCl.1.5H 2 O.0.66EtOH (496.93): C, H, N.
[0081] 2,5-Bis(4-guanidino-2-methoxyphenyl)furan dihydrochloride (Compound 5c). Light brown solid. 1 H NMR (DMSO-d 6 ): 3.95 (s, 6H), 6.92 (dd, 2H), 6.99 (d, 2H), 7.02 (s, 2H), 7.58 (br s, 8H), 7.95 (d, 2H), 10.08 (br s, 2H). MS (EI): m/z 352 (M + -NH 2 CN, 38.0), 310 (100), 267 (38.9), 251 (8.8), 155 (18.7). Anal. Calcd. for C 20 H 22 N 6 O 3 .2HCl.1.0H 2 O.0.33EtOH (500.57): C, H, N.
[0082] 2,5-Bis(2-chloro-4-guanidinophenyl)furan dihydrochloride (Compound 5d). Tan solid, mp 300-304° C. dec. 1 H NMR (DMSO-d 6 ): 7.31 (s, 2H), 7.33 (d, 2H), 7.47 (s, 2H), 7.72 (br s, 8H), 8.04 (d, 2H). MS (DCI, ammonia): m/z 365, 363, 361 (M + -NH 2 CN, 8, 52, 78), 323, 321, 319 (11, 66, 100). Anal. Calcd. for C 18 H 16 Cl 2 N 6 O.2HCl.0.5H 2 O (485.21): C, H, N, Cl.
[0083] 2,5-Bis(4-guanidine-2-trifluoromethylphenyl)furan dihydrochloride (Compound 5e). Orange/red solid. 1 H NMR (DMSO-d 6 ): 6.99 (s, 2H), 7.63 (d, 2H), 7.69 (s, 2H), 7.79 (br s, 8H), 7.91 (d, 2H), 10.37 (br s, 2H). MS (CI, isobutane): m/z 471 (MH + , 14), 429 (100), 387 (19). Anal. Calcd. for C 20 H 16 F 6 N 6 O.2HCl.0.67H 2 O.0.67EtOh (586.24): C, H, N.
[0084] 2,5-Bis(4-guanidino-2,6-dimethylphenyl)furan dihydrochloride (Compound 5f). Off-white solid. 1 H NMR (DMSO-d 6 ): 2.20 (s, 12H), 6.56 (s, 2H), 7.01 (s, 4H), 7.57 (br s, 8H), 10.09 (br s, 2H). MS (FAB, thioglycerol): m/z 391.2 (MH + , 100). Anal. Calcd. for C 22 H 26 N 6 O.2HCl.0.5H 2 O (472.41): C, H, N.
EXAMPLE 6
Preparation of 2-[5(6)-Amidino-2-benzimidazoyl]-5-(4-nitrophenyl)furan
[0085] A mixture of 5-(4-nitrophenyl)furfural (0.651 g, 0.003 mol), 4-amidino-1,2-phenylenediamine (0.614 g, 0.003 mol) and 1,4-benzoquinone (0.324 g, 0.003 mol) in 40 ml of ethanol (under nitrogen) was heated at reflux for 8 h. The volume of the reaction mixture was reduced to 20 ml under reduced pressure, cooled and the resultant solid was collected by filtration. The solid was washed with cold ethanol and ether. The product was dried to yield the mono hydrochloride salt 0.8 g (70%). The mono salt (0.65 g) was dissolved in 120 ml of ethanol and acidified with HCl-saturated ethanol and after standing overnight in a refrigerator the resultant solid was filtered, washed with ether and dried for 24 h in a vacuum oven at 70° C. to yield 0.6 g (85%) mp 300° C. 1 H NMR (DMSO-d 6 ): 9.3 (br s, 2H), 9.09 (br s, 2H), 8.33 (d, J=7.6 Hz, 2H), 8.20 (d, J=7.6 Hz 2H), 8.19 (s,1H), 7.79 (d, J=8.4 Hz, 1H), 7.73 (d, J=8.4 Hz, 1H),7.56 (d, J=3.6 Hz, 1H), 7.51 (d, J=3.6 Hz 1H). 13 C NMR (DMSO-d 6 ): 165.9, 152.6, 146.4, 145.4, 145.3, 141.6, 138.7, 134.7, 124.6, 124.0, 122.1, 121.5, 116.0, 114.6, 114.0, 111.9. FABMS m/e 348(M + +1). Anal. Calcd for C 18 H 13 N 5 O 3 .2HCl.: C, 51.44; H, 3.59; N, 16.66. Found: C, 51.24; H, 4.03; N, 16.92.
EXAMPLE 7
Preparation of 2-[5(6)-amidino-2-benzimidazoyl]-5-(4-aminophenyl)furan
[0086] The above nitro analog (0.5 g, 0.0013 mol) and 0.3 g of 10% Pd/C in 130 ml of methanol was subjected to hydrogenation at 50 psi for 4 h. The catalyst was removed by filtration over filteraid and the solvent was removed under reduced pressure. The solid was taken up in methanolic HCl, warmed on a water bath for 0.5 h and the solvent was removed under reduced pressure. The residue was treated with ether and the solid was collected by filtration and dried under vacuum at 75° C. for 12 h to yield 0.44 g (73%) mp>360° C. 1 H NMR (DMSO-d 6 /D 2 O): 8.07 (d, J=1.6 Hz, 1H), 7.74(d, J=8.4 Hz, 2H), 7.66 (dd, J=1.6 and 8.4 Hz 2H), 7.39 (d, J=3.6 Hz, 1H), 6.91 (d, J=3.6 Hz, 1H),6.89 (d, J=8.4 Hz, 2H). 13 C NMR (DMSO-d 6 /D 2 O): 166.2, 156.7, 145.8, 142.0, 141.0, 138.1, 126.2, 123.2, 122.3, 119.2, 116.6, 116.0, 115.1, 107.5. FABMS m/e 318(M + +1). Anal. Calcd. for C 18 H 15 N 5 O.3HCl.2H 2 O: C, 43.59; H, 6.09; N, 16.92. Found: C, 43.71, H, 6.01, N, 16.81.
EXAMPLE 8
Preparation of 2-[5(6)-{2-imidazolinyl}-2-benzimidazoyl]-5-(4-nitrophenyl)furan
[0087] A mixture of 5-(4-nitrophenyl)furfural (0.434 g, 0.002 mol), 4-(2-imidazolinyl)-1,2-phenylenediamine hydrochloride hydrate (0.461 g, 0.002 mol) and 1,4-benzoquinone (0.216 g, 0.002 mol) in 40 ml of ethanol (under nitrogen) was heated at reflux for 8 h. The volume of the reaction mixture was reduced to 20 ml under reduced pressure, cooled and the resultant solid was collected by filtration. The solid was washed with cold ethanol and ether. The product was dried to yield 0.52 g (63%). The compound was dissolved in 200 ml of ethanol and acidified with HCl-saturated ethanol and was stirred at room temperature for 3 h. The mixture was cooled on ice and the solid was filtered, washed with ether and dried for 24 h in a vacuum oven at 75° C. to yield 0.51 g (90%) Mp >300° C. 1 H NMR (DMSO-d 6 /D 2 0): 8.31 (d, J=8.4 Hz, 2H), 8.30 (s, 1H), 8.15 (d, J=8.4 Hz, 2H), 7.81 (s, 2H), 7.52 (d, J=4.0 Hz, 1H), 7.46 (d, J=4.0 Hz, 1H), 4.03 (s,4H). 13 C NMR (DMSO-d 6 /D 2 0): 165.6, 153.1, 146.8, 145.7, 145.2, 134.7, 124.9; 124.2, 122.8, 116.9, 115.8, 115.1, 115.0, 112.1, 105.6, 104.7, 44.2. FABMS m/e 374 (M + +1). Anal. Calcd for C 20 H 15 N 5 O 3 .2HCl: C, 53.82; H, 3.88; N, 15.69. Found: C, 53.94; H, 3.93; N, 15.84.
EXAMPLE 9
Preparation of 2-[5(6)-{2-imidazolinyl}-2-benzimidazoyl]-5-(4-aminophenyl)furan
[0088] The mono hydrochloride salt of the above nitro analog (0.5 g, 0.0013 mol) and 0.2 g of 10% Pd/C in 130 ml of methanol was subjected to hydrogenation at 50 psi for 4 h. The catalyst was removed by filtration over filteraid, washed with warm methanol. The solvent volume was reduced to approximately half under reduced pressure. The flask containing the solution was placed in an ice bath and saturated with HCl gas. The mixture was stirred at room temperature for 4 h and treated with dry ether and the solid was collected by filtration. The solid was dried under vacuum at 75° C. for 24 h to yield 0.55 g (86%) mp>300° C. 1 H NMR (DMSO-d 6 /D 2 0): 8.24 (d, J=1.2 Hz 1H), 7.88 (d, J=8.0 Hz, 2H), 7.80 (s, 2H), 7.51(d, J=3.6 Hz, 1H), 7.21 (d, J=8.4 Hz, 2H),7.10 (dd, J=1.2,3.6 Hz, 1H), 4.0 (s,4H). 13 C NMR (DMSO-d 6 /D 2 0): 165.8, 156.4, 145.8, 142.0, 140.9, 137.9, 126.2, 123.7, 121.0, 117.0, 116.8, 115.3, 108.5, 44.6. FABMS n/e 344(M + +1). Anal. Calcd for C 20 H 17 N 5 O.3HCl 2 .1H 2 O: C, 48.96; H, 4.97; N, 14.27. Found: C, 48.58; H, 4.32; N, 14.27.
EXAMPLE 10
Preparation of 2-[5(6)-{N-isopropylamidino}-2-benzimidazoyl]-5-(4-nitrophenyl)furan
[0089] A mixture of 5-(4-nitrophenyl)furfural (0.434 g, 0.002 mol), 4-N-isopropylamidino-1,2-phenylenediamine hydrochloride hydrate (0.493 g, 0.002 mol) and 1,4-benzoquinone (0.216 g, 0.002 mol) in 40 ml of ethanol (under nitrogen) was heated at reflux for 6 h. The volume of the reaction mixture was reduced to about 15 ml under reduced pressure, the mixture was cooled and the resultant solid was collected by filtration to yield the mono hydrochloride salt 0.66 g (80%). The mono salt was dissolved in 100 ml of ethanol and acidified with HCl-saturated ethanol and after cooling in an ice bath the resultant solid was filtered, washed with ether and dried for 24 h in a vacuum oven at 75° C. to yield 0.7 g (91%) mp>300° C. 1 H NMR (DMSO-d 6 /D 2 0): 8.26 (d, J=8.8 Hz, 2H), 8.11 (d, J=8.8 Hz 2H), 8.01 (d, J=1.2 Hz, 1H), 7.77 (d, J=8.8 Hz, 1H), 7.59 (dd, J=1.2, 8.8 Hz, 1H),7.50(d, J=7.6 Hz, 1H), 7.42 (d, J=7.6 Hz 1H),4.04 (septet, J=6.8 Hz,1H), 1.3(d, J=6.8 Hz,6H). 13 C NMR (DMSO-d 6 ): 162.7, 153.8, 147.2, 145.2, 144.8, 140.7, 138.2, 135.2, 125.4, 124.7, 124.0, 123.5, 116.3, 115.9, 115.3, 112.6, 45.6, 21.4. FABMS m/e 376(M + +1). Anal. Calcd for C 21 H 19 N 5 O 3 .2HCl.2.0H 2 O: C, 49.71; H, 5.16; N, 13.80. Found: C, 49.65; H, 5.11; N, 13.50.
EXAMPLE 11
2-[5(6)-N-isopropylamidino-2-benzimidazoyl]-5-(4-aminophenyl)furan
[0090] The mono hydrochloride salt of the above nitro analog (0.411 g, 0.001 mol) and 0.3 g of 10% Pd/C in 120 ml of methanol was subjected to hydrogenation at 50 psi for 4 h. The catalyst was removed by filtration over filteraid, washed with warm methanol. The solvent volume was reduced to approximately half under reduced pressure. The flask containing the solution was placed in an ice bath and saturated with HCl gas. The mixture was stirred at room temperature for 4 h and treated with dry ether and the solid was collected by filtration. The solid was dried under vacuum at 80° C. for 24 h to yield 0.41 g (87%) mp >300° C. 1 H NMR (DMSO-d 6 /D 2 0): 8.04 (d, J=1.6 Hz, 1H), 7.91 (d, J=8.4 Hz 2H), 7.80 (d, J=8.4 Hz 1H), 7.64 (dd, J=1.6,8.4 Hz, 1H), 7.60 (d, J=4.0 Hz, 1H),7.24(d, J=8.4 Hz, 2H), 7.14 (d, J=4.0 Hz 1H),4.05 (septet, J=6.4 Hz,1H), 1.3(d, J=6.4 Hz,6H). 13 C NMR (DMSO-d 6 ): 162.4, 156.8, 144.4, 140.9, 138.8, 137.6, 135.0, 126.3, 125.4, 124.6, 124.1, 121.1, 118.0, 115.6, 114.9, 108.6, 45.6, 21.3. FABMS m/e 360(M + +1). Anal. Calcd for C 21 H 21 N 5 O 3 .3HCl: C, 53.80; H, 5.15; N, 14.93. Found: C, 54.22; H, 4.75; N, 15.05.
EXAMPLE 12
2,5-Bis(2-Benzimidazolyl-4-cyanophenyl)furan
[0091] A mixture of 5-[4-cyanophenyl]-2-furancarboxaldehyde (1.97, 0.01 mol), 1,2-phenylenediamine (1.06 g, 0.01 mol) and 1,4-benzoquinone (1.08 g, 0.01 mol) in 50 ml dry ethanol was heated at reflux (under nitrogen) for 8 h. The reaction mixture was cooled and diluted with ether and filtered. The solid was collected and stirred with 1:3 mixture of EtOH and ether for 20 min and the yellow brown solid was filtered, washed with ether and dried in vacuum at 70° C. for 12 h. which yielded 1.96 g (69%), mp227-8° C. dec, 1 H-NMR(DMSO-d6): 8.06 (d, 2H, J=8.8 Hz), 7.91(d, 2H,J=8.8 Hz), 7.60 (dd, 2H, J=3.2 Hz, J=6.4 ), 7.38 (d, 1H, J=3.6 Hz), 7.32(d, 1H, J=3.6 Hz), 7.23 (dd, 2H, J=3.2 Hz, J=6.4 Hz). 13 C-NMR(DMSO-d6): 152.1, 146.0, 142.7, 138.7, 133.2, 132.6, 124.1, 122.3, 118.4, 114.9, 112.5, 111.1, 109.8, MS: m/e 285 (M+). Anal. calcd. for: C18H11N3O: C, 75.79; H, 3.86; N, 14.73. Found: C, 75.88; H, 3.77; N, 14.55.
2,5-Bis[2-Benzimidazolyl-4-(amidino)phenyl]furan dihydrochloride
[0092] The above cyano compound (2.85 g, 0.01 mol) in 60 ml ethanol was saturated with dry HCl gas at 0-5° C. The reaction mixture was stirred at room temperature for 12 days (monitored by IR and TLC). The mixture was diluted with ether and the yellow imidate ester hydrochloride was filtered, washed with ether and dried under vacuum for 6 h 3.73 g (92%). The solid was used in next step without further purification. A suspension of the imidate ester hydrochloride (0.808 g, 0.002 mol) in 35 ml ethanol was saturated with ammonia gas at 0-5° C. and stirred for 24 h at room temperature. The solvent was reduced to one-third under reduced pressure, diluted with ether and filtered. The yellow solid was resuspended in 10 ml ethanol and treated with 4 ml saturated ethanolic HCl and stirred at 35° C. for 2 h. The solvent was removed under vacuum and the residue triturated with ether, filtered, washed with ether and dried under vacuum at 45° C. for 24 h to yield 0.61 g (81%) yellow solid mp>280° C. dec. 1 H-NMR(DMSO-d6/D2): 8.15(d, 2H, J=8.7 Hz), 7.93 (d, 2H, J=8.7 Hz), 7.78 (d, 1H, J=3.6 Hz), 7.75 (dd, 2H, J=3 Hz, J=6.3 Hz), 7.50 (d, 1H, J=3.6 Hz), 7.49 (dd, 1H, J=3 Hz, J=6.3 Hz). 13 C-NMR(DMSO-d6): 165.0, 155.9, 139.8, 139.7, 133.4, 132.4, 129.3, 127.8, 126.3, 125.2, 119.5, 114.3, 112.0. FABMS: m/e 303 (M++1). Anal. calcd. for: C18H14N4O.2HCl: C,57.61; H,4.29; N, 14.93. Found; C, 57.45; H, 4.46; N, 14.64.
2,5-Bis[2-Benzimidazolyl4-(2-imidazolino)phenyl]furan dihydrochloride
[0093] A mixture of the imidate ester hydrochloride (0.808 g, 0.002 mol) from above, ethylenediamine (0.12 g, 0.002 mol) in 20 ml of dry ethanol was heated at reflux for 12 h. The solvent volume was reduced to 8 ml under reduced pressure and diluted with ether. The resultant solid was filtered and dried. This solid was dissolved in 35 mL hot ethanol and saturated with HCl gas at room temperature. The mixture was stirred at 50° C. for 2 h and concentrated under reduced pressure and 30 ml dry ether was added. The precipitated yellow salt was filtered, washed with ether and dried under vacuum at 70° C. for 24 h to yield 0.69 g (84%) yellow solid mp>300° C. dec. 1 H-NMR(DMSO-d6/D2): 8.06(d, 2H, J=8.7 Hz), 7.91 (d, 2H, J=8.7 Hz), 7.71 (dd, 2H, J=3 Hz, J=6 Hz), 7.64 (d, 1H, J=3.9 Hz), 7.47(dd, 1H, J=3 Hz, J=6.3 Hz), 7.44 (d, 1H, J=3.9 Hz), 3.94 (s, 4H). 13 C-NMR(DMSO-d6): 164.6, 155.7, 140.3, 140.1, 133.9, 132.9, 129.7, 126.7, 125.4, 122.1, 119.2, 114.6, 112.5, 44.8, FABMS: m/e 303 (M++1). Anal. calcd for: C20H16N4O.2HCl.0.5H2O: C,58.54; H,4.67; N, 13.65. Found; C, 58.54; H, 4.67; N, 13.66.
EXAMPLES 13-24
[0094] Anti-BVDV Properties of Inventive Compounds
EXAMPLE 13
[0095] Screening of Antiviral Compounds for Anti-BVDV Activity
[0096] 2.0 cm 2 wells in a 24-well plate were seeded with 50 μl of medium from 12 ml of MEM-eq (minimum essential medium (MEM) with Earle's salts supplemented with 10% (v/v) equine serum, sodium bicarbonate (0.75 mg/ml), L-glutamine (0.29 mg/ml), penicillin G (100 U/ml), streptomycin (100 μg/ml), and amphotericin B (0.25 μg/ml)), which was derived by trypsinization of a confluent monolayer of Madin Darby Bovine Kidney (MDBK) cells in a 25 cm 2 flask. Cells were incubated at 38.5° C. with 5% CO 2 for 24 hours. The average number of cells per well was determined and later used to calculate appropriate multiplicities of infection (MOI) of BVDV virus.
[0097] Cells were inoculated with BVDV in medium containing test antiviral compounds (12.5 μM, 200 μL total volume), as follows:
two wells had no BVDV, and no antiviral compound one well had BVDV at 0.05 MOI, and no antiviral compound one well had BVDV at 1.0 MOI, and no antiviral compound ten wells had BVDV at 0.05 MOI, and 12.5 μM of antiviral compound ten wells had BVDV at 1.0 MOI, and 12.5 μM of antiviral compound.
[0103] The inoculated cells incubated for one hour at 38.5° C. with 5% CO 2 in humidified air. The medium was removed from the wells, and the cells washed one time with Ca 2+ and Mg 2+ -free PBS comprising antiviral compound (12.5 μM) (cells in the wells not initially treated with antiviral compounds were washed without antiviral compound). One ml of MEM-eq comprising antiviral compound (12.5 μM) was added to wells initially treated with antiviral compound; those not treated with antiviral compound initially did not receive antiviral compound at this step. Three days post-inoculation, medium was removed and stored at −20° C. for assay. One ml of fresh medium containing 200 μL total (12.5 μM) antiviral compound was is added to wells initially treated with antiviral compound; those not treated with antiviral compound initially did not receive antiviral compound at this step. Seven days post-inoculation, medium was removed and stored at −80° C. for serial dilution & assay.
[0104] The MDBK cells were resuspended in MEM-eq with no antiviral compound. Uterine tubal cells (UTC) were freeze-thawed and stored at −80° C. for analysis. UTC lysates were serially diluted with medium from Day 7 and assayed by immunoperoxidase for the presence of BVDV.
EXAMPLE 14
[0105] Immunoperoxidase Monolayer Assay for BVDV
[0106] All samples were assayed for BVDV using the immunoperoxidase monolayer assay as described in A. Afshar et al., Can J Vet Res; 55:91-93 (1991). Samples were assayed in triplicate by adding 50 μL of MEM-eq containing approximately 2.5×10 3 MDBK cells to 50-μL of each sample supplemented with 50 μL of fresh MEM-eq in a 96-well culture plate. Plates were incubated for 72 h at 38.5° C. in a humidified atmosphere of 5% CO2 and air before the immunoperoxidase labeling technique was performed as follows:
[0107] After fixation, potentially infected cells were incubated with monoclonal antibodies D89 (M. L. Vickers et al., J Vet Diagn Invest 2, 300-302 (1990); Xue W et al., J Clin Microbiol 28,1688-1693 (1990)) specific for E2/gp53, a major envelope glycoprotein of BVDV (Xue W et al., Vet Microbiol 57,105-118 (1997)) and 20.10.6 specific for NS3-p80, a conserved nonstructural protein (W. V. Corapi et al., Am J Vet Res 51, 1388-1394 (1990)). After washing with PBS and Tween 20 to remove unbound antibodies, peroxidase-conjugated rabbit anti-mouse IgG (Jackson Immuno Research Lab, West Grove, Pa.) was added. After a short incubation period, unbound peroxidase-conjugated antibody was removed by washing with PBS and Tween 20. Finally, the enzyme substrate, aminoethyl carbazole (Zymed Laboratories, Inc., South San Francisco, Calif.), which produces a reddish-brown color when oxidized by horseradish peroxidase, was added. Color change was visualized under light microscopy and compared to known positive and negative controls on each plate.
EXAMPLE 15
[0108] Tissue Culture Passage
[0109] All samples other than stock virus aliquots were also passaged in tissue culture to optimize isolation of BVDV. Upon initial thawing, 200 μL of each sample was inoculated onto a 2 cm 2 well seeded 24 h previously with MDBK cells. Passages were incubated 5 days (d) at 38.5° C. in an atmosphere of 5% CO 2 and humidified air. Passages were frozen at −80° C. for storage. Tissue culture passage samples were thawed and assayed by virus isolation if isolation of BVDV was unsuccessful from the original sample. Samples were reported to be free of BVDV by virus isolation only if virus was not detected after each of two serial passages.
EXAMPLE 16
[0110] Reverse Transcription Nested Polymerase Chain Reaction Assay (RT-nPCR)
[0111] A reverse transcription nested polymerase chain reaction assay for detecting BVDV was performed on all samples other than stock virus aliquots. Upon initial thawing, RNA was isolated from samples using the QIAamp® viral RNA mini kit (Qiagen, Valencia, Calif.) according to the manufacturer's instructions. RNA samples were stored at −80° C. until RT-nPCR was performed.
[0112] All steps of complementary DNA production (cDNA) and amplification were carried out in a single closed-tube reaction using a modification of the protocol of McGoldrick et al. (see Duffell S J et al., Vet Rec 1985;117:240-245; Givens M D, et al., Theriogenology 2000;54:1093-1107; Lang-Ree J R, et al., Vet Rec 1994;135:412-413). In the first step, 5 μL of trehalose (22% w/v stock; Sigma, St Louis, Mo., cat #T5251) was used to store and maintain the following mixture in the lid of a 200-μL, thin-walled tube: 0.4 μL of each inner primer BVD 180 and HCV 368(50 μM); 1 μL of dNTPs (10 mM) and 0.25 μL of Taq Polymerase (1.25 U, Promega, Madison, Wis.). The tubes were left to dry for 2 h at room temperature prior to storage.
[0113] In the second step, the initial reverse transcription polymerase chain reaction was performed in the bottom of the tubes containing the dried trehalose mixture within the lid. Two μL of RNA were added through the overlaid mineral oil (50 μL) to the initial reaction volume (48 μL) containing the following reagents (Promega): 5 μL 10× buffer, 8 μL of MgCl2 (25 mM), 2 μL of dNTPs (10 mM), 1 μL of each outer primer BVD 100 and HCV 368 (5 μM), 1 μL of Triton X-100 (10% stock), 0.25 μL of dithiothreitol (100 mM), 0.25 μL (10 U) RNAsin, 0.5 μL (2.5 U) of Taq polymerase, and 0.5 μL (100 U) of MMLV (Moloney Murine Leukemia Virus) reverse transcriptase. The tubes were then subjected to the following cycle parameters: 37° C. for 45 min 95° C. for 5 min and then 20 cycles at 94° C. for 1 min, 55° C. for 1 min and 72° C. for 1 min.
[0114] A final elongation step of 72° C. for 10 min completed the initial amplification reaction. In the third step, the tubes were inverted several times to mix the samples in the lid and in the base to initiate the nested polymerase chain reaction (nPCR). The tubes were then centrifuged at 14,000×g for 12 sec before returning to the thermocycler for nPCR, using 30 cycles of 94° C. for 1 min, 55° C. for 1 min and 72° C. for 45 sec. A final elongation step of 72° C. for 10 min completed the amplification process prior to maintaining the reactions at 4° C. Five microliter aliquots of PCR products were separated by 1.5% agarose gel electrophoresis. The agarose gels contained 0.5 μg/ml ethidium bromide to allow visualization of RT-nPCR products using an ultraviolet transilluminator.
[0115] The outer primers, BVD 100 (5′-GGCTAGCCATGCCCTTAG-3′) (SEQ ID NO. 1) and HCV 368 (5′-CCATGTGCCATGTACAG-3′) (SEQ ID NO. 2) amplified a 290 base pair sequence of the 5′ untranslated region of the viral genome. The inner primers, BVD 180 (5′-CCTGAGTACAGGGDAGT CGTCA-3′) (SEQ ID NO. 3) and HCV 368 amplified a 213 base pair sequence within the first amplicon. The novel BVD 180 primer was degenerate at the 14th base (D=G+A+T) to accommodate differences within the 5′ untranslated sequences of virus strains used in this research as determined by automated dye terminator nucleotide sequencing (Nucleic Acid Resource Facility, Auburn University, AL) of the initial PCR products from viral stocks.
EXAMPLE 17
[0116] Oocyte Collection and Maturation
[0117] Cow ovaries were collected at an abattoir in Omaha, Neb., and placed in PBS for transport to a nearby laboratory. The contents of 1- to 10-mm follicles were aspirated at a vacuum rate of 21.5 ml/min and poured onto a 70 μm filter. Cellular components of the pooled follicular aspirate were rinsed with TL-HEPES and searched for oocytes surrounded by multiple layers of dense cumulus cells. Useable cumulus oocyte complexes (COCs) were washed two additional times in TL-HEPES, then placed in 7.5 ml of maturation media that had previously equilibrated at 38.5° C. in an atmosphere of 5% CO 2 and humidified air. The maturation media was then sealed and maintained at 38.5° C. for 20 to 22 h while being transported to the experimental laboratory.
EXAMPLE 18
[0118] Media for in vitro Fertilization/Embryo Assays
[0119] Oocytes were matured in cell culture medium 199 (CCM 199) with Earle's salts (GIBCO-BRL, Grand Island, N.Y., USA) supplemented with 10% (v/v) heat-inactivated fetal bovine serum (FBS; HyClone Lab., Inc., Logan, Utah, USA), sodium pyruvate (11 μg/ml), bovine FSH (0.01 U/ml), bovine LH (0.01 U/ml), penicillin (100 U/ml) and streptomycin (100 μg/ml).
[0120] Matured oocytes were fertilized in CR2 medium (C. F. Rosenkrans et al., Theriogenology 35, 266 (1991)) supplemented with BSA (6 mg/ml), heparin (10 μg/ml), penicillamine (0.3 μg/ml), hypotaurine (0.2 μg/ml), penicillin (100 U/ml) and streptomycin (100 μg/ml).
[0121] The first three days (d) of in vitro culture (IVC) was in CR2 medium supplemented with BSA (6 mg/ml), penicillin (100 U/ml) and streptomycin (100 μg/ml). The last four d of IVC was in CR2 medium supplemented with 10% (v/v) FBS, penicillin (100 U/ml) and streptomycin (100 μg/ml).
EXAMPLE 19
[0122] Exposure to Bovine Viral Diarrhea Virus (BVDV)
[0123] After in vitro maturation (IVM), COCs were washed 5 times in 3 ml of MEM-eq. After washing, COCs were exposed to a noncytopathic strain of BVDV in 3 ml of MEM-eq or maintained separately as negative controls in BVDV-free MEM-eq. Exposed and unexposed COCs were incubated for 1 h at 38.5° C. in an atmosphere of 5% CO2 and humidified air, and then washed 3 times in 3 ml of TL-HEPES before addition to IVF drops.
[0124] The noncytopathic strains of BVDV used in this research included 2 diverse Genotype I strains (SD-1 and NY-1) and 2 diverse Genotype II strains (CD-87 and PA-131). Givens M D et al., Theriogenology 2000;54:1093-1107. All stocks were propagated in BVDV-free MDBK cells cultured in MEM-eq. Virus was harvested by freezing and thawing and was stored in cryovials at −80° C. until needed.
EXAMPLE 20
[0125] In vitro Fertilization
[0126] Matured COCs were placed in 42-μL drops of fertilization medium under mineral oil. Cryopreserved bovine semen from a single collection was used for fertilization. This semen was confirmed to be free of BVDV by virus isolation and RT-nPCR. After PERCOLL®-gradient (45 to 90%) separation, 1.5×10 5 spermatozoa were added to each fertilization drop, which was incubated for approximately 18 h at 38.5° C. in a humidified atmosphere of 5% CO 2 and air.
EXAMPLE 21
[0127] In vitro Culture
[0128] After the IVF period, presumptive zygotes were removed, washed 4 times in TL-Hepes, equilibrated in IVC medium with BSA, and placed with cumulus cells still attached in 30 μl drops (10 to 12 per drop) of the IVC medium with BSA under mineral oil. The IVC plates were incubated for 3 d at 38.5° C. in a humidified atmosphere of 5% CO 2 and air. After the first 3 d in IVC, embryos were washed 3 times in TL-Hepes, and most of the cumulus cells were removed by gentle aspiration in and out of a sterile pipette. The nearly nude embryos were examined for cleavage, and those at the 5-cell stage or greater were washed 1 more time in IVC medium and placed with pieces of detached cumulus in 60-μl drops (20 to 25 per drop) of the IVC medium with 10% (v/v) FBS under mineral oil. These developed embryos were incubated an additional 4 d. After the final 4 d in IVC, embryos were transferred into 3 ml of MEM-eq, separated from cumulus cells, and development to the morula or blastocyst stage was noted.
EXAMPLE 22
[0129] Washing and Trypsin Treatment of Embryos
[0130] Washing and trypsin treatment of Day 7 embryos conformed to procedures recommended by the International Embryo Transfer Society for treatment of in vivo-derived bovine embryos. (Stringfellow D A, et al., Manual of the International Embryo Transfer Society Third Edition., Savoy Ill.: International Embryo Transfer Society, 1998;79-84). Degenerate and developed Day 7 embryos were washed 12 times in 1 ml of MEM-eq in 2-cm2 wells.
[0131] For trypsin treatment, twelve 3-ml washes in 35-mm Petri dishes were used. The first 5 and last 5 washes were PBS supplemented with 0.4% BSA, penicillin (100 U/ml) and streptomycin (100 μg/ml). The 6th and 7th washes were trypsin diluted 1:250 in 3 ml of Hank's balanced salt solution without Ca 2+ and Mg 2+ . Embryos were treated in trypsin for approximately 90 sec (45 sec/wash) before proceeding through the last 5 washes.
EXAMPLE 23
[0132] Samples Assayed for BVDV
[0133] During each of 12 research replicates (3 replicates with 4 diverse strains of BVDV), 140 to 180 COCs were exposed to virus while 50 to 80 COCs were maintained as negative controls. For each replicate, samples were obtained from exposed and unexposed cultures to be assayed for BVDV. All samples other than stock virus aliquots were assayed for BVDV using virus isolation with (a) immunoperoxidase assay for viral detection, (b) tissue culture passage prior to virus isolation to optimize viral detection, and (c) RT-nPCR. Samples included:
[0134] Stock virus aliquots. The viral aliquot to which the COCs were exposed was serially diluted and assayed by virus isolation using immunoperoxidase assay.
[0135] Day 3 cumulus cells. On Day 3 of IVC, some detached cumulus cells were removed from the 3rd wash of TL-Hepes, transferred into 3 ml of MEM-eq, and then placed in 500 μL of MEM-eq within a cryovial. Cells were lysed by freezing at −80° C. and thawing to release any intracellular virus prior to assay for BVDV.
[0136] Day 7 cumulus cells. On Day 7 of IVC, cumulus cells from exposed and unexposed cultures were transferred from the 3 ml of MEM-eq into 500 μL of MEM-eq within a cryovial. Cells were lysed by freezing at −80° C. and thawing to release any intracellular virus prior to assay for BVDV.
[0137] Day 7 individual embryos. If sufficient numbers of BVDV-exposed M/B developed by Day 7 of each research replicate, a group of 10 M/B was washed as previously described and a group of 10 M/B was trypsin-treated as previously described. Virus-exposed, washed M/B were individually placed into 500 μL of MEM-eq (4 to 5 per replicate) or were individually cryopreserved and thawed before placement in MEM-eq (4 to 5 per replicate). Virus-exposed, trypsin-treated M/B were individually placed into 500 μL of MEM-eq (3 to 5 per replicate) or were individually cryopreserved and thawed before placement in MEM-eq (4 to 5 per replicate). All samples were sonicated before viral assay.
[0138] If sufficient numbers of non-exposed M/B developed by Day 7 of each replicate, a group of 10 M/B was washed as previously described. Non-exposed, washed M/B were individually placed directly into 500 μL of MEM-eq (5 per replicate) or were individually cryopreserved and thawed before placement in MEM-eq (5 per replicate). Samples were sonicated before viral assay.
EXAMPLE 24
[0139] Statistical Analysis and Results
[0140] The tissue culture infective dose 50% (TCID 50 )/ml of the exposure aliquot was determined by the method of Reed and Muench (L. J. Reed and H. Muench, Am J Hygiene 27, 493-497 (1938). Results of viral detection assays were compared using a Pearson Chi-square test statistic (J. Sall and A. Lehman, JMP Start Statistics (Duxbury Press, Belmont, Calif. (1996),195-211).
[0141] Table 2 sets forth the results of the analysis of in vitro culture media and cell lysates that have been treated with the indicated antiviral compound for the indicated time at a concentration of 12.5 μM, after exposure to BVDV at a MOI of 0.05 (see Example 12).
TABLE 2 Day 3 Media Day 7 Media Day 7 Cell Lysates Antiviral drug TCID 50 /mL % Control TCID 50 /mL % Control TCID 50 /mL % Control No antiviral 2.00E+05 5.20E+05 2.00E+06 DB619 3.50E+02 0.18% 2.00E+05 38.46% 1.10E+06 55.00% DB673 1.00E+02 0.05% 6.20E+03 1.19% 3.50E+04 1.75%
[0142] Table 3 sets forth the results of the analysis of in vitro culture media and cell lysates that have been treated with the indicated antiviral compound for the indicated time at a concentration of 12.5 μM, after exposure to BVDV at a MOI of 1.0 (see Example 12).
TABLE 3 Day 3 Media Day 7 Media Day 7 Cell Lysates Antiviral drug TCID 50 /mL % Control TCID 50 /mL % Control TCID 50 /mL % Control No antiviral 3.50E+05 3.50E+04 6.20E+05 DB619 6.20E+04 17.71% 3.50E+04 100.00% 3.50E+05 56.45% DB673 3.50E+02 0.10% 2.00E+05 571.43% 2.70E+05 43.55%
[0143] Table 4, below sets forth the results of the analysis of Day 3 in vitro culture media and Day 3 cell lysate that has been treated with the indicated antiviral compound at a concentration of 12.5 μM, after exposure to BVDV at a MOI of 0.5 (see Example 12).
TABLE 4 Day 3 Media Day 3 Cell Lysates Antiviral drug TCID 50 /mL % Control TCID 50 /mL % Control No antiviral 3.50E+06 6.20E+06 DB 457 1.00E+02 0.0029% 3.50E+02 0.0056% DB 458 Negative Negative DB 459 Negative 1.00E+02 0.0016% DB 606 Negative Negative DB 680 Negative Negative DB 701 6.20E+03 0.1771% 3.50E+04 0.5645% DB 705 Negative Negative DB 708 Negative Negative DB 711 2.40E+05 6.8571% 2.00E+07 322.5806% DB 752 Negative 6.20E+02 0.01%
[0144] Table 5 sets forth the results of the analysis of Day 3 cell lysates that have been treated with the indicated antiviral compound for three days at the indicated concentration, after exposure to BVDV at a MOI of 0.05.
TABLE 5 Day 3 Media Day 3 Cell Lysates Antiviral drug TCID 50 /mL % Control TCID 50 /mL % Control No antiviral 2.00E+06 3.50E+05 DB 456 25 μm 3.50E+03 0.1750% 2.00E+03 0.5714% DB 456 12 μm 6.20E+02 0.0310% 3.50E+03 1.0000% DB 456 6 μm 3.50E+04 1.7500% 3.50E+04 10.0000% DB 456 3 μm 3.50E+05 17.5000% 6.20E+05 177.1429% DB 456 1.5 μm 5.10E+05 25.5000% 3.50E+06 1000.0000% DB 456 0.7 μm 6.30E+05 31.5000% 3.50E+06 1000.0000% DB 456 0.4 μm 6.30E+05 31.5000% 3.50E+06 1000.0000% DB 456 0.2 μm 6.30E+05 31.5000% 3.50E+05 100.0000%
[0145] In the specification, and examples there have been disclosed typical preferred embodiments of the invention and, although specific terms are employed, they are used in a generic and descriptive sense only and not for the purposes of limitation, the scope of the invention being set forth in the following claims.
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The present invention relates to novel compounds and methods that are useful in treating members of the Flaviviridae family of viruses. Compounds of the present invention will have a structure according to Formulas (I)-(VI) as recited throughout the application.
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BACKGROUND OF THE INVENTION
[0001] The invention relates to a hydraulic system for utility vehicles, in particular agricultural tractors, for supplying primary and/or auxiliary pressure medium consumers with pressure medium, comprising a pump sucking from a pressure medium tank, said pump being controlled as a function of the load pressure of the pressure medium consumers and supplying a pump pressure exceeding the load pressure by a predetermined control pressure differential, whereby in order to produce a first control pressure differential for operating a primary pressure medium consumer its load pressure acts upon the pressure and flow controller of the pump and in order to produce a second, higher control pressure differential for operating auxiliary pressure medium consumers a pressure exceeding their load pressure is produced by means of an amplifier device, which acts upon the pressure and flow controller.
[0002] European Patent EP 110 70 852 A2 describes such hydraulic system with a fixed displacement pump. Assigned to that pump is a device consisting of a pressure control valve with an inlet for an actuating pressure that enables the pump to deliver pressure medium to the pressure medium consumers at a necessary pressure and (flow) output. In the case of this system, for operating both the vehicle external (hereafter: primary and auxiliary) pressure medium consumers, the actuating pressure for the pressure control valve of the pump is picked up between the two orifices of the amplifier device. In order to provide different control pressures as they are needed to produce the various control pressure differentials for these pressure medium consumers, the line containing the orifices is blocked off by means of an additional pressure regulator, whenever a primary pressure medium consumer is in operation and open whenever an auxiliary pressure medium consumer is in operation. A disadvantage here is that the load pressure of the primary pressure medium consumers, which is utilized as actuating pressure for operating said pressure medium consumers is subject to restriction when passing through the one orifice. As a consequence the actuating pressure takes longer to build up and finally the system dynamics are lower as a result.
[0003] A further disadvantage of the prior art hydraulic system is apparent if no implement is mounted on the vehicle, i.e. no auxiliary pressure medium consumer is connected to the hydraulic system of the vehicle. In this case it is possible that due to thermal expansion of the pressure medium inside the load pressure line for auxiliary pressure medium consumers or due to a leakage in the pressure regulator adjacent to the orifices, pressure medium flows to the pressure control valve of the pump. The effect of this is automatic restriction of the pump even as far as actuation of the assigned pressure relief valve (pump short-circuit).
[0004] The object of the invention is seen as providing a hydraulic system of the type mentioned at the beginning, wherein the disadvantages described are eliminated and which in particular without any time delay makes available the load pressure of a primary pressure medium consumer as actuating pressure for the device assigned to the pump.
BRIEF SUMMARY OF THE INVENTION
[0005] The object is achieved by the fact that the amplifier device consists of a proportionally controllable pressure reducing valve with a control piston, a pressure inlet connected to a pressure pipe, a load pressure inlet connected to a load pressure reporting pipe conducting the load pressure of the auxiliary pressure medium consumers and a load pressure outlet, whereby the control piston is subjected on the one side to the variable force of an electromagnet and the load pressure prevailing at the load pressure inlet of the auxiliary pressure medium consumers and on the other side to the force of an adjustable spring and the pressure prevailing at the load pressure outlet.
[0006] This arrangement enables the cost of the amplifier device to be kept to a minimum, in order to make available the control pressure differential needed for operating the primary or auxiliary pressure medium consumers respectively. The necessary control pressure differential can be adjusted by corresponding actuation (excitation) of the electromagnet. In this case a differential pressure is added to the load pressure at the load pressure inlet of the pressure reducing valve and thus the load pressure at the load pressure outlet is increased accordingly. In the technically simplest way this can be effected by the vehicle driver while he is working if a suitable control element is provided at his workplace.
[0007] Since the load pressure of the primary pressure medium consumers is not conducted via an orifice of the amplifier device, but is supplied directly to the pressure and flow controller of the pump without manipulation, whenever a primary pressure medium consumer is actuated the pump responds with rapid pressure build-up and delay-free supply of the necessary pressure medium.
[0008] In this case the flow control valve according to claim 2 reliably prevents pressure from building up in the amplifier device due for example to thermal expansion of the pressure medium, which may affect the pressure and flow controller of the pump in an undesirable way.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The invention is described below in detail on the basis of a drawing showing a circuit diagram for a hydraulic system.
DETAILED DESCRIPTION OF THE INVENTION
[0010] In the circuit diagram for a hydraulic system of an agricultural tractor, a variable volume displacement pump referenced with 1 sucks pressure medium via a suction line 2 from a pressure medium tank 3 and supplies this via pressure pipes 4 , 41 to a tractor-mounted control block 5 . From here the pressure medium is distributed to primary pressure medium consumers 6 , directly connected to the hydraulic system. The pressure medium is further distributed to auxiliary pressure medium consumers 11 , 12 by means of an auxiliary control block 7 , connected with hydraulic couplings 8 , 9 , 10 to the hydraulic system of the tractor. “Pressure medium consumers” here are understood as single and double acting hydraulic actuators (linear actuators and rotating actuators) for driving different implements such as, for example, the primary cylinder of the 3-point linkage for implements or the auxiliary actuating cylinder of an externally mounted front loader.
[0011] A pressure and a flow controller 13 is mounted on the pump 1 , the purpose of that device consists in controlling, via an adjustment piston 14 , the flow rate of the pump 1 as a function of the load pressure of the operating pressure medium consumers (communicated via a load pressure reporting line 15 ) in such a way that a defined pressure gradient, also called control pressure differential, always prevails between the pressure pipe 4 and the load pressure reporting line 15 . The pressure gradient of approx. 20 bar required for operating primary pressure medium consumers 6 is adjusted by pre-tensioning a compression spring 16 . In all other respects such a pressure and flow controller 13 is presumed to be familiar and therefore is not described in detail.
[0012] The primary control block 5 consists of an inlet section 5 a, a valve section 5 b and a sealing plate 5 c, which are all bolted together to form a unit. Several valve sections 5 b can be provided depending on the number of pressure medium consumers 6 to be operated.
[0013] The valve section 5 b contains a solenoid-operated main slide valve 17 of the load pressure sensing type, a section pressure regulator 18 and a shuttle valve 19 . The primary pressure medium consumer 6 is connected to the connections A and B communicating with the main slide valve 17 . Its pressure medium is supplied via the pressure pipe 41 . Its load pressure is supplied to the pressure and flow controller 13 via load pressure reporting line 20 , shuttle valve 19 and load pressure reporting line 15 . The section pressure regulator 18 lies in a pressure pipe 21 branching off from the pressure pipe 41 to the main slide valve 17 and by the corresponding pre-tensioning of a spring 22 permits a desired pressure gradient to be adjusted between the pressure pipe 21 and the load pressure reporting line 20 .
[0014] Customary values for the pressure gradient are approx. 8 bar. Therefore a pressure differential of approx. 12 bar is available to compensate for any flow losses between the pump 1 and the valve section 5 b. Such adjustment of the pressure gradient ensures low-loss and reliable operation of all primary pressure medium consumers 6 connected to the valve sections 5 b.
[0015] The auxiliary control block 7 is arranged on an implement, a potato digger for example, and consists of an inlet section 7 a, several valve sections 7 b, whereby a valve section 7 b is present and a sealing plate 7 c for each pressure medium consumer 11 , 12 operated with the implement. Each auxiliary valve section 7 b includes a section pressure regulator 24 with a solenoid-operated main slide valve 23 of the load pressure sensing type, and a shuttle valve 25 similar in design and operation to that of a primary valve section 5 b. Load pressure reporting lines 26 leading from the main slide valves 23 conduct the load pressure of the auxiliary pressure medium consumers 11 , 12 to shuttle valves 25 . From these the highest load pressure in each case is transmitted to the auxiliary load pressure reporting line 27 , which leads to the hydraulic coupling 9 . From there a primary load pressure reporting line 28 conducts the highest load pressure of the auxiliary pressure medium consumers 11 , 12 to an amplifier device 29 , integrated into the sealing plate 5 c.
[0016] The amplifier device 29 consists of a proportionally controllable pressure reducing valve 39 with a control range from 0 to 26 bar and a low volume flow controller (flow control valve) 40 adjusted to a nominal value of approx. 0.5 litre per minute. In the embodiment described the pressure reducing valve 39 is installed in such a way that its pressure inlet 42 is connected to the pressure pipe 41 , the inlet 43 to the load pressure reporting line 28 a branching off from the load pressure reporting line 28 and the outlet 44 to a load pressure reporting line 45 . The load pressure present at the outlet 44 is conducted via the shuttle valve 19 and the load pressure reporting line 15 to the pressure and flow controller 13 .
[0017] As regards forces the control piston 46 of the pressure reducing valve 39 is in a state of equilibrium, whereby the adjustable force of an electromagnet 47 as well as the pressure at the inlet 43 acts upon the one side of the control piston 46 and the force of a spring 48 as well as the return pressure at the outlet 44 acts upon the other side of the control piston 46 .
[0018] Typically such pressure reducing valves are used to reduce pressure at the pressure inlet 42 by controlled excitation of the electromagnet 47 and to make the reduced pressure, whose amount is proportional to the excitation, available to the outlet 44 . Otherwise than proposed in the present embodiment with conventional circuitry of the pressure reducing valve 39 the connection actually used as inlet 43 for the load pressure of the auxiliary pressure medium consumers 11 , 12 therefore represents a tank inlet, while the pressure at the outlet 44 is used to actuate further valves.
[0019] The low volume flow controller (flow control valve) 40 lies in a branch line 28 b of the load pressure reporting line 28 . Consequently it is guaranteed that if attachments are not mounted no unintentional load pressure reporting occurs through a thermally-induced pressure increase in the load pressure reporting line 28 .
[0020] Load pressure of the control block 7 according to the circuit diagram lies on the inlet 43 of the pressure reducing valve 39 . With the electromagnet 47 not excited this load pressure is looped to the outlet 44 in the ratio 1:1 by the pressure reducing valve. By exciting the electromagnet 47 a differential pressure is added to the load pressure at the inlet 43 . The electromagnet 47 is excited from the workplace of the driver, where a control element suitable for this is provided. In this case the amount of the differential pressure can be selected by the driver from between 0 and 26 bar and also changed while he is driving. In this way a differential pressure determined by the driver depending on different attachments and operating temperatures can therefore be added to the constantly changing load pressure of the control block 7 . The load pressure increased by the differential pressure is now reported to the pressure and flow controller 13 via the load pressure reporting lines 45 and 15 . This ensures that the pump 1 supplies a substantially higher flow compared to the operation of a primary pressure medium consumer 6 and thus guarantees trouble-free operation of the pressure medium consumers 11 , 12 .
[0021] The invention has been described on the basis of a hydraulic system with a variable volume displacement pume. Should the invention be used in conduction with a fixed displacement pump then is nothing to do but to connect the pressure reporting line 15 to the corresponding inlet of the pressure and flow controller of the fixed displacement pump. Such pressure and flow controllers are well known therefore a closer description thereof is unnecessary.
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Disclosed is a hydraulic system for utility vehicles, in particular agricultural tractors, for supplying primary and/or auxiliary pressure medium consumers ( 6, 11, 12 ) with pressure medium, comprising a pump ( 1 ), whose pressure and flow are controlled as a function of the load pressure of the pressure medium consumers by a pressure and flow controller ( 13 ) to which whenever auxiliary pressure medium consumers ( 11, 12 ) are operating, a higher load pressure compared to the actual load pressure is reported through an amplifier device. In order to obtain rapid response of an actuated auxiliary pressure medium consumer it is proposed that the amplifier device ( 29 ) consists of a proportionally controllable pressure reducing valve ( 39 ).
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BACKGROUND OF THE INVENTION
This invention relates to cardiovascular agents and in particular to certain 1,4-dihydropyridines which combine both calcium antagonist and alpha 1 -antagonist activity and which are useful for the treatment of hypertension, heart failure and angina.
The dihydropyridine calcium antagonists are well known as a class of therapeutic agents, the most widely used example being the compound nifedipine. Dihydropyridine derivatives substituted at the 2-position by side chains which include varous groups have been described in our published European patent applications nos. 60674 and 100189. Such compounds can reduce the movement of calcium into the cell and they are thus able to delay or prevent the cardiac contracture which is believed to be caused by an accumulation of intracellular calcium under ischaemic conditions. Excessive calcium influx during ischaemia can have a number of additional adverse effects which would further compromise the ischaemic myocardium. These include less efficient use of oxygen for ATP production, activation of mitochondrial fatty acid oxidation and possibly, promotion of cell necrosis. Thus calcium antagonists are useful in the treatment or prevention of a variety of cardiac conditions, such as angina pectoris, cardiac arrythmias, heart attacks and cardiac hypertrophy. Calcium antagonists also have vasodilator activity since they are thus also useful as antihypertensive agents and for the treatment of coronary vasospasm. Howver, with respect to the vasculature, calcium antagonists are primarily arteriolar dilators and the reflex sympathetic activation which occurs with nifedipine-like agents can be detrimental for both hpertensive and anginal patients. Alpha- 1 -antagonits such as prazosin and doxazosin are also effective antihypertensive drugs but, since these agents act on both venous and arteriolar tone, heart rate changes are minor. In addition, alpha 1 -antagonists have beneficial effects on high-density/low-density lipoprotein levels.
Combination of calcium- and alpha 1 -antagonist properties in accordance with the present invention is advantageous since the clinical benefits associated with both pharmacological activities can be provided by a single agent. For example, these compounds possess anti-ischaemic, venodilator and arteriolardilator properties and are effective for the treatment of a wide range of cardiovascular disorders, particularly hypertension, heart failure and angina.
Quinazoline-dihydropyridines are disclosed as useful cardiovascular agents in U.S. application Ser. No. 562,482 filed Dec. 16, 1983 now U.S. Pat. No. 4,572,908.
SUMMARY OF THE INVENTION
Thus, according to the present invention, there are provided 1,4-dihydropyridine derivatives of the formulae: ##STR2## and pharmaceutically acceptable salts thereof where R is chlorothienyl or mono- or disubstituted phenyl where said substituent is fluoro, chloro, bromo or trifluoromethyl; R 1 and R 2 are each alkyl of one to three carbon atoms; R 3 and R 4 when taken separately are each hydrogen or alkyl of one to three carbon atoms; R 3 and R 4 when taken together with the nitrogen to which they are attached are pyrrolidine or piperidine; R 5 is alkyl of one to three carbon atoms or 2-hydroxyethyl; R 6 is hydrogen or methoxy; X and Z are each hydrogen or methoxy; Y is alkylene of two to three carbon atoms; R 7 is chlorophenyl or chloro-trifluoromethylphenyl; p is an integer of 0 or 1; and Q is CH or N.
A preferred group of compounds are of formula 1 where R 1 is methyl, R 2 is ethyl, R 3 and R 4 are each hydrogen, R 5 is said alkyl; R 6 is hydrogen, X and Z are each methoxy, Y is ethylene and Q is N. Especially preferred are those compounds where R 5 is methyl and R is 2-chlorophenyl, 2-chloro-3-fluorophenyl, 2,3-dichlorophenyl, 2-chloro-3-trifluoromethylphenyl, 2,3-difluorophenyl, 2-fluoro-3-chlorophenyl, 2-bromophenyl or 2-trifluoromethylphenyl.
Also preferred are compounds of formula 2 where R 1 is methyl and R 2 is ethyl. Especially preferred is the compound where R 7 is 2-chlorophenyl.
Also within the scope of the present invention is a pharmaceutical composition comprising a compound of formula 1 or 2 together with a pharmaceutically acceptable carrier or diluent, and a method for treating hypertension in a mammal comprising administering to said mammal an effective antihypertensive amount of a compound of formula 1 or 2.
The pharmaceutically acceptable salts of the compounds of the formulae 1 and 2 are those formed from acids which form non-toxic acid addition salts, for example the hydrochloride, hydrobromide, sulphate or bisulphate, phosphate or acid phosphate, acetate, citrate, fumarate, gluconate, lactate, maleate, succinate and tartrate salts.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of formula 1 are prpared by a number of different processes according to the invention.
(a) In one process the compounds of formula 1 wherein Q is N can be prepared by reacting a compound of the formula: ##STR3## with a compound of the formula: ##STR4## wherein R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y and Z are as previously defined and Hal is a halogen atom, preferably chloro.
Similarly, this route is applicable to the synthesis of compounds of formula 2 as follows: ##STR5## with a compound of the formula ##STR6## wherein R 1 , R 2 , R 7 and p are as previously defined and Hal is a halogen atom, preferably chloro.
The reaction is generally performed with more or less equimolar proportions of the reactants dissolved in a reaction-inert organic solvent. Suitable solvents are alkanols such as n-butanol and iso-amyl alcohol or dimethylsulphoxide. A base may also be present, to remove the acid formed in the reaction. A suitable example is 4-dimethylaminopyridine.
The reaction is typically achieved by heating the mixture at a temperature of from 100°-150° C. and is generally complete within a period of from 2 to 24 hours.
The starting materials of formula II and II 1 are prepared by conventional methods, for example by the Hantzsch synthesis as described in European Patent Application publication number 0089167. The quinazoline starting materials of formula III and III 1 generally known compounds prepared in accordance with published procedures, for example as described in British Patent number 1156973 and European Patent application publication number 100200.
(b) In an alternative process, compounds of the formula 1 wherein Q is N and R 3 and R 4 are both hydrogen can be prepared by reacting a compound of the formula: ##STR7## with a 2-amino-benzonitrile of the formula: ##STR8## wherein R, R 1 , R 2 , R 5 , R 6 , X, Y and Z are as previously defined.
The reaction is conveniently performed by adding sodium hydride (2 equivalents) to a solution of the 2-amino-benzonitrile (V) in tetrahydrofuran. After a short while at a room temperature the dihydropyridine (IV) is added. The mixture is refluxed for one or two hours and the product isolated and purified by conventional methods.
In a similar manner, starting with the appropriate reagents compounds of formula 2 can also be prepared by this route.
The starting materials may be prepared from the corresponding 2-dialkylaminoalkoxymethyldihydropyridines, described for example in European patent application publication no. 60674, by reaction with cyanogen bromide.
(c) In a further process, compounds of the formula 1 wherein Q is CH and R 3 and R 4 are both hydrogen can be prepared by cyclising a compound of the formula: ##STR9## wherein R, R 1 , R 2 , R 5 , R 6 , X, Y and Z are as previously defined.
The cyclisation can be carried out using a Lewis acid, e.g. zinc chloide, or a base, e.g. lithium diisopropylamide. The reaction with zinc chloride is typically carried out by heating the reactants, preferably at reflux, in a suitable organic solvent, e.g. dimethylacetamide for up to about 4 hours. The reaction with lithium diisopropylamide is typically carried out at low temperature (e.g. -70° C.) in a suitable organic solvent, e.g. tetrahydrofuran, following which the reaction mixture is allowed to warm to room temperature. In some cases heating may be necessary to complete the reaction. The product can then be isolated and purified conventionally.
The starting materials of formula (VI) may be prepared from the appropriate 2-aminoalkoxymethyl-1,4-dihydropyridine and an appropriate substituted alkyl N-(2-cyanophenyl)acetimidate by conventional reactions, for example using the procedures described in European patent application publication number 100200.
The ability of the compounds to inhibit the moement of calcium into the cell is shown by their effectiveness in reducing the contraction of vascular tissue in vitro which is the consequence of calcium influx caused by a high extracellular concentration of potassium ions. The test is performed by mounting spirally cut strips of rat aorta with one end fixed and the other attached to a force transducer. The tissue is immersed in a bath of physiological saline solution containing calcium ions at a concentration of 2.5 millimolar and potassium ions at a concentration of 5.9 millimolar. Potassium chloride solution is added to the bath with a pipette to give a final potassium ion concentration of 45 millimolar. The change in tension caused by the resulting contraction of the tissue is noted. The bath is drained and refilled with fresh saline solution containing the particular compound under test. After 45 minutes, the procedure is repeated and the contraction again noted. The concentration of compound required to reduce the response by 50% is determined.
The in-vitro alpha 1 adrenoceptor binding affinity of the compounds is determined by measuring their ability to displace tritium labelled prazosin from a rat brain membrane preparation in accordance with the procedure of P. M. Greengrass and R. M. Bremner, European Journal of Pharmacology, 55, 323, 1979.
The in-vivo pharmacological profile of the compounds is assessed using chloralose anaesthetised cats measuring blood pressure, heart rate and contractions of the nictitating membrane. The compounds are injected intravenously. Alpha 1 adrenoceptor antagonist activity is assessed by measuring inhibition of responses of the nictitating membrane to electrical stimulation of he cervical sympathetic nerve. Calcium antagonist activity is assessed by measuring the reduction of pressor responses to injections of angiotensin II.
The antihypertensive activity of the compounds is evaluated after oral administration by measuring the fall in blood pressure in spontaneously hypertensive rats or renally hypertensive dogs.
For administration to man in the curative or prophylactic treatment of cardiac conditions and hypertension, oral dosages of the compounds will generally be in the range of from 2-200 mg daily for an average adult patient (70 kg). Thus for a typical adult patient, individual tablets or capsules contain from 1 to 20 mg of active compound, in a suitable pharmaceutically acceptable vehicle or carrier. Dosages for intravenous administration would typically be within the range 1 to 10 mg per single dose as required. In practice in physician will determine the actual dosage which will be most suitable for an individual patient and it will vary with the age, weight and response of the particular patient. The above dosages are exemplary of the average case but there can, of course, be individual instances where higher or lower dosage ranges are merited, and such are within the scope of this invention.
For human use, the compounds of the formulae 1 and 2 can be administered alone, but will generally be administered in admixtue with a pharmaceutical carrier selected with regard to the intended route of administration and standard pharmaceutical practice. For example, they may be administered orally in the form of tablets containing such excipients as starch or lactose, or in capsules or ovules either alone or in admixture with excipients, or in the form of elixirs or suspensions containing flavouring or coloruing agents. They may be injected parenterally, for example, intravenously, intramuscularly or subcutaneously. For parenteral administration, they are best used in the form of a sterile aqueous solution which may contain other substances, for example, enough salts or glucose to make the solution isotonic with blood.
Thus in a further aspect the invention provides a pharmaceutical composition comprising a compound of the formula 1 or 2, or a pharmaceutically acceptable salt thereof, together with a pharmaceutically acceptable diluent or carrier.
The invention also includes a compound of the formula 1 or 2, or a pharmaceutically acceptable salt thereof, for use in medicine, in particular in the prevention or treatment of cardiac conditions including ischaemic heart disease, angina and heart failure or for treatment of hypertension in a human being.
4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquijazol-2-yl)-N-methylamino]ethoxy-methyl}-1,4-dihydropyridine hemihydrate
A mixture of 4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxy-carbonyl-6-methyl-2-(2-N-methylaminoethoxymethyl)-1,4-dihydropyridine (9.0 g), 4-amino-2-chloro-6,7-dimethoxyquinazoline (5.1 g), 4-dimethylaminopyridine (3.0 g) and n-butanol (150 ml) was heated under reflux for 18 hours. The mixture was cooled and filtered and the filtrate was evaporated. The residue was chromatographed on silica gel. Elution with dichloromethane containing 1% methanol first gave impurity; increasing the methanol concentration to 5% then gave the pure product. The product fractions were combined and evaporated and the residue was triturated with di-isopropyl ether to give the title compound (1.49 g), m.p. 139°-141° C. Found: C, 58.60; H, 5.81; N, 11.09. C 31 H 36 ClN 5 O.1/2H 2 O requires: C, 58.62; H, 5.87; N, 11.02%.
EXAMPLES 2-8
The following compounds were prepared by the method described in Example 1 using the appropriate quinazoline starting materials of formula III
______________________________________ ##STR10## Analysis %Exam- (Theoreticalple m.p. in brackets)No. R.sup.3 R.sup.4 R.sup.6 (°C.) C H N______________________________________2 CH.sub.3 H H -- 59.95 6.05 10.81 (60.04 5.98 10.94)3 CH.sub.3 CH.sub.3 H -- .sup.(a)4 C.sub.2 H.sub.5 H H -- 60.80 6.27 10.29 (60.59 6.16 10.71)5 CH(CH.sub.3).sub.2 H H 148 57.34 5.96 10.09 (57.95 6.15 9.94)6 (CH.sub.2).sub.4 H 209- 58.62 6.09 9.56 212 (58.65 6.05 9.777 H H OCH.sub.3 -- 58.74 5.86 10.55 (58.57 5.84 10.67)8 CH.sub.3 C.sub.2 H.sub.5 H 146- 58.16 5.86 9.48 149.sup.(b) (57.95 6.15 9.94)______________________________________ .sup.(a) Characterised by .sup.1 H NMR (CDCl.sub.3): 1.17 (t, 3H, J = 7.1 Hz, CO.sub.2 CH.sub.2.sub.----Me); 2.04 (s, 3H, 6Me); 3.20 (s, 6H, NMe.sub.2); 3.31 (s, 3H, NMe); 3.57 (s, 3H, CO.sub.2 Me); ca 3.9 (m, 4H, OCH.sub.2 CH.sub.2 N); 3.91 (s, 3H, OMe), 3.96 (s, 3H, OMe); 4.03 (q, 2H, J = 7.1 Hz, CO.sub.2 CH.sub.2 Me); 4.70 (d, 1H) and 4.78 (d, 1H, J = 16.2 Hz), CH.sub.2 O; 5.34 (s, 1H 4H); 6.92 (s, 1H) and 7.19 (s, 1H, quinazoline CH); 6.98-7.31 (m, aromatic CH and dihydropyridine NH). .sup.(b) Hydrochloride salt
EXAMPLE 9
4-(2-Trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-methyl-amino)]ethoxymethyl}-1,4-dihydropyridine
(i) 4-(2-Trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-(2-N-benzyl-N-methylaminoethoxymethyl)-1,4-dihydropyridine
A solution of 2-trifluoromethylbenzaldehyde (6.96 g) methyl 3-aminocrotonate (4.60 g) and ethyl 4-(2-N-benzyl-N-methylaminoethoxy)acetoacetate (11.72 g) in ethanol (80 ml) was heated under reflux with stirring for 20 hours and then evaporated. The residue was chromatographed on silica gel. Elution with a 4.1 mixture of petrol and chloroform first gave some impurity. Gradually increasing the concentration of chloroform gave more impurity and then finally the product was eluted with pure chloroform. The product fractions were combined and evaporated to give the title compound as a gum (6.0 g). Found: C, 64.34; H, 6.00; N, 4.79. C 29H33 F 3 N 2 O 5 requires: C, 63.72; H, 6.09; N, 5.13%.
(ii) 4-(2-Trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-(2-N-methylaminoethoxymethyl)-1,4-dihydropyridine
The above product (5.3 g) was dissolved in a mixture of methanol (100 ml) and concentrated hydrochloric acid (2 ml) and hydrogenated at 22° C. and 4 atm. pressure in the presence of 10% palladium on charcoal catalyst (0.5 g). When no further hydrogen was taken up, the catalyst was filtered off and the filtrate was evaporated. The residue was chromatographed on silica gel eluting with a 10:1 mixture of chloroform and methanol containing a trace of triethylamine. Evaporation of the product fractions gave the title compound (2.20 g), m.p. 106°-107° C. (from ethyl acetate/petrol). Found: C, 57.47; H, 5.93; N, 6.02. C 22 H 27 F 3 N 2 O 5 requires: C, 57.88; H, 5.96; N, 6.14%.
(iii) 4-(2-Trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-methylamino]ethoxymethyl-1,4-dihydropyridine
Treatment of the above compound with 4-amino-2-chloro-6,7-dimethoxyquinazoline by the method of Example 1 (7 hours reflux time) gave the title compound, m.p. 135°-136° C. (from di-isopropyl ether). Found: C, 58.23; H, 5.61; N, 10.52. C 32 H 36 N 5 O 7 requires: C, 58.26; H, 5.50; N, 10.62%.
EXAMPLE 10-19
The following examples were prepared following the procedure of Example 8 using the appropriate dihydropyridine starting materials.
__________________________________________________________________________ ##STR11## Analysis %Example (Theoretical in brackets)No. R.sup.1 R.sup.2 R.sup.5 R.sup.8 R.sup.9 n m.p. °C. C H N__________________________________________________________________________10 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F H 2 -- (a)11 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F 3-F 2 160 55.89 5.65 10.36 (56.06 5.46 10.54)12 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F 3-Cl 2 -- 57.64 5.55 10.66 (57.80 5.48 10.87)13 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 3-F 2 -- (b)14 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 6-F 2 -- 58.10 5.66 10.72 (57.80 4.58 10.87)15 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 3-CF.sub.3 2 124-126 55.53 5.17 9.83 (55.37 5.08 10.09)16 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl H 3 -- 60.27 6.12 10.59 (60.04 5.98 10.94)17 CH.sub.3 CH.sub.3 CH.sub.3 Cl H 2 -- 59.18 5.87 11.63 (58.87 5.60 11.44)18 CH.sub.2 H.sub.5 CH.sub.3 CH.sub.3 Cl H 2 -- (c)19 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl H 2 -- (d)__________________________________________________________________________ (a) .sup.1 HNMR (CDCl.sub.3): 1.17 (t, 3H, J = 7.2 Hz, CO.sub.2 CH.sub.2.sub.-- --Me); 2.08 (s, 3H, 6Me); 3.27 (s, 3H, NMe); 3.57 (s, 3H, CO.sub.2 Me); ca 3.85 and ca 3.95 (m, 4H, OCH.sub.2 CH.sub.2 N); 3.93 (s, 3H, OMe); 3.96 (s, 3H, OMe); 4.02 (q, 2H, J = 7.2 Hz, CO.sub.2 CH.sub.2 Me); 4.74 (d, 1H) and 4.85 (d, 1H, J = 16.1 Hz), CH.sub.2 O; 5.10 (s, 2H, NH.sub.2); 5.19 (s, 1H, 4H); 6.75 (s, 1H) and 6.90 (s, 1H), quinazoline CH; 6.85-7.25 (m, 5H aromatic CH and dihydropyridine NH). (b) .sup.1 HNMR (CDCl.sub.3): 1.17 (t, 3H, J = 7.1 Hz, CO.sub.2 CH.sub.2.sub.----Me); 2.07 (s, 3H, 6Me); 3.27 (s, 3H, NMe); 3.57 (s, 3H, CO.sub.2 Me); ca 3.85 and ca 3.95 (m, 4H, OCH.sub.2 CH.sub.2 N); 3.91 (s, 3H, OMe); 3.95 (s, 3H, OMe); 4.04 (q, 2H, J = 7.1 Hz, CO.sub.2.sub.----CH.sub.2 Me); 4.75 (d, 1H) and 4.84 (d, 1H, J = 16.3 Hz) CH.sub.2 O; 5.14 (s, 2H, NH.sub.2); 5.37 (s, 1H, 4H), 6.68 (s, 1H) and 6.76 (s, 1H), quinazoline CH; 6.85-7.15 (m, 4H, aromatic CH and dihydropyridine NH). (c) .sup.1 HNMR (CDCl.sub.3): 1.16 (t, 3H, J = 7.1 Hz, CO.sub.2 CH.sub.2.sub.----Me); 2.09 (s, 3H, 6Me); 3.27 (s, 3H, NMe); 3.59 (s, 3H), CO.sub.2 Me); ca 3.83 and ca 4.0 (m, 4H, OCH.sub.2 CH.sub.2 N); 3.93 (s, 3H, OMe); 3.96 (s, 3H, OMe); 4.03 (q, 2H, J = 7.1 Hz, CO.sub.2.sub.----CH.sub.2 Me); 4.74 (d, 1H) and 4.84 (d, 1H, J = 16.2 Hz) CH.sub.2 O; 5.10 (s, 2H, NH.sub.2); 5.35 (s, 1H, 4H); 6.75 (s, 1H) and 6.90 (s, 1H), quinazoline CH; 6.98-7.35 (m, 5H, aromatic CH an dihydropyridine NH). (d) .sup.1 HNMR (CDCl.sub.3): 1.18 (t, 3H, J = 7.1 Hz, CO.sub.2 CH.sub.2.sub.----Me); 1.23 (t, 3H, J = 7.0 Hz, NCH.sub.2.sub.----Me); 2.1 (s, 3H, 6Me); 3.58 (s, 3H, CO.sub.2 Me); 3.76 (q, 2H, J = 7.0 Hz, N.sub.----CH.sub.2 Me); ca 3.8-4.0 (m, 4H, OCH.sub.2 CH.sub.2 N; 3.92 (s, 3H, OMe); 3.96 (s, 3H, OMe); 4.04 (q, 2H, J = 7.1 Hz, CO.sub.2.sub.----CH.sub.2 Me); 4.78 (d, 1H) and 4.86 (d, 1H, J = 16.4 Hz) CH.sub.2 O; 5.12 (s, 2H, NH.sub.2), 5.35 (s, 1H, 4H); 6.75 (s, 1H) and 6.88 (s, 1H) quinazoline CH; 6.98-7.35 (m, 5H, aromatic CH and dihydropyridine NH).
EXAMPLE 20
4-(2-Bromophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
(i) 4-(2-Bromophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-(2-N,N-dimethylaminoethoxymethyl)-1,4-dihydropyridine
2-Bromobenzaldehyde (5.60 g) was added dropwise to a stirred solution of ethyl 4-(2-dimethylaminoethoxy)acetoacetate (6.52 g) and the solution was warmed to 50° C. for 5 minutes and then cooled. Methyl 3-aminocrotonate (3.46 g) was added and the solution was heated under reflux for 20 hours and then evaporated. The residue was chromatographed on silica gel. The column was eluted with a 1:1 mixture of petrol and chloroform, gradually increasing the concentration of CHCl 3 to remove a small amount of by-product. The product was eluted with a 20:1 mixture of chloroform and methanol. The product fractions were combined and evaporated to give the title compound (3.2 g), m.p. 109°-110° C. (from ethyl acetate/hexane). Found: C, 54.75; H, 6.08; N, 5.88. C 22 H 29 BrN 2 O 5 requires: C, 54.89; H, 6.07; N, 5.82%.
(ii) 4-(2-Bromophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-(2-N-methylaminoethoxymethyl)-1,4 -dihydropyridine
2,2,2-Trichloroethyl chloroformate (1.20 g) was added dropwise to a stirred solution of the above product (2.60 g) in dry toluene (30 ml) at 5° C. and the resulting solution was heated under reflux for 18 hours. It was cooled and 2N hydrochloric acid (30 ml) was added. The mixture was stirred for 10 minutes, diluted with diethylether and the organic phase was separated, washed with water and dried over sodium sulphate. Evaporaton of the solvent gave a gum which was dissolved in 90% acetic acid (35 ml). The solution was cooled to 0° C. and zinc dust (4.50 g) was added portionwise with stirring. The mixture was stirred at room temperature for 20 hours and then filtered. The filtrate was evaporated and the residue was partitioned between ethyl acetate and water. The organic layer was separated, washed with concentrated ammonia solution, water and dried over sodium sulphate. Evaporation of the solvent gave a gum which was chromatographed on silica gel. Elution with a 50:1 mixture of chloroform and methanol initially gave some impurity. When the product started to appear the ratio of chloroform:methanol was changed to 10:1 and finally a trace of triethylamine was included to elute all the product. The product fractions were combined and evaporated to give the tiele compound (0.80 g), m.p. 88°-89° C. (from ethyl acetate/hexane). Found: C, 53.89; H, 5.83; N, 5.73. C 21 H 27 N 2 O 5 requires: C, 53.96; H, 5.82; N, 6.00%.
(iii) 4-(2-Bromophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
Treatment of the above compound with 4-amino-2-chloro-6,7-dimethoxyquinazoline according to the method of Example 1 (8 hours reflux time) gave the title compound as an amorphous glass. Found C, 55.35; H, 5.41; N, 9.70. C 31 H 36 BrN 5 O 7 requires: C, 55.52; H, 5.41; N, 10.45%.
EXAMPLE 21
4-(2,3-Dichlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
(i) 4-(2,3-Dichlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-[2-N,N-dimethylaminoethoxymethyl]-1,4-dihydropyridine
Reaction of 2,3-dichlorobenzaldehyde with ethyl 4-(2-dimethylaminoethoxy)acetoacetate and ethyl 3-aminocrotonate by the method of Example 20(i) gave the title compound, m.p. 101°-103° C. Found: C, 55.93; H, 5.76; N, 6.20. C 22 H 28 Cl 2 N 2 O 5 requires: C, 56.05; H, 5.99; N, 5.94%.
(ii) 4-(2,3-Dichlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-[2-N-methylaminoethoxymethyl]-1,4-dihydropyridine
Treatment of the above compound with 2,2,2-trichloroethyl chloroformate followed by zinc dust in acetic acid according to the method of Example 20(ii) gave the title compound which was used directly in the next stage.
(iii) 4-(2,3-Dichlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
Treatment of the above compound with 4-amino-2-chloro-6,7-dimethoxyquinazoline by the method of Example 1 gave the title compound as an amorphous glass, (CDCl 3 ): 1.17 (t, 3H, J=7.1 Hz, CO 2 CH 2 Me); 2.05 (s, 3H, 6-Me); 3.28 (s, 3H, NMe); 3.57 (s, 3H, CO 2 Me), ca 3.85 (m, 2H) and ca 3.95 (m, 2H), OCH 2 CH 2 N; 3.92 (s, 3H, OMe); 3.95 (s, 3H, OMe); 4.05 (q, 2H, J=7.1 Hz, CO 2 CH 2 Me); 4.74 (d, 1H) and 4.82 (d, 1H, J=16.2 Hz), CH 2 O; 5.10 (s, 2H, NH 2 ); 5.40 (s, 1H, 4-H); 6.74 (s, 1H) and 6.89 (s, 1H, quinazoline CH); 6.95-7.25 (m aromatic CH); 7.06 (s, 1H, NH).
EXAMPLE 22
1-(4-Amino-6,7-dimethoxyquinazol-2-yl-4-[4-(2-chloro-3-trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
(i) Ethyl 4-(1-methylpiperid-4-yloxy)acetoacetate
Sodium hydride (5.0 g of 50% dispersion in mineral oil) was added portionwise to a stirred solution of 4-hydroxy-1-methyl-piperidine (11.5 g) in dry dimethylformamide (80 ml). The mixture was stirred at room temperature for 1 hour and then cooled to 10° C. A solution of ethyl 4-chloroacetoacetate (8.2 g) in dry dimethylformamide (20 ml) was added dropwise with stirring and stirring was continued for a further 20 hours at room temperature. Ethanol (10 ml) was added and the solution was evaporated to dryness. The residue was partitioned between dichloromethane and dilute hydrochloric acid. The organic layer was separated, dried over sodium sulphate and evaporated to given an oil which was partitioned between acetonitrile and petrol to remove mineral oil. The acetonitrile extract was evaporated to give the title compound as an oil (10.3 g) which was used without further purification.
(ii) 1-Methyl-4-[4-(2-chloro-3-trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
A mixture of the above product (9.72 g), 2-chloro-3-trifluoromethylbenzaldehyde (8.34 g), methyl 3-aminocrotonate (4.61 g), acetic acid (4 ml) and ethanol (30 ml) was heated under reflux for 6 hours and then evaporated. The residue was partitioned between toluene and 2N hydrochloric acid. The acidic layer was separated and the toluene layer was washed with 2N hydrochloric acid. The combined acidic layers were extracted several times with dichloromethane. The organic extracts were combined and washed well with ammoniacal brine, dried over sodium sulphate and evaporated. The residual oil was chromatographed on silica gel. Elution with a 10:1 mixture of chloroform and methanol gave the product (9.0 g), m.p. 180°-181° C. (from chloroform/petrol). Found: C, 56.40; H, 5.67; N, 5.17. C 25 H 30 ClF 3 N 2 O 5 requires: C, 56.55; H, 5.70; N, 5.28%.
(iii) 4-[4-(2-chloro-3-trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
Treatment of the above product with 2,2,2-trichloroethyl chloroformate followed by zinc and acetic acid according to the method of Example 2(ii) gave the title compound, m.p. 162°-163° C. (from ethyl acetate/petrol). Found: C, 55.78; H, 5.50; N, 5.37. C 24 H 28 ClF 3 N 2 O 5 requires: C, 55.76; H, 5.46; N, 5.42%.
(iv) 1-(4-Amino-6,7-dimethoxyquinazol-2-yl)-4-[4-(2-chloro-3-trifluoromethylphenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
Treatment of the above product with 4-amino-2-chloro-6,7-dimethoxyquinazoline according to the method of Example 1 gave the title compound, m.p. 145°-146° C. (from ether). Found: C, 56.77; H, 5.26; N, 9.80. C 34 H 37 ClF 3 H 5 O 7 requires: C, 56.70; H, 5.18; N, 9.73%.
EXAMPLE 23
1-(4-Amino-6,7-dimethoxyquinazol-2-yl)-4-[4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
(i) 1-Methyl-4-[4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
Reaction of 2-chlorobenzaldehyde, ethyl 4-(1-methylpiperid-4-yloxy)acetoacetate and methyl 3-aminocrotonate according to the method of Example 22(ii) gave the title compound which was used directly in the next stage.
(ii) 4-[4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
Treatment of the above intermediate with 2,2,2-trichloroethyl chloroformate followed by zinc and acetic acid according to the method of Example 20(ii) gave the title compound as a gum. A portion was converted to the fumarate hemihydrate, m.p. 175°-176° C. (from ethyl acetate/methanol). Found: C, 56.26; H, 5.87; N, 4.87. C 23 H 29 ClN 2 O 5 .C 4 H 4 O 4 .1/2H 2 O requires: C, 56.49; H, 5.97; N, 4.88%.
(iii) 1-(4-Amino-6,7-dimethoxyquinazol-2-yl)-4-[4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxy]piperidine
Treatment of the above intermediate with 4-amino-2-chloro-6,7-dimethoxyquinazoline according to the method of Example 1 gave the title compound as an amorphous glass, (CDCl 3 ) 1.20 (t, 3H, J=7.1 Hz, CO 2 CH 2 Me); 1.6-1.75 (m, 2H, piperidine CH); 2.0-2.15 (m, 2H, piperidine CH); 2.33 (s, 3H, 6-Me); 3.25-3.4 (m, 2H, piperidine CH); 3.62 (s, 3H, CO 2 Me); ca 3.7 (m, 1H, piperidine 4-H); 3.93 (s, 3H, OMe); 3.98 (s, 3H), OMe); 4.06 (q, 2H, J=7.1 Hz, CO 2 CH 2 Me); 4.4-4.55 (m, 2H, piperidine CH); 4.75 (d, 1H) and 4.84 (d, 1H, J=16.3 Hz), CH 2 O; 5.11 (s, 2H, NH 2 ); 5.42 (s, 1H, 4-H); 6.78 (s, 1H) and 6.92 (s, 1H, quinazoline CH); 7.0-7.4 (m, aromatic CH and dihydropyridine NH).
EXAMPLE 24
1-(4-Amino-6,7-dimethoxyquinazol-2-yl)-4-[4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxymethyl]piperidin
(i) Ethyl 4-(1-benzylpiperid-4-ylmethoxy)acetoacetate
Treatment of ethyl 4-chloroacetoacetate with 1-benzylpiperidine-4-methanol according to the method of Example 22(i) gave the title compound as an oil which was used directly in the next step.
(ii) 1-Benzyl-4-[4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxymethyl]piperidine
Treatment of the above intermediate with 2-chlorobenzyaldehyde and methyl 3-aminocrotonate according to the method of Example 9(i) gave the title product as an oil. Found: C, 67.13; H, 6.71; N, 5.09. C 31 H 37 ClN 2 O 5 requires: C, 67.32; H, 6.74; N, 5.07%.
(iii) 4-[4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl-methoxymethyl]piperidine
Hydrogenation of the above product according to the method of Example 9(ii) gave the title compound as an oil which was used directly in the next step.
1-(4-Amino-6,7-dimethoxyquinazol-2-yl)-4-[4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,-4-dihydropyrid-2-yl-methoxymethylmethyl]piperidine
Treatment of the above intermediate with 4-amino-2-chloro-6,7-dimethoxyquinazoline by the method of Example 1 (3 hours reflux time) gave the title compound as an amorphous solid. Found: C, 61.19; H, 6.11; N, 10.09. C 34 H 40 ClN 5 O 7 requires: C, 61.30; H, 6.05; N, 10.51%.
EXAMPLE 25
4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl--6-methyl-2-{2-[N-(4-aminoquinazol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine hydrochloride sesquihydrate
(i) 4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-[2-(N-cyano-N-methyl)aminoethoxymethyl]-1,4-dihydropyridine
A solution of 4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-(2-dimethylaminoethoxy)methyl-1,4-dihydroypyeisinw (10.0 g) in chloroform (100 ml.) was added dropwise to a stirred solution of cyanogen bromide (2.43 g) in chloroformm (20 ml) at room temperature. The solution was stirred for 11/2 hours and then washed with dilute hydrochloric acid. The aqueous layer was washed with chloroform and the organic layers were combined, washed with water and dried over sodium sulphate. Evaporation of the solvent gave a solid which was chromatographed on silica gel. Elution with chloroform/petroleum ether (b.p. 40°-60° C.) (1:1) gradually increasing the ratio to 4:1 gave the title compound (6.79 g), m.p. 150°-151° C. (from ethyl acetate). Found: C, 59.25; H, 5.71; N, 9.39. C 22 H 26 ClN 3 O 5 requires: C, 58.99; H, 5.85; N, 9.38%.
(ii) 4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(3-aminoquinazol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine hydrochloride sesquihydrate
Sodium hydride (118 mg. of 50% dispersion in mineral oil) was added to a stirred solution of anthranilonitrile (132 mg.) in dry tetrahydrofuran (10 ml) and the mixture was stirred at room temperature for 45 minutes. A solution of the product from (i) above (500 mg.) in dry tetrahydrofuran was added dropwise with stirring. The mixture was heated under reflux for 11/2 hours, cooled and ethanol (1 ml.) was added. The solution was evaporated and the residue was chromatographed on silica gel. Elution with chloroform/petroleum ether (b.p. 40°-60° C.) (1:1) first gave mineral oil followed by product was a gum (240 mg.). The gum was dissolved in diethyl ether and an excess of ethereal hydrogen chloride was added. The solid was filtered off and dried go give the title compound as the hydrochloride sesquihydrate, m.p. ca. 120° C. (decomp.) Found: C, 55.48; H, 5.49; N, 10.92. C 29 H 32 ClN 5 O 5 .HCl.1.5 H 2 O requires: C, 55.37; H, 5.61; N, 11.13%.
EXAMPLE 26
4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6-methoxyquinazol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
Treatment of 4-(2-chlorophenyl)-3-ethoxycarbonyl-6-methoxycarbonyl-6-methyl-2-[2-N-cyano-N-methyl)aminoethoxymethyl]-1,4-dihydropyridine with 2-amino-5-methoxybenzonitrile according to the method of Example 25(ii) gave the title compound as a gum, (CDCl 3 ): 1.18 (t, 3H, J=7.1 Hz, CO 2 CH 2 Me); 2.05 (s, 3H, 6-Me); 3.28 (s, 3H, NMe); 3.57 (s, 3H, CO 2 Me), 3.79-3.92 (m, 6H, OCH 2 CH 2 N); 3.85 (s, 3H, OMe), 4.04 (q, 2H, J=7.1 Hz, CO 2 CH 2 Me); 4.75 (d, 1H) and 4.85 (d, 1H, J=16.2 Hz), CH 2 O; 5.22 (s, 2H, NH 2 ); 5.34 (s, 1H, 4-H); 6.81 (d, 1H, J=2.6 Hz, quinazoline H-5): 6.97-7.30 (m, 5H, aromatic CH and dihydropyridine NH); 7.45 (d, 1H, J=8.5 Hz, quinazoline H-8).
EXAMPLE 27
4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-7-methoxyquinazol-2-yl)-N-methylamino]ethoxy-methyl}-1,4-dihydropyridine
Treatment of 4-(2-chlorophenyl)-3-ethoxycarbonyl-6-methoxycarbonyl-6-methyl-2-[2-(N-cyano-N-methyl)aminoethoxymethyl]-1,4-dihydropyridine with 2-amino-4-methoxybenzonitrile according to the method of Example 25(ii) gave the title compound as a gum, CDCl 3 ): 1.20 (t, 3H, J=7.1 Hz, CO 2 CH 2 Me), 2.08 (s, 3H, 6-Me); 3.31 (s, 3H, NMe); 3.60 (s, 3H, CO 2 Me); ca 3.8-4.1 (m, 4H, OCH 2 CH 2 N), 3.89 (s, 3H, OMe); 4.06 (q, 2H, J=7.1 Hz, CO 2 CH 2 Me); 4.77 (d, 1H) and 4.86 (d, 1H, J=16.2 Hz), CH 2 O; 5.22 (s, 2H, NH 2 ); 5.37 (s, 1H, 4-H); 6.70-7.42 (8H, aromatic CH and dihydropyridine NH).
EXAMPLE 28
4-(2-Chlorothien-3-yl)-3 -ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-methyl-amino]-ethoxy}methyl-1,4-dihydropyridine
(i) 4-(2-Chlorothien-3-yl)-3-ethoxycarboyl-5-methoxycarbonyl-6-methyl-2-(2-dimethylaminoethoxymethyl)-1,4-dihydropyridine
Reaction of 2-chlorothiophene-3-carboxaldehyde with ethyl 4-(2-dimethylaminoethoxy)acetoacetate and methyl 3-aminocrotonate in ethanol according to the method of Example 9(i) gave the title compound, m.p. 110°-112° C. (from ethyl acetate/petrol b.p. 60°-80° C.). Found: C, 53.72; H, 6.26; N, 6.09. C 20 H 27 ClN 2 O 5 S requires: C, 54.22; H, 6.14; N, 6.32%.
(ii) 4-(2-Chlorothien-3-yl)-3-ethoxycarbonyl-5-ethoxycarbonyl-6-methyl-2-[2-(N-cyano-N-methyl)aminoethoxymethyl]-1,4-dihydropyridine
Treatment of the above intermediate with cyanogen bromide according to the method of Example 25(i) gave the title compound, m.p. 151°-152° C. (from ethyl acetate). Found: C, 52.83; H, 5.32; N, 8.95. C 20 H 24 ClN 3 O 5 S requires: C, 52.91; H, 5.32; N, 9.26%.
(iii) (4-(2-Chlorothien-3-yl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(2-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
Treatment of the above intermediate with 2-amino-4,5-dimethoxybenzonitrile according to the method of Example 25(ii) gave the title compound as an amorphous solid, (CDCl 3 ): 1.25 (t, 3H, J=7.1 Hz, CO 2 CH 2 Me); 2.09 (s, 3H, 6-Me); 3.29 (s, 3H, NMe), 3.64 (s, 3H, CO 2 Me): ca 3.85 and ca 3.95 (m, 4H, OCH 2 CH 2 N); 3.95 (s, 3H, OMe); 3.98 (s, 3H, OMe), 4.09 (q, 2H, J=7.1 Hz, CO 2 CH 2 Me); 4.77 (d, 1H) and 4.85 (d, 1H, J=16.2 Hz), CH 2 O; 5.12 (br s, 3H, NH 2 and 4-H), 6.68 (d, 1H, J=5.8 Hz, thiophene H-4), 6.80 (d, 1H, J=5.8 Hz, thiophene H-5), 6.76 (s, 1H) and 6.91 (s,1H), quinazoline CH; 7.08 (s, 1H, NH).
EXAMPLE 29
4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-(2-hydroxyethyl)-amino]ethoxymethyl}-1,4-dihydropyridine
(i) 4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-(2-hydroxyethyl)-amino]ethoxymethyl}-1,4-dihydropyridine
A mixture of 4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-(2-methylamino-ethoxymethyl)-1,4-dihydropyridine (3.80 g.), 2-benzyloxyethyl chloride (1.54 g.), sodium iodide (1.35 g.) and anhydrous sodium carbonate (0.95 g.) in acetone (80 ml.) was heated under reflux with stirring for 18 hours. The mixture was cooled, filtered and the residue was washed with acetone. The filtrate and wasings were evaporated and the residue was chromatographed on silica gel. Elution with chloroform gave the product as an oil (2.30 g.). Found: C, 64.85; H, 6.91; N, 5.29. C 30 H 37 ClN 2 O 6 requires: C, 64.68; H, 6.70; N, 5.03%.
(ii) 4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-2-{2-[N-cyano-N-(2-benzyloxyethyl)-amino]ethoxymethyl}-1,4-dihydropyridine
Treatment of the above intermediate with cyanogen bromide according to the method of Example 25(i) gave the title product, m.p. 102°-103° C. Found: C, 63.56; H, 6.09; N, 7.63. C 30 H 34 ClN 3 O 6 requires: C, 63.43; H, 6.03; N, 7.40%.
(iii) 4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarboyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-(2-benzyloxyethyl)amino]ethoxymethyl}-1,4-dihydropyridine
Treatment of the above intermediate with 2-amino-4,5-dimethoxybenzonitrile according to the method of Example 25(ii) gave the title product as an amorphous solid. Found: C, 62.66; H, 6.11; N, 8.72. C 39 H 44 ClN 5 O 8 requires: C, 62.77; H, 5.94; N, 9.39%.
(iv) 4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-amino-6,7-dimethoxyquinazol-2-yl)-N-(2-hydroxyethyl)amino]ethoxymethyl}-1,4-dihydropyridine
A solution of the above intermediate (0.18 g.) in ethanol (30 ml.) and concentrated hydrochloric acid (0.2 ml.) was hydrogenated at 22° C. and 4 atm. pressure in the presence of 10% palladium on carbon (18 mg.). When no further hydrogen was absorbed the solution was filtered and evaporated. The residue was partitioned between sodium bicarbonate solution and ethyl acetate. The aqueous layer was washed with ethyl acetate and the combined organic layers were dried over sodium sulphate and evaporated. The residue was chromatographed on silica gel. Elution with chloroform/hexane (1:1) first gave impurity; further elution with chloroform followed by chloroform/methanol (20:1) gave the title compound as an amorphous solid (0.08 g.). Found: C, 58.29; H, 6.31; N, 9.88. C 32 H 38 ClN 5 O 8 requires: C, 58.57; H, 5.84; N, 10.67%.
EXAMPLE 30
4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-aminoquinol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
(i) N-{2-[4-(2-Chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-1,4-dihydropyrid-2-yl]methoxyethyl}-N-methyl-N'-(2-cyanophenyl)acetamidine
A mixture of 4-(2-chlorophenyl)-3-ethoxycarbonyl-5-methoxycarbonyl-6-methyl-2-(2-methylaminoethoxymethyl)-1,4-dihydropyridine (2.5 g.), ethyl N-(2-cyanophenyl)acetimidate (1.1 g.) and p-toluenesulphonic acid (0.1 g.) was heated at 150° C. for 4 hours, cooled, and then dissolved in chloroform. The solution was washed with sodium bicarbonate solution, water and dried over sodium sulphate. Evaporation of the solvent gave an oil which was chromatographed on silica gel. Elution with chloroform/hexane (1:1) gave the product as an oil (0.95 g.) which was used directly in the next stage.
(ii) 4-(2-Chlorophenyl)-3-ethoxycarabonyl-5-methoxycarbonyl-6-methyl-2-{2-[N-(4-aminoquinol-2-yl)-N-methylamino]ethoxymethyl}-1,4-dihydropyridine
n-Butyllithium (4.5 ml. of 1.6M solution in hexane) was added dropwise to a stirred solution of di-isopropylamine (0.72 g.) in dry tetrahydrofuran (15 ml.) at -70° C. and the solution was stirred at -70° C. for 10 minutes. A solution of the above intermediate (0.5 g.) in dry tetrahydrofuran (10 ml.) was added dropwise with stirring over 5 minutes. The resulting solution was stirred at -70° C. for 31/2 hours and then at room temperature for 18 hours. The solution was poured into water and the mixture was extracted several times with chloroform. The combined extracts were washed with water, dried over sodium sulphate and evaporated. The residue was chromatographed on silica gel. Elution with chloroform/hexane (1:1) gave some starting material; further elution with chloroform and finally with chloroform/methanol (10:1) gave the title compound as an amorphous solid (0.25 g.). Found: C, 63.31; H, 6.07; N, 10.01. C 30 H 33 ClN 4 O.sub. 5 requires: C, 63.76; H, 5.88; N, 9.92%.
PREPARATION 1
The following starting materials of formula II were prepared as described in Example 9(i) and 9(ii). The products were used for Examples 9-19.
__________________________________________________________________________ ##STR12## Analysis % (Theoretical in Brackets)R.sup.1 R.sup.2 R.sup.5 R.sup.8 R.sup.9 R.sup.10 n m.p. °C. C H H__________________________________________________________________________CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F H CH.sub.2 Ph 2 91-92 67.91 6.73 5.56 (67.72 6.70 5.64)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F H H 2 -- USED WITHOUT CHARACTERIZATIONCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F 3-F CH.sub.2 Ph 2 73-74 65.18 6.20 5.13 (65.35 6.27 5.44)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F 3-F H 2 168-171 54.55 5.79 6.17 (54.72 5.90 6.08)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F 3-Cl CH.sub.2 Ph 2 -- 63.71 6.15 4.92 (63.33 6.08 5.28)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 F 3-Cl H 2 188-189 52.80 5.73 5.92 (52.83 5.70 5.87)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 3-F CH.sub.2 Ph 2 82-83 62.72 6.12 5.12 (63.33 6.08 5.28)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 3-F H 2 101.102 56.97 5.95 6.12 (57.20 5.94 6.36)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 6-F CH.sub.2 Ph 2 87.88 63.63 6.06 5.44 (63.33 6.08 5.28)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 6-F H 2 .sup. 165-166.sup.a 53.22 5.81 5.83 (52.83 5.70 5.87CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 3-CF.sub.3 CH.sub.2 Ph 2 145-148 56.21 5.50 4.62 (56.40 5.39 4.54)CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl 3-CF.sub.3 H 2 184-187 49.97 5.22 5.31 (50.10 5.16 5.31).sup.d CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl H CH.sub.2 Ph 3 -- USED WITHOUT CHARACTERIZATIONCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl H H 3 -- USED WITHOUT CHARACTERIZATION.sup.d CH.sub.3 CH.sub.3 CH.sub.3 Cl H CH.sub.2 Ph 2 -- USED WITHOUT CHARACTERIZATIONCH.sub.3 CH.sub.3 CH.sub.3 Cl H H 2 .sup. 175-177.sup.a 53.60 5.82 6.21 (53.94 5.88 6.29).sup.d C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 Cl H CH.sub.2 Ph 2 -- USED WITHOUT CHARACTERIZATIONC.sub.2 H.sub.5 CH.sub.3 CH.sub.3 Cl H H 2 .sup. 101-120.sup.b 58.66 6.55 6.61 (58.39 6.53 6.49).sup.d CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl H CH.sub.2 Ph 2 .sup. 104-107.sup.c 61.21 6.06 4.41 (61.63 6.11 4.35)CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 Cl H H 2 .sup. 185-187.sup.a 55.51 6.30 5.91 (55.81 6.37 6.00)__________________________________________________________________________ .sup.a Hydrochloride;- .sup.b Hemihydrate;- .sup.c Fumarate;- .sup.d starting betaketo ester prepared by analogous method to Example 22(i).
PREPARATION 2
2-Chloro-3-fluorobenzaldehyde
(i) To a stirred solution of 2-(3-fluorophenyl)-4,4-dimethyloxazoline (36.7 g) in dry tetrahydrofuran (500 ml.) at -65° C. was added dropwise n-butyl-lithium (119 ml. of 1.6M solution in hexane). The solution was stirred at the same temperature for 1 hour and then a solution of 4-toluenesulphonic chloride (36.2 g.) in dry tetrahydrofuran (250 ml.) was added over 45 minutes, maintaining the temperature below -50° C. The mixture was stirred at -50° C. for 1 hour and then allowed to warm up to room temperature and stirred for a further 2 hours. An excess of water was added and the mixture was evaporated to a low volume and extracted several times with diethyl ether. The combined extracts were washed with diluted sodium hydroxide solution, water and then dried over sodium sulphate. Evaporation of the solvent gave an oil which was distilled to give 2-(2-chloro-3-fluorophenyl)-4,4-dimethyloxazoline (29.0 g.), b.p. 138°-140° C. at 15 m.m. Found: C, 57.93; H, 4.77; N, 6.20. C 11 H 11 ClFNO requires: C, 58.03; H, 4.87; N, 6.15%.
(ii) 2-(2-Chloro-3-fluorophenyl)-3,4,4-trimethyloxazolinium iodide
Iodomethane (9.4 g.) was added dropwise to a stirred solution of the above product (10.0 g.) in nitromethane (22 ml.). The mixture was stirred at 70° C. for 4 hours, cooled and diluted with diethylether. The solid was filtered off, washed with diethyl ether and dried to give the title product (15.5 g.), m.p. 197° C. (decomp.). Found: C, 38.83; H, 3.67; N, 3.67. C 12 H 14 ClFlNO requires: C, 38.99; H, 3.82; N, 3.79%.
(iii) 2-Chloro-3-fluorobenzaldehyde
The above product (15.5 g) was suspended in ethanol (50 ml) at 5° C. and sodium borohydride (1.6 g) was added portionwise with stirring. The mixture was stirred at 5° for 15 minutes and then at room temperature for 2 hours to give a clear solution. The solution was evaporated and the residue was dissolved in 2N hydrochloric acid (50 ml), heated to 50° C. for a few minutes and cooled. The resulting oil was extracted with diethyl ether. The ether extracts were washed with water, dried over sodium sulphate and evaporated. The residue was distilled to give 2-chloro-3-fluorobenzaldehyde (5.0 g), b.p. 86°-88° C. at 15 m.m. Found: C, 53.16; H, 2.54. C 7 H 4 ClFO requires: C, 53.02; 2.54%.
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Dihydropyridines of the formulae ##STR1## wherein R is chlorothienyl or mono- or disubstituted phenyl where said substituent is fluoro, chloro, bromo or trifluoromethyl; R 1 and R 2 are each alykl; R 3 and R 4 when taken separately are each hydrogen or alkyl; R 3 and R 4 when taken together with the nitrogen to which they are attached are piperidine or pyrrolidine; R 5 is alkyl or 2-hydroxyethyl; R 6 is hydrogen or methoxy; X and Z are each hydrogen or methoxy; Y is alkylene; R 7 is chlorophenyl or trifluoromethyl-chlorophenyl; p is 0 or 1; and Q is CH or N are useful in the treatment of hypertension, heart failure and angina.
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CROSS REFERENCE TO RELATED APPLICATION
This application claims priority to Provisional Applications Ser. No. 60/237,142, filed Oct. 2, 2000, and Ser. No. 60/243,022, filed Oct. 25, 2000, the entirety of which are incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to recording media, ink compositions, methods of making recording media and inks, nanoparticles, and methods of making nanoparticles.
BACKGROUND OF THE INVENTION
Typically, recording media used in printing processes degrade when exposed to chemical or physical processes involving the environment or involving the printing process itself. A recording medium is a composition capable of providing an indicator, a surface modification, or an aesthetic attribute on a substrate. Recording media can include, for example, inks used in printing on paper and textiles, surface modifiers that provide gloss or texture, colorless compositions that change to color when irradiated with UV or visible radiation, various coatings for surfaces, and the like.
Photodegradation occurs when the recording medium fades when exposed to electromagnetic radiation such as sunlight or artificial light and the like. These degradation mechanisms include photooxidation or -reduction of the recording medium depending upon the environmental conditions experienced. Product analysis of stable photoproducts and intermediates in various recording media has revealed several important modes of photodegradation. These include electron ejection from the recording medium, reaction with ground-state or excited singlet state oxygen, bond cleavage to form various products, reduction to form the colorless leuco dyes, and electron or hydrogen atom abstraction to form radical intermediates.
Various environmental factors such as temperature, humidity, gaseous reactants including O 2 , O 3 , SO 2 , and NO 2 , and water soluble nonvolatile photodegradation products have been shown to influence fading of colorants. The factors that effect fading appear to exhibit a certain amount of interdependence. It is due to this complex behavior that observations for the fading of a particular colorant on a particular substrate cannot be applied to colorants and substrates in general.
The ability of a light source to cause photodegradation in a recording medium is also dependent upon the spectral distribution of the light source, that is the proportion of radiation of wavelengths most effective in causing a change in the recording medium and the quantum yield of degradation as a function of wavelength. On the basis of photochemical principles, it might be expected that light of higher energy (short wavelengths) would be more effective at causing fading than light of lower energy (long wavelengths). Studies have revealed that this is not always the case. Over 100 colorants of different classes were studied and found that generally the most unstable were faded more efficiently by visible light while those of higher lightfastness were degraded mainly by ultraviolet light (McLaren, K., J. Soc. Dyers Colour, 1956, 72, 86).
In addition, the influence of a substrate on recording medium stability can be extremely important. Due to the complex behavior of recording media, the mechanisms causing fading of a particular recording medium on a particular substrate cannot be applied to recording media and substrates in general. Fading may be retarded or promoted by a chemical group within the substrate. Such a group can be a ground-state species or an excited-state species. The porosity of the substrate is also an important factor in recording medium stability. For example, a high porosity can promote fading by facilitating penetration of moisture and gaseous reactants into the substrate. A substrate may also act as a protective agent by screening the recording medium from light of wavelengths capable of causing degradation.
The purity of the substrate is also an important consideration whenever the photochemistry of dyed technical polymers is considered. For example, technical-grade cotton, viscose rayon, polyethylene, polypropylene, and polyisoprene are known to contain carbonyl group impurities. These impurities absorb light of wavelengths greater than 300 nm, which are present in sunlight, and so, excitation of these impurities may lead to reactive species capable of causing fading (van Beek, H. C. A., Col. Res. Appl., 1983, 8(3), 176).
Under conditions of constant temperature it has been observed that an increase in the relative humidity of the atmosphere increases fading of a colorant for a variety of colorant-substrate systems (e.g., McLaren, K., J. Soc. Dyers Colour, 1956, 72, 527). For example, as the relative humidity of the atmosphere increases, a fiber may swell because the moisture content of the fiber increases. This aids diffusion of gaseous reactants through the substrate structure.
In addition to fading, recording media tend to bleed when applied to certain substrates, especially textiles. Accordingly, a recording medium capable of demonstrating enhanced stability and light fastness when applied to any type of substrate is desired.
There is also a need for a recording medium that not only provides increased stability and lightfastness, but also one that is capable of being printed on substrates without special treatment or other limitations. In addition, a superior textile recording medium with substrate independent durability performance is needed.
What is also desired is a recording medium that not only provides increased stability and lightfastness, but also one in which color intensity and hue are capable of being finely manipulated.
There also exists a need for methods and compositions which are capable of stabilizing a wide variety of recording media from the effects of both sunlight and artificial light. In addition, methods and compositions are needed that can stabilize a recording medium from the deleterious effects of humidity and oxygen and other gaseous reactants such as O 3 , SO 2 , and NO 2 .
SUMMARY OF THE INVENTION
The present invention is directed to providing, among other things, new recording media comprising nanoparticles, methods for stabilizing recording media against photodecomposition and environmental degradation, methods for finely manipulating color intensity and hue, and processes for printing on varied substrates. This invention also provides the new nanoparticles themselves, methods of making these nanoparticles, and methods of making nanoparticle based recording media and inks.
In general, the present invention is directed to recording media comprising particles or nanoparticles with a polymeric core. These particles or nanoparticles are formed in an oil/water system by high shear emulsification. The polymeric core can be used as a surface upon which to bind colorants, functional additives, charged polymers, and colorant-charged polymer layers. The polymeric core itself and the charged polymer layers can incorporate any number of functional agents, including but not limited to, colorants, colorant stabilizers, functional additives, and any combinations thereof. The nanoparticle can further comprise a protective coating such a charged polymer or crosslinked polymer. The ability to incorporate colorants into the polymeric core, as well as in the sequential layers of charged polymers, provides the ability to finely adjust the color and other properties of the recording medium.
Accordingly, one aspect of the present invention is multiple layers of charged polymer-colorant (or polyelectrolyte-colorant) being assembled on the surface of a nanoparticle core. Because these layers are typically characterized by alternating charges, layer integrity is maintained by coulombic forces, as well as by van der Waals and other physical and chemical forces. Different colorants may be used in sequential charged polymer-colorant layers to afford unusual or hard-to-obtain colors. Additionally, a charged polymer-colorant layer may alternate with charged polymer void of colorant, in order to protect the colorant below the void charged polymer layers, or to manipulate particle charge. Charged polymer layers may also contain “functional additives” such as UV or visible radiation filters or screening agents to protect dyes from harmful radiation, leuco dyes or colorless predyes that develop color upon irradiation, or reactive species generators that react to fade colors upon irradiation. A final outside layer, comprised of a protective stratum of transparent charged polymer, may optionally be added to the nanoparticle. When assembled in this fashion, the final charge of this protective outer layer (zeta potential) is employed to adhere the dye particle to the fabric surface during printing. Thus, by matching the nanoparticle charge to the opposite charge of the printing substrate or textile coating, strong coulombic attraction can be achieved, in addition to van der Waals and other physical and chemical forces.
The present invention is also directed to recording media containing the above-described nanoparticles. The recording media can be applied to any substrate and can be used, for example, to impart a color to a substrate, provide a functional coating on a substrate, provide lightfastness, provide a texture, gloss or finish to a substrate, and for other uses to modify, stabilize, or protect a substrate. For example, one aspect of the present invention is that, a colorant composition comprising the nanoparticles described above, a liquid medium and a pre-polymer is coated onto a substrate and subsequently exposed to radiation to fix the nanoparticle to the substrate via the polymerization of the pre-polymer. The present invention includes methods for enhancing the substrate-independent durability performance of recording media.
The present invention is further directed to a method of stabilizing a colorant by assembling multiple layers of charged polymer-colorant and colorless charged polymer on a nanoparticle surface. In one aspect of the present invention, one or more colorant stabilizers are also incorporated in the charged polymer layers, thereby providing multiple levels of colorant protection from photodegradation mechanisms.
The present invention includes methods to stabilize recording media against environmental degradation. The present invention also includes methods to stabilize recording media against photodecomposition.
The present invention is also directed to nanoparticles and methods of making these nanoparticles.
The present invention also provides a series of methods and compositions for more finely manipulating color density and hue on various substrates.
The present invention is further directed to methods of making recording media comprising particles.
The present invention is also directed to printing processes using recording media comprising nanoparticles.
These and other features and advantages of the present invention will become apparent after a review of the following detailed description.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 illustrates one aspect of the present invention, depicting the formation of a nanoparticle by adding multiple layers of charged polymer-colorant or alternating layers of charged polymer-colorant/colorless charged polymer onto a nanoparticle template. The size of the resulting colored nanoparticle will increase accordingly, as shown.
FIG. 2 . illustrates one aspect of the present invention, depicting the formation of a nanoparticle by adding multiple layers of alternating charge of charged polymer-colorant and colorless charged polymer onto a nanoparticle template comprising a polymeric core. Among other things, this figure demonstrates how the integrity of the layers is maintained by coulombic forces in addition to van der Waals and other physical and chemical forces, how a final outside layer comprised of a protective stratum of charged polymer may be added to the nanoparticle, and how the coulombic and other forces that increase the stability of the colored nanoparticle provide greater colorfastness of the resultant inks.
FIG. 3 depicts the formation of final protective coating on a nanoparticle of the present invention by associating a charged polymer comprising a crosslinkable group (here, an anhydride) with the nanoparticle, followed by adding a crosslinking agent (here, a diamine) to form the final protective coating. In the example presented in this figure, the final coating is a polyamide.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to recording media containing new types of nanoparticles. The use of nanoparticles in the recording media of the present invention, among other things, intensifies the colors and stabilizes the colorants when they are exposed to light and other potentially degrading conditions. The present invention is useful for printing processes on all substrates. The recording media can be applied to any substrate to impart a color to the substrate, coat the surface of the substrate, or provide texture or aesthetic factors to the substrate. The recording media of the present invention typically comprise nanoparticles and a liquid medium. However, the present invention also encompasses a pre-polymer/nanoparticle mixture that is coated onto a substrate and subsequently exposed to radiation or heat to fix the nanoparticle to the substrate by polymerization of the pre-polymer. The recording media of the present invention can also be a polymer coating of a heat transfer product, such as that used for transferring graphic images onto clothing.
The recording media of the present invention can be very effective in ink jet inks. Recording media used in ink jet printers are described in U.S. Pat. No. 5,681,380, assigned to Kimberly-Clark Worldwide, Inc., which is incorporated herein by reference in its entirety. Additionally, the recording media of the present invention are effective in coatings for paper products and textiles.
In one aspect of the present invention, the nanoparticle of the recording medium has multiple layers of charged polymer-colorant and colorless charged polymer or “void” charged polymer (without a colorant) layers assembled on the polymeric nanoparticle core surface. Another aspect of the present invention is multiple, alternating layers of charged polymer-colorant being assembled on the polymeric nanoparticle core surface without void charged polymer layers between the charged polymer-colorant layers. In one embodiment, the nanoparticle is coated with colorant or other functional additive prior to any coating comprising a charged polymer. The nanoparticle core itself comprises a polymer that can include a colorant and/or functional additive. In one aspect, different colorants may be used in sequential charged polymer-colorant layers and/or within the core to afford tailored colors. Charged polymer layers may also contain “functional additives” such as UV or visible radiation screening agents or filters to protect dyes from harmful radiation, leuco dyes or colorless predyes that develop color upon irradiation, or reactive species generators that react to fade colors upon irradiation. Because, in one aspect, layers are characterized by alternating or different charges, the integrity of the layers is maintained by coulombic forces, as well as by van der Waals and other physical and chemical forces. Changes in the zeta potential after each layer confirms that substantially uniform and substantially complete coating has been achieved. Charged polymers that are useful in the present invention include, but are not limited to, the polycations polyethylenimine, permethylated, perbromide (MW=1800, Polysciences, Warrington, Pa.), and poly(2-methacryloxyethyl trimethylammonium bromide). Examples of polyanions used herein are poly(vinylsulfonic acid, sodium salt) MW=2000, Polysciences, Warrington, Pa.) and poly(styrene sulfonic acid, sodium salt).
The present invention is also directed to recording media comprising nanoparticles of less than or about 1000 nanometers (nm) comprising a polymeric core. The polymeric core can have at least one colorant disposed within, and typically dispersed substantially throughout, the polymeric material. Optionally, the core may be coated with one or more colorant layers, colorless charged polymer layers, charged polymer-colorant layers, or any combination thereof disposed on its surface. Moreover, the nanoparticle may further comprise at least one surface modifying layer disposed on and substantially covering the polymeric material. The colorants of the core and charged polymer layers can be the same or different. Likewise, the colorant of the charged polymer layers can differ in alternating layers, or the charged polymer-colorant layers and the void charged polymer layers can alternate in any fashion. By carefully choosing the colorants in each layer in the manner known to one of ordinary skill in the art, fine color control can be achieved. The nanoparticle can optionally comprise an outer crosslinked protective coating that encapsulates the layers below. Of course, the recording media can comprise any suitable carrier for the nanoparticles.
This layer-by-layer self-assembly of alternately-charged and/or differently-charged, charged polymer-colorant polymers (including, in some embodiments, colorless charged polymer) bound to the polymeric nanoparticle core provides the resulting recording medium or ink with enhanced light fastness, unlimited use of water soluble dyes (containing charge centers), control of color density, and strong fabric bonding via coulombic, van der Waals, and other forces, leading to enhanced durability. In addition, control of color density may also be achieved by adjusting reaction times between the polymeric nanoparticle substrate and the charged polymer-colorant where the extent of coating the particle dictates color density.
One aspect of the present invention is directed to a recording medium comprising a polymer core of an organic polymer that comprises a colorant disposed within, and typically dispersed substantially throughout, the polymer up to about 30% by weight. A solution of dye and polymer in a solvent is subjected to high shear emulsification in an oil/water system, resulting in nanoparticle formation. The resultant nanoparticles are then coated with charged polymer layers, in which some of the charged polymer can have another colorant complexed with it. By employing a nanoparticle core that already comprises a colorant, high color intensities may be achieved by coating the resultant nanoparticles with multiple charged polymer layers comprising another colorant complexed therewith. Additionally, the resultant polymer-colorant nanoparticles may be coated with colorant, charged polymer layers, colorant-charged polymer layers comprising a different or the same colorant to achieve fine control over color hue, intensity and stability. The nanoparticles are combined with a suitable carrier to form a recording medium such as an ink.
The polymeric core can comprise any suitable organic polymer, an inorganic polymer, a semiorganic polymer (primarily organic backbone with pendant inorganic groups), a semi-inorganic polymer (primarily inorganic backbone with pendant organic groups), an organometallic polymer, or combinations thereof, capable of forming a particle and having a zeta potential. Organic polymers suitable for the polymeric core include, but are not limited to, polymer particles, such as particles of polyacetals, polyacetaldehydes, polyacetates, polyacetylenes, polyacrylamides, polyamideimides, polyacrylates, polyacrylic acids, polyacrylonitriles, poly(melamine formaldehyde), polyalkylsilynes, poly(amic acids), polyamides, polycaproic acids, polyanilines, polyaramides, polyarylates, polybenzimidazoles, polybenzothiazones, polybenzoxazoles, polyalkadienes (such as polybutadienes or polypentadienes), polybutenes, poly(alkylene terphahalates), poly(caprolactams), poly(caprolactones), polycarbonates, polycarbosilanes, polychloroprenes, polyalkylenes (such as polyethylenes, polypropylenes, and polybutenes), polyalkylene oxides (such as polyethylene oxides or poly-p-phenyleneoxides), polyalkylenesulfides (such as polyethylene sulfides), polysilanes, polysiloxanes, polysilylenes, polyepichlorohydrins, polyesteramides, polyesters, polyimides, polyethers, polyalkylene glycols, polyglycols, polyether glycols, polyetherimides, polyketones, polysulfones, polyethyleneimines, polyimidosulfides, polyketones, polyisoprenes, polyphosphates, polynitriles, polystyrenes, polyurethanes, polytriazoles, polyterpenes, polynitrides, polysulfides, mixtures thereof, and copolymers thereof. Preferred organic polymers can include but are not limited to polyamines such as poly(melamine formaldehyde), polyamides, polyesters, poly-isoprenes, poly-butadienes, poly(acrylonitrile-cobutadiene), poly(acrilonitrile-co-butadiene-co-styrene), poly(α-methylstyrene), poly(vinyl acetate), copolymers thereof, combinations thereof, and crystallites of organic compounds. Most useful are polymers capable of forming nanoparticles of 50 nm or less.
The discussion is directed to particles of less than about 1000 nanometers (nm), however, the same principles can apply to a particle having a size of greater than 1000 nm. Before coating with charged polymer layer, the polymeric core can have an average particle size of less than about 100 nm, typically less than about 40 nm. In accordance with the present invention, the polymeric core can also have an average size of about 25 nm or even about 12 nm. However, the size of the charged polymer-coated core varies according to the number of layers of charged polymer that are layered on the nanoparticle, and whether or not a final protective coating is employed.
In accordance with the present invention, the resultant size of the nanoparticle after deposition of charged polymer layers on the polymer core is typically less than about 1000 nm. Typically the size of the resultant nanoparticle is less than about 500 nm and more typically less than about 300 nm. The size of the particle is related to the performance of the invention. Smaller nanoparticles are less likely to settle out of a recording medium over a period of time and provide greater stability. In addition, the nanoparticles must be capable of ejection through small orifices for applications such as ink jet printers, therefore nanoparticles in a smaller range are preferred. Furthermore, smaller nanoparticles provide for greater durability in textile printing applications due to the increased surface area of the nanoparticles, which enhances the adherence of the nanoparticle to the textile. Nanoparticles can comprise any shape, such as, for example, spheres, crystals, rods, discs, tubes, and the like.
The term “charged polymer” or the term “polyelectrolyte” are, in general, used interchangeably herein to include, without limitation any polymer or oligomer that is charged. Therefore, this term includes any polymer comprising an electrolyte, that is, a polymer comprising formal charges and its associated counter ions, the identity and selection of which will be well known to one of ordinary skill in the art. However, this term is also used to include polymers that can be induced to carry a charge by, for example, adjusting the pH of their solutions. For example, the charged polymer poly(butyl acrylate-methacryloxyethyl) trimethylammonium bromide is included in the use of the term “charged polymer”, as is the polymer poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine] which can readily be protonated so that it becomes charged. Additional terms “polyelectrolyte-polymer”, “colorless charged polymer”, “colorless polyelectrolyte”, “void charged polymer”, “void polyelectrolyte”, or “transparent charged polymer”, and so forth, are used herein to refer to a charged polymer. These terms are used to distinguish a charged polymer that does not comprise a colorant associated therewith, from one that does. Examples of polycations used herein are polyethyleneimine permethylated perbromide and poly(2-methacryloxyethyltrimethylammonium bromide). Examples of polyanions used herein are poly(vinyl sulfonic acid, sodium salt) and poly(styrene sulfonic acid, sodium salt).
Any charged polymer can be used that has a positive charge, a negative charge, or can be induced to carry a positive or negative charge by, for example, adjusting the pH of their solutions. Suitable charged polymers with positive charge include but are not limited to polyethyleneimines of less than about 5,000 molecular weight (M W ). More preferable are polyethyleneimines of from about 1000 molecular weight to about 2000 molecular weight. Most preferable are poly(ethyleneimines) and methylated derivatives thereof, of about 1200 M W and 1800 M W . Suitable polymers and methylated polymers with a positive charge (polycations) also include but are not limited to poly(2-butylmethacryloxyethyltrimethylammonium bromide). Suitable polymers with a negative charge (polyanions) include but are not limited to poly(styrenesulfonic acid), poly(vinylsulfonic acid), polyethylene imine permethylated perbromide, and salts (for example, sodium salts) thereof
The term “zeta potential” is used herein to mean without limitation a potential gradient that arises across an interface. This term especially refers to the potential gradient that arises across the interface between the boundary layer in contact with the nanoparticle of the present invention and the moveable diffuse layer in which the nanoparticle is suspended. Zeta potential measurements were taken using a Zetapals Instrument (Brookhaven Instrument Corporation, Holtsville, N.Y.), by adding 1–3 drops of sample into a cuvet containing 1 mM KCl solution, using the instrument's default functions preset for aqueous solutions.
The polymeric core and/or the charged polymer coatings can have an agent or “functional agent” disposed within the polymer. Typically, the agent is dispersed throughout the polymer. “Agents” or “functional agents” for the purposes of this invention, are compositions capable of providing a functional or aesthetic benefit and can include, for example, colorants, colorant stabilizers, UV absorbers, and various functional additives.
As used herein, the term “colorant” is meant to include, without limitation, any material which typically will provide tint or color to a substrate. The term is meant to include a single material or a mixture of two or more materials. Suitable colorants for use in the present invention include, but are not limited to, dyes and pigments. The colorant can be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-α-[4-(dimethylamino)phenyl]-α-phenyl-benzene-methanol}, Malachite Green Carbinol hydrochloride {N-4-[[4-(dimethylamino)phenyl]phenyl-methylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)phenyl]phenylmethylium chloride}, and Malachite Green oxalate {N-4-[[4-(dimethylamino)-phenyl]-phenylmethylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)-phenyl]phenylmethylium oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine monohydrochloride], Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and β-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt]; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2-[(hydrazinocarbonyl)amino]-2,3-dihydro-1,3-dioxo-1H-benz[de]iso-quinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as Janus Green B {3-(diethylamino)-7-[[4-(dimethyl-amino)phenyl]azo]-5-phenylphenazinium chloride}; cyanine dyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz[e]indol-2-ylidene]-1,3,5-heptatrienyl]-1,1-dimethyl-3-(4-sulfobutyl)-lH-benz[e]indolium hydroxide inner salt sodium salt}; indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-3-one}; coumarin dyes, such as 7-hydroxy-4-methyl-coumarin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 [bisbenzimide or 2-(4-hydroxyphenyl)-5-(4-methyl-1-piperazinyl)-2,5-bi-1H-benzimidazole trihydro-chloride pentahydrate]; paraquinoidal dyes, such as Hematoxylin {Natural Black 1; 7,11b-dihydrobenz[b]-indeno[1,2-d]pyran-3,4,6a,9,10(6H)-pentol}; fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein); diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxy-benzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4-dinitrophenyl)-1,4-phenylenediamine or Solvent Orange 53]; diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)-naphthalene]; anthra-quinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone], and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo-1-naphthalenyl)-azo]-1-naphthalenyl)azo]-1,5-naphthalenedisulfonic acid tetrasodium salt}; xanthene dyes, such as 2,7-dichloro-fluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)-[29H,31H-phthalocyanato(2-)-N 29 , N 30 ,N 31 ,N 32 ]-copper}; carotenoid dyes, such as trans-β-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-a-D-glucopyranosyl-9, 10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9, 10-dioxo-2-anthracene-carbonylic acid); azure dyes, such as Azure A [3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or 7-(dimethyl-amino)-3-imino-3H-phenothiazine hydrochloride]; and acridine dyes, such as Acridine Orange [Basic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridinium chloride mixture with 3,6-acridine-diamine).
Suitable colorants for use in the present invention also include a family of subphthalocyanine compounds having the following general formula:
wherein R 1 to R 12 and Z each independently represent —H; a halogen; an alkyl group; a substituted alkyl group; an aryl group; a substituted aryl group; an alkoxide group; a substituted alkoxide group, a phenoxy group; a substituted phenoxy group; an alkyl sulfide; an aryl sulfide; a nitrogen-containing group; a sulfonic acid; a sulfur-containing group; —OR′, —NR′R″, or —SR′, wherein R′ and R″ each independently represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. In accordance with the present invention, R 1 to R 12 each independently represent —H, a halogen, an alkyl group, a nitrogen-containing group, or a sulfur-containing group. Typically, R 1 to R 12 each independently represent —H, chlorine, bromine, fluorine, iodine, a tert-butyl group, —NO 2 , —SO 3 H, —SO 3 Na, —SO 3 Cl, or —SO 3 − pyH + .
Suitable Z substituents may be selected from a variety of substituents, which provide desirable properties to the resulting subphthalocyanine compound. In accordance with the present invention, Z comprises a moiety which stabilizes the subphthalocyanine compound; a moiety which renders the subphthalocyanine compound water soluble; or a moiety which both stabilizes and renders the subphthalocyanine water soluble. Examples of suitable Z include, but are not limited to, a hydroxyl group; a halogen; an alkyl group; an alkoxy group; an ether group; a polyol group; an aromatic group; a substituted aromatic group; a nitrogen-containing group; a sulfur-containing group; —OR′, —NR′R″, or —SR′, wherein R′ and R″ each independently represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and so forth. Typically, Z comprises one of the following moieties:
where x is an integer from 3 to 30, and R″′ is a hydrogen or an alkyl group having up to six carbon atoms.
Specific examples of subphthalocyanine compounds suitable for use in the present invention include, but are not limited to, the following compounds given below, wherein
and wherein abbreviations such as R 1-4 represent the substituents R 1 to R 4 :
In a further aspect of the present invention, the lightfastness properties of the subphthalocyanine dye may be greatly improved to archival levels by the presence of a perfluorotetraphenylporphine. The present invention encompasses both the physical mix and the covalent attachment of the perfluorotetraphenylporphine and the subphthalocyanine dye. For example, when the subphthalocyanine dye shown below (where R 1 to R 12 are H, and Z is —OC 6 H 3 -3,5-Me 2 ) is physically admixed with copper-meso-perfluorotetraphenylporphine (abbreviated CuF 20 TPP) in a polymer matrix, the absorption (λ MAX ) of the subphthalocyanine dye did not change even after exposure for 10 hours to radiation from an Atlas Suntest CPS+ xenon lamp (R.B. Atlas Inc., Toronto, Canada). Thus, this invention encompasses both the admixture of subphthalocyanine dye and perfluoroporphine such as CuF 20 TPP and the covalent attachment of these moieties.
The covalent attachment of the perfluorotetraphenylporphine and the subphthalocyanine dye moieties is represented by the complex shown above, wherein Z comprises a copper-meso-perfluorotetraphenylporphine and a “linker” between the subphthalocyanine dye portion of the molecule and a phenyl ring of porphine. Therefore, in this example, Z can represent —NXCuF 19 TPP, —PXCuF 19 TPP, —AsXCuF 19 TPP, —BXCuF 19 TPP, —OCuF 19 TPP, —SCuF 19 TPP, —CX 2 CuF 19 TPP, —SiX 2 CuF 19 TPP, —GeX 2 CuF 19 TPP, —SnX 2 CuF 19 TPP, and the like, where X can independently represent H, alkyl, aryl, halide, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxide, phenoxide, substituted derivatives thereof, and so forth. These complexes are prepared by synthetic methods known to one of ordinary skill in the art. For example, the complex in which Z is —NHCuF 19 TPP was synthesized by reacting the bromo subphthalocyanine with the amino derivative of the perfluroporphine to obtain the subphthalocyanine-NHCuF 19 TPP compound.
Also suitable for use in the nanoparticles of the present invention are two subphthalocyanine compounds reacted with a third reactant to obtain a colorant compound having the following general formula:
wherein R 21 to R 36 , Z 1 , and Z 2 each independently represent moieties as described above with respect to R 1 to R 12 and Z. In the formation of the above compound, the third reactant may be selected from 1,3,4,6-tetracyanobenzene or 1,3,4,6-tetracyanobenzene further substituted with one or more electron-withdrawing groups, E 1 and E 2 Suitable electron-withdrawing groups include, but are not limited to, —NO 2 .
Charged polymer layers that are used to coat a nanoparticle can incorporate functional additives and colorant stabilizers. The term “colorant stabilizer” is used to refer to compositions that are capable of stabilizing the colorant against degradation by any mechanism. Colorant stabilizers include, but are not limited to, a porphine, a metal, a metal salt, a molecular includant, an ultraviolet radiation stabilizer or absorber, a quencher, a radical scavenger, or a combination thereof. Suitable colorant stabilizers in the form of Porphines are disclosed in U.S. Pat. Nos. 5,885,337; 5,782,963; 5,855,655; and 5,891,229; all of which are assigned to Kimberly-Clark Worldwide, Inc., the entirety of which are incorporated herein by reference. Other suitable colorant stabilizers for use in the present invention include, but are not limited to, colorant stabilizers disclosed in the U.S. patents cited above.
Suitable porphines for use as colorant stabilizers include, but are not limited to, porphines having the following structure:
wherein R is any proton-donating moiety and M is iron, cobalt or copper. Typically, R is SO 3 H,
COOH, R 1 COOH wherein R 1 is an alkyl group of from 1 to 6 carbons, or the corresponding salt thereof.
In accordance with the present invention, the colorant stabilizer is represented by one or more porphines such as Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine (designated CuTMPS4), having the following structure:
In the above-described porphines, the copper ion can also be substituted with an iron or cobalt. It is also understood that in the case of FeTPPS4, CuTPPS4 or CoTPPS4, the hydrogen ion of the sulfuric acid moieties may be substituted with other cations when in solution, and therefore constitute salts such as sodium salts.
Molecular includants are another form of colorant stabilizers that may be used in the present invention. The term “molecular includant,” as used herein, is intended to mean any substance having a chemical structure which defines at least one cavity. That is, the molecular includant is a cavity-containing structure. As used herein, the term “cavity” is meant to include any opening or space of a size sufficient to accept at least a portion of the colorant.
The term “functionalized molecular includant” is used herein to mean a molecular includant to which one or more molecules of a colorant stabilizer are covalently coupled to each molecule of the molecular includant.
The term “derivatized molecular includant” is used herein to mean a molecular includant having more than two leaving groups covalently coupled to each molecule of molecular includant. The term “leaving group” is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of molecular includants include, but are not limited to, the cyclodextrins.
Suitable molecular includants can be inorganic or organic in nature. In certain aspects, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular includants are, by way of illustration only, clathrates or intercalates, zeolites, and cyclodextrins. Examples of cyclodextrins include, but are not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α-cyclodextrin, carboxymethyl α-cyclodextrin, carboxymethyl β-cyclodextrin, carboxymethyl γ-cyclodextrin, octyl succinated α-cyclodextrin, octyl succinated β-cyclodextrin, octyl succinated γ-cyclodextrin and sulfated β-cyclodextrin and sulfated γ-cyclodextrin (Cerestar U.S.A., Inc., Hammond, Ind.).
The term “derivatized cyclodextrin” as used herein means a cyclodextrin having more than two leaving groups covalently coupled to each molecule of cyclodextrin. The term “leaving group” is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of derivatized cyclodextrin include, but are not limited to, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β and γ-cyclodextrin. A useful derivatized cyclodextrin is ethylhydroxy γ-cyclodextrin.
Typical molecular includant used in the present invention include, but are not limited to γ-cyclodextrin and β-cyclodextrin. In other embodiments, the molecular includant is an ethyl hydroxy β-cyclodextrin. Although not wanting to be bound by the following hypothesis, it is believed that the molecular includant inhibits the aggregation of the colorant molecule in solution. Other aggregation inhibitors that can be used in practicing the present invention are starches, pectins, amyloses, clathrates and the crown ethers.
A wide range of other visible light or ultraviolet (UV) screening agents, filters, or absorbers may be used in the present invention, the selection of which will also be apparent to one of ordinary skill in the relevant art. The terms “screening agent”, “absorber”, or “filter” is used interchangeably herein to mean any substance that absorbs radiation of a desired wavelength, whether that wavelength be in the ultraviolet or visible radiation range. The term is meant to include a single material or a mixture of two or more materials. Thus, ultraviolet filter molecules may be used in the present invention to filter out harmful UV radiation that would fade or decompose the colorant. Examples of suitable ultraviolet radiation absorbers for use in the present invention include, but are not limited to, a family of hydroxybenzophenones (wherein R and R′ each independently represent OH, SO 3 Na, CO 2 Na, H, alkyl, aryl, halide, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxide, phenoxide, substituted derivatives thereof, and so forth), as shown below, or a series of benzotriazoles (wherein R and R′ each independently represent OH, SO 3 Na, CO 2 Na, H, alkyl, aryl, halide, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxide, phenoxide, substituted derivatives thereof, and so forth), also shown below.
Radical scavengers can serve as colorant stabilizers and include, but are not limited to, triiodophenols and tertiary amines, such as those having the following structure, wherein R and R′ each independently represent OH, SO 3 Na, CO 2 Na, H, alkyl, aryl, halide, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxide, phenoxide, substituted derivatives thereof, and so forth.
Various quencher molecules can also be used as colorant stabilizers. For example, the following formula represents a suitable quencher species, wherein R and R′ each independently represent OH, SO 3 Na, CO 2 Na, H, alkyl, aryl, halide, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxide, phenoxide, substituted derivatives thereof, and so forth.
The present invention also encompasses reactive species generators that would produce reactive species such as free radicals when irradiated. These species would be useful when it is desired to react and alter the chromaphore of a colorant and thereby fade the color rapidly allowing for photo decoloration or photoerasing indicators on a substrate.
In another aspect of the present invention, colorant stabilizers can also be in the form of a metal or metal salt, such as a lanthanide or lanthanide salt. Although lanthanides and lanthanide salts are useful metals, other main group or transition metals may also be used in the present invention, alone or in combination, such as magnesium, iron or zinc.
Functional additives that provide certain physical or chemical properties to the nanoparticle can also be incorporated into the charged polymer layers and/or the polymeric core. Suitable functional additives include, but are not limited to, a charge carrier, a thermal oxidation stabilizer, a light-stabilizer, a viscoelastic property modifier, a crosslinking agent, a plasticizer, a charge control additive, a flow control additive, a filler, a surfactant, a metal solubility enhancing agent, a chelating agent, a leuco dye, or combinations thereof. Examples of such additives include, but are not limited to, charge control additives such as a quaternary ammonium salt; flow control additives such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinylstearate, and polyethylene powders; fillers such as calcium carbonate, clay and/or talc; light-stabilizers such as TINUVIN® compounds; among other additives used by those having ordinary skill in the art. Charge carriers are well known to those having ordinary skill in the art and typically are polymer-coated metal particles. Useful surfactants include, but are not limited to, C 12 to C 18 surfactants such as cetyl trimethyl ammonium chloride and carboxymethylamylose. Light-stabilizers such as TINUVIN® compounds are a class of compounds produced by Ciba-Geigy Corporation, which includes benzophenones, benzotriazoles and hindered amines. Useful TINUVIN® compounds include, but are not limited to, 2-(2′-hydroxy-3′-sec-butyl-5′-tert-butylphenyl)-benzo-triazole, poly-(N-β-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate and 2-(2′-hydroxy-3′,5′-ditertbutylphenyl)-5-chlorobenzotriazole. The identities and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art. To improve the solubility of the metal or metal salt in solution, metal solubility-enhancing agents may be added. Useful metal solubility-enhancing agents include, but are not limited to, chelating agents, including, but not limited to, EDTA (ethylenediaminetetraacetic acid) or EGTA (ethylene glycol-bis(β-aminoethyl ether)).
In addition, colorless dyes can be functional additives. By associating a leuco dye or a colorless “pre-dye” on the charged polymer, then adsorbing the charged polymer-dye combination on the nanoparticle, the colorless dye is converted to a colored dye when the nanoparticle is irradiated with UV light. This embodiment can be used in photodevelopment applications.
A final outside layer, comprising a protective stratum of transparent charged polymer, may optionally be added to the nanoparticle. When assembled in this fashion, the final charge of this protective outer layer (zeta potential) is employed to adhere the nanoparticle to the substrate during printing processes. Thus, by matching the nanoparticle charge to the opposite charge of the substrate, strong coulombic forces that augment the van der Waals and other physical and chemical attractions between the nanoparticle and the substrate can be achieved. Examples of protective coatings include, but are not limited to, an outer charged polymer layer comprising the sodium salt of poly(styrenesulfonic acid-co-vinyl alcohol), subsequently crosslinked with a diamine to form a polyamide-coated nanoparticle, or crosslinked with a diol to form a polyester-coated nanoparticle. Also by way of illustration, an outer coating of a charged polymer containing polyhydroxy functional groups could be readily crosslinked by one of the several methods well known to one skilled in the relevant art. In one embodiment, the final protective coat can comprise the sodium salt of poly(styrenesulfonic acid-co-maleic acid) that is exposed to a solution of a diamine which reacts with the poly(styrenesulfonic acid-co-maleic acid) layer, forming an polyamide protective layer which typically encapsulates the entire nanoparticle. A protective layer would be useful, for example, to achieve enhanced oxygen impermeability and protection of the nanoparticle against oxidation and other degradation reactions.
The recording media comprises the nanoparticles present in a carrier, the nature of which is well known to one of ordinary skill in the art. For many applications, the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common. Examples of suitable thermosetting and thermoplastic polymers are disclosed in U.S. Pat. No. 5,855,655 cited above. One suitable application is the incorporation of nanoparticles of the present invention into a polymer coating of a heat transfer product, such as is used for transferring graphic images onto clothing. Further examples of carriers include, but are not limited to, various organic solvents, co-solvents, surfactants, or water which are used to form inks comprising the nanoparticles of the present invention.
Another aspect of the present invention is directed towards the recording medium of the present invention containing a nanoparticle having a surface modifier or surface gloss modifying agent disposed upon the particle template. Examples of such surface modifiers include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, chitosans, polysiloxanes, polyacrylic acid, polysiloxane polyethylene oxide copolymer, polysiloxane polypropylene oxide copolymer, linear dextrins, cyclodextrins, combinations thereof, or copolymers thereof. The addition of the surface modifiers results in a surface with enhanced properties, such as glossy, matt, dull or textured.
FIG. 1 depicts the formation of a nanoparticle by adding multiple layers of charged polymer onto the polymeric core surface in a sequential fashion. The nanoparticle can comprise a polymeric core that has colorant disposed within or dispersed throughout, or a polymeric core without colorant. The charged polymer layers can be alternating charged polymer-colorant layers and void polyelectolyte layers that do not comprise a colorant. In another embodiment, various colorants can be incorporated into each charged polymer layer that is adsorbed onto the nanoparticle core. In either case, the colorant in the different charged polymer layers may differ from the colorant in adjacent layers. The layering process can involve an alternation of charged polymer-colorant polymer and charged polymer layers, such that sequential layers produce a nanoparticle that is characterized by opposite, or different, zeta potential charges. This process maintains layer integrity by a variety of chemical and physical forces, including coulombic forces, van der Waals forces and others.
In one aspect of the present invention, the nanoparticles of the recording medium are formed by adding multiple, oppositely-charged or differently-charged layers of charged polymer-colorant and charged polymer onto a charged polymeric core.
FIG. 2 . illustrates one aspect of the present invention, depicting the formation of a nanoparticle by adding multiple, layers of alternating charge of charged polymer-colorant and colorless charged polymer onto a nanoparticle template comprising a polymeric core. Among other things, this figure demonstrates how the integrity of the layers is maintained by coulombic, van der Waals forces and others forces, how a final outside layer comprised of a protective stratum of charged polymer may be added to the nanoparticle, and how the coulombic and other forces that increase the stability of the colored nanoparticle provide greater colorfastness of the resultant inks. We note however, that it is not necessary that a nanoparticle that is being formed in this manner exhibit an opposite zeta potential from the polymer charge that is being applied or coated thereto. Thus, the layer-by-layer self-assembly of differently-charged polymers (with or without colorant associated therewith) may be effected in the same way as assembling a nanoparticle with alternately-charged layers.
In another aspect of the invention, the nanoparticles (illustrated in FIG. 3 ) of the recording medium comprise a final protective coating on a nanoparticle comprising charged polymer-colorant and charged polymer layered on a polymeric core. This figure is also intended as a general illustration of how multiple levels of colorant protection are achieved, as well as the methods of controlling color intensity and hue. Typically, a nanoparticle can be coated with a final polyeletrolyte layer comprising a protective coating. In one embodiment, the final charged polymer layer comprises a reactive functional group. For example, FIG. 3 illustrates an outer charged polymer layer comprising anhydride groups that can be crosslinked with diamines to form an outer protective layer of nylon.
Surface charges on nanoparticles are utilized in the present invention to adhere the charged polymers to a nanoparticle core, as well as to adhere the assembled nanoparticle to the printing substrate. The presence of surface charges on suspended polymer particles can arise by a variety of phenomena. Possibilities include the presence of various chemical reactions on the surface (e.g. dissociation of functional surface groups), the presence of surface-adsorbed ions, and adsorption or dissociation of charge-bearing molecules. The dissociation of functional surface groups that are charged and/or adsorption of ions are among the most important processes. The surface adsorption of larger molecules containing charged groups such as surfactants and charged polymers of oligomers may also play a vital role. The surface charge of the particles is compensated in the liquid phase by counter ions, thereby ensuring the condition of electrical neutrality in the system as a whole.
The strong coulombic, van der Waals, and other chemical and physical forces between the nanoparticle and the printing substrate are important in providing enhanced stability, durability, and lightfastness. The term “light-fast” is used herein to mean that the colorant, when 5 associated with a charged polymer which itself is associated with a nanoparticle, is more stable to electromagnetic radiation, including, but not limited to, sunlight or artificial light, than when the colorant is not associated with a nanoparticle. In addition, by alternating colorant layers with a protective charged polymer outer sheath layer, lightfastness may be enhanced. Further improvements in lightfastness are obtained by incorporating colorant stabilizers, ultraviolet radiation screening agents, absorbers, or filters in charged polymer layers. Yet further improvements in lightfastness are obtained by coating the nanoparticle with a final charged polymer layer which can be crosslinked upon exposure to a crosslinking agent to form a protective layer. The layer-by-layer self-assembly of alternately-charged, charged polymer-colorant polymer and charged polymer bound to a polymeric core provides the resulting recording medium with enhanced lightfastness, unlimited use of water soluble colorants (containing charge centers), control of color density, and strong substrate bonding via coulombic, van der Waals, and other forces leading to enhanced durability.
The present invention is also directed to recording medium comprising nanoparticles that contain more than one colorant and optionally contain colorant stabilizers. The ability to incorporate colorant both within the nanoparticle polymeric core, and within the charged polymer-colorant polymer coating, provides excellent control over color intensity and hue. In addition, control of color density may also be achieved by adjusting reaction times between the nanoparticle substrate and the charged polymer-colorant where the extent of coating the particle dictates color density. The nanoparticles comprise a charged polymer membrane or coating which prevents colorant degrading materials or reactants from interacting with the colorant. In addition, the nanoparticles may be incorporated into a variety of liquid media to form colorant compositions.
The present invention is further directed to a method of stabilizing a colorant by assembling multiple, alternating layers of charged polymer-colorant and colorless charged polymer on a nanoparticle surface. This method optionally includes the incorporation of ultraviolet radiation screening agents in charged polymer layers and/or coating of the nanoparticle with a final charged polymer layer which can be crosslinked by an appropriate crosslinking agent. In one aspect of the present invention, one or more colorant stabilizers are also incorporated in the charged polymer layers, thereby providing multiple levels of colorant protection from photodegradation mechanisms.
In one aspect of the present invention, the nanoparticles of the recording medium comprise an organic polymeric core that is already colorant-loaded, i.e. having a colorant dispersed throughout it, up to about 30% colorant by weight. This invention is further directed to organic polymeric cores that have up to about 20% colorant by weight, and further, up to about 15% by weight. Nanoparticles comprising polymeric cores are typically formed in a two phase oil/water emulsion system by high shear emulsification using a microfluidizer. The resultant nanoparticles are then coated with charged polymer layers, in which some of the charged polymer has another colorant complexed with it.
The present invention is also directed to methods and compositions that stabilize a recording medium from the effects of sunlight and artificial light, and from the deleterious effects of humidity, oxygen, and other gaseous reactants such as O 3 , SO 2 , and NO 2 . In another aspect of this invention, a protective stratum of transparent charged polymer, may be added to the nanoparticle after it has been coated with alternating charged polymer-colorant, colorless charged polymer layers, for additional colorant protection and stability. In yet another aspect of the present invention, further protection is achieved by incorporating ultraviolet radiation absorbers in charged polymer layers, especially outer charged polymer layers. Yet further enhancements in colorant protection and stability are obtained by coating the nanoparticle with a final charged polymer layer which can be crosslinked upon exposure to an appropriate crosslinking agent, as outlined above for the aspect in which an outer protective layer is formed.
Although not wanting to be limited by the following hypothesis, it is theorized that, in addition to the protection provided by the polymeric coating on the nanoparticle, the above colorant stabilizing compounds act by quenching the excited state of a colorant molecule within the nanoparticle by efficiently returning it to a ground state. This quenching process reduces the likelihood of an oxidative or other chemical reaction occurring which would render the colorant chromophore colorless.
The quenching effect can occur by a number of processes. One such process is referred to as the heavy atom effect (internal or external) in which atoms with a high atomic number, such as iodine and/or lanthanides, can effect the excited electronic transitions of the colorant molecule by allowing heretofore forbidden electronic transitions to occur and by decreasing the excited state lifetimes. This effect permits the rapid return of the colorant to its ground state. Another quenching process involves back electron transfer. In this case, quenching of the excited colorant molecule occurs through sequential electron transfer. The additive or quencher, and colorant form an ion pair through electron donation within which back electron transfer leads to an overall deactivation of the excited energy donor, i.e., the colorant. Another quenching process involves a condition in which the quencher (additive) molecule has an excited energy state lower than the excited colorant. In this case, it may be possible to transfer the excited energy to the quencher thereby allowing the colorant molecule to return to its ground state. These mechanisms are more fully discussed in Chemistry and Light , Suppan, P., Published by The Royal Society of Chemistry, 1994, pgs 65–69 which is incorporated herein by reference.
In some aspects of the present invention, the colorant and/or colorant stabilizer of the nanoparticle is associated with a molecular includant. The term “associated” in its broadest sense means that the colorant and/or colorant stabilizer is at least in close proximity to the molecular includant. For example, the colorant and/or colorant stabilizer may be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. In one embodiment, the colorant and/or colorant stabilizer may be covalently bonded to the molecular includant. As a further example, the colorant and/or colorant stabilizer may be at least partially included within the cavity of the molecular includant.
The present invention encompasses recording media such as ink jet inks comprising the nanoparticles disclosed herein. Inks used in ink jet printers are described in U.S. Pat. No. 5,681,380, assigned to Kimberly-Clark Worldwide, Inc., which is incorporated herein by reference in its entirety. Ink jet inks will usually contain water as the principal solvent, preferably deionized water in a range of between about 20 to about 95 percent by weight, various co-solvents in an amount of between about 0.5 and about 20 percent by weight, and the nanoparticles of the present invention.
Various co-solvents may be included in the ink formulation. Examples of such co-solvents include a lactam such as N-methyl pyrrolidone. However, other examples of optional co-solvents include N-methylacetamide, N,N-dimethylacetamide, N-methylmorpholino-N-oxide, N-methyl formamide, propyleneglycol-monomethylether, tetramethylene sulfone, and tripropyleneglycolmonomethylether. Still other solvents which may be used include propylene glycol and triethanolamine (TEA). If an acetamide-based cosolvent is also included in the formulation it is typically present at about 5 percent by weight, within a range of between about 1.0–12 percent by weight.
Optionally, one or more humectants in an amount between about 0.5 and 20 percent by weight may be included in the ink formula. Further, other co-solvents in an amount of between about 1.0 and about 7.0 percent by weight may be added to the formulation. Additional humectants for optional use in the formulation include, but are not limited to, ethylene glycol, diethylene glycol, glycerine, and polyethylene glycol 200, 400, and 600, propane 1,3 diol, other glycols, a propyleneglycolmonomethyl ether, such as Dowanol PM (Gallade Chemical Inc., Santa Ana, Calif.), polyhydric alcohols, or combinations thereof.
Other additives may also be included to improve ink performance, such as a chelating agent to sequester metal ions that could become involved in chemical reactions that could spoil the ink over time, for example for use with metal complex dyes, a corrosion inhibitor to help protect metal components of the printer or ink delivery system, a biocide or biostat to control unwanted bacterial, fungal, or yeast growth in the ink, and a surfactant to adjust the ink surface tension. However, the use of a surfactant may be dependent on the type of printhead to be used. If a surfactant is included, it is typically present in an amount of between about 0.1 to about 1.0 percent by weight. If a corrosion inhibitor is included, it is typically present in an amount between about 0.1 and about 1.0 percent by weight. If a biocide or biostat is included, it is typically present in an amount between about 0.1 and about 0.5 percent by weight.
If a biocide or biostat is added to the ink formulation, it may be exemplified by Proxel GXL from Zeneca Corporation of Wilmington, Del. Other examples include Bioban DXN from Angus Chemical Company of Buffalo Grove, Ill. If a corrosion inhibitor is added to the formulation, it may be exemplified by Cobratec available from the PMC Specialty Group Distributing of Cincinnati, Ohio. Alternate corrosion inhibitors include sodium nitrite, triethanolamine phosphate, and n-acyl sarcosine. Still other examples include benzotriazole from Aldrich. If a surfactant is included in the formulation, it is typically a nonionic surfactant exemplified by Surfynol 504 available from Air Products and Chemicals, Inc. of Allentown, Pa. Still other examples include Surfynol 465, and Dynol 604 also available from Air Products. If a chelating agent is included in the formulation it may be exemplified by an ethylene diaminetetraacetic acid (EDTA). Other additives such as pH stabilizers/buffers, (such as citric acid and acetic acid as well as alkali metal salts derived therefrom), viscosity modifiers, and defoaming agents such as Surfynol DF-65, may also be included in the formulation, depending on the product application.
The recording media or colorant compositions of the present invention may be applied to any substrate to impart a color to the substrate. The substrates to which the nanoparticles may be applied include, but are not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal and the like. Examples of suitable substrates are disclosed in U.S. patent application Ser. No. 08/843,410, assigned to Kimberly-Clark Worldwide, Inc., the entire content of which is hereby incorporated by reference. In one aspect of the present invention, nanoparticles are applied to a textile article, such as clothing. A very thin coating having a thickness of about one nanoparticle may be applied to a textile surface.
The nanoparticles of the present invention can provide a method of finely manipulating color density and hue. Unusual or hard to obtain colors can be provided by assembing alternating charged polymer layers with different colorants. For example, a magenta layer followed by a cyan layer would provide a lilac color. Thus by mixing layers of color a uniform recording medium of unusual color would be obtained. Simple mixtures of different colorants would not result in a similar true color, but rather hues and shades of the original component colorants.
Further discussion on nanoparticles, and methods of making nanoparticles may be found in U.S. patent applications Ser. No. 09/969,539, entitled Nanoparticle Based Inks and Methods of Making the Same, filed contemporaneously herewith.
The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples, all parts are parts by weight unless stated otherwise.
EXAMPLE 1
Preparation of Organic Polymer Nanoparticles Containing a Subphthalocyanine Dye
Poly(α-methylstyrene) polymer (1 g) was dissolved in xylene solvent (9 g) to which the subphthalocyanine dye “KCSUBP” (0.1 g), shown in the structure below (where R 1 -R 2 ═H; Z═OC 6 H 3 -3,5-Me 2 ), was added.
This organic phase was kept at ca. 10–12% wt/wt combined polymer+dye in xylene. The concentration of dye was 9% wt/wt of dye in dye+polymer. Additionally, Texanol® plasticizer (0.05 g, Eastman Chemical Company, Kingsport, Tenn.) was added at a concentration of 5 wt % on the polymer. Ten grams of the organic phase (polymer+solvent) were mixed with 90 grams of the aqueous phase in a narrow glass vessel containing 1.5 wt % surfactant mixture of 50:50 wt/wt of NF-EO20 (Berol 292), 0.675 g; and NF-E06 (Berol 02), 0.675 g (Chemax Inc., Greenville, S.C.); in 88.65 g water.
The solution was subjected to 2 minutes of shearing in an Ultra-Turrax T25 from Janke & Kunkel GMBH at 12,000 rpm followed by 2 minutes of homogenization in a Microfluidizer M110-F homogenizer from Microfluidics International Corporation (Newton, Mass.). The air pressure was kept at 5 bars giving an approximate pressure of 650 bars in the reaction chamber and a flow of 800 m/min. A water bath at 25° C. was used to cool the interaction chamber of the Microfluidizer. The emulsion was further cooled with ice directly after treatment in the Microfluidizer.
The solution was filtered through a serum exchange cell with a pore size of 220 nm. The organic solvent was removed by means of dialysis. Dialysis tubes with a cut off value of 12,000–14,000 were used. The dialysis liquid consisted of 1 M sodium xylene sulfonate. The dialysis liquid was changed four times with at least 8 hours equilibrium time. The fourth time only, surfactant was present in the dialysis liquid, such that the dialysis liquid consisted of 1 M sodium xylene sulfonate+1.5% wt surfactant mixture NF-EO20 (Berol 292) and NF-E06 (Berol 02) (Chemax Inc., Greenville, S.C.). The dialysis liquid was stirred with a magnetic stirrer during the dialysis. After dialysis, a highly-colored suspension of nanoparticles was obtained.
EXAMPLE 2
Preparation of Organic Polymer Nanoparticles Containing Various Dyes
The preparation of a dye-containing nanoparticle was undertaken as described in Example 1, using chlorinated polyisoprene polymer in place of poly(α-methylstyrene) polymer to afford a dye-containing nanoparticle. Mixtures of poly(α-methylstyrene) and chlorinated polyisoprene polymers could also be used. Similarly, the preparation of a dye-containing nanoparticle was undertaken as described in Example 1, using Unigraph red 1971 and/or Uniplas red 1458 dyes (United Color Manufacturing, Inc., Philadelphia, Pa.), in place of the subphthalocyanine dye, to afford a dye-containing nanoparticle. In each case, after dialysis, a colored suspension of nanoparticles was obtained.
EXAMPLE 3
Preparation of Organic Polymer Nanoparticles Comprising Polyvinyl Alcohol and Sudan III
The preparation of a dye-containing nanoparticle was undertaken as described in Example 1, using polyvinyl alcohol polymer. Thus, nanoparticles were produced by using 50,000–70,000 molecular weight (M n ) polyvinyl alcohol polymer in the two phase oil/water emulsion system described above. Sudan III dye was incorporated into the nanoparticle system by dissolving it in the oil phase (toluene) along with the preformed polyvinyl alcohol polymer, and then mixing oil phase with a water/surfactant phase. High shear mixing was accomplished using a microfluidizer (Model 110F, Microfluidics Corp., Newton, Mass.) to form nanoparticles from about 21 to about 29 nm in diameter. Using this method, nanoparticles containing from about 1% wt/wt up to about 15% wt/wt dye were prepared.
EXAMPLE 4
Preparation of Charged Polymer-Rhodamine B-Coated Organic Polymer Nanoparticles
A sample of Sudan III dye was dissolved in polymethylstyrene and formed into nanoparticles in an oil/water system by high shear emulsification, by the method described in Example 1. The resultant polymer-dye nanoparticles averaged approximately 20 nm in diameter. These nanoparticles were then coated with charged polymer containing a Rhodamine B dye, specifically, a sufficient amount of poly(styrene sulfonic acid) salt with Rhodamime B dye in deionized water to coat the particle. After stirring this mixture for approximately 20 min, the sample was placed in a dialysis bag overnight (ca. 16 h) with water as the partition to remove any unassociated poly(styrene sulfonic acid). After dialysis, an intensely-colored suspension of nanoparticles was obtained.
EXAMPLE 5
Preparation of Organic Polymer Nanoparticles Containing High Subphthalocyanine Dye Concentrations
To prepare nanoparticles with high dye concentrations, the compatibility of KCSUBP with poly(α-methylstyrene) and chlorinated polyisoprene was examined. The dye concentration was kept at 1% by weight on xylene while the dye concentration on the polymer was increased to 27% by weight in the presence of 5% by weight Texanol™. It was found that the chlorinated polyisoprene crystallized at 9% by weight dye in the presence of 1–10% by weight Texanol®. The poly(α-methylstyrene) formed a homogenous smooth layer at 27% by weight dye in the presence of 5% by weight Texanol® as observed from AFM (atomic force microscopy), indicating the compatibility of KCSUBP with poly(α-methylstyrene) at this high concentration, and the dye being substantially dispersed throughout the polymer. After dialysis, an intensely-colored suspension of nanoparticles was obtained.
EXAMPLE 6
Preparation of Organic Polymer Nanoparticles Containing a Subphthalocyanine Dye and a Porphine Colorant Stabilizer
A mixture of 1 g of poly(α-methylstyrene), 0.1 g of the subphthalocyanine dye KCSUBP, 0.1 g of the colorant stabilizer CuF 20 TPP, and 0.05 g of Texanol were dissolved in 9 g of xylene solvent. Organic polymer nanoparticles containing dye and stabilizer were prepared from this mixture according to the experimental details of Example 1, using 90 g of an aqueous phase containing NF-EO20 (Berol 292), 0.675 g; and NF-E06 (Berol 02), in 88.65 g water. After dialysis, a colored suspension of nanoparticles was obtained. The concentration of the CuF 20 TPP stabilizer was varied from 0.01 g to 0.10 g to provide both low concentration and high concentration stabilizer solutions for lightfastness tests.
EXAMPLE 7
Preparation of Organic Polymer Nanoparticles Containing No Dye
For technical comparisons, nanoparticles of poly(α-methylstyrene) were prepared according to the method of the present inventin. A sample of poly(α-methylstyrene) polymer (ca. 1 g) was dissolved in xylene solvent (ca. 9 g), but no dye was added to solution. Organic polymer nanoparticles of this polymer were prepared according to the experimental details of Example 1. Zeta potential measurements were taken using a Zetapals Instrument (Brookhaven Instrument Corporation, Holtsville, N.Y.), by adding 1–3 drops of sample into a cuvet containing 1 mM KCl solution, using the instrument's default functions preset for aqueous solutions. The zeta potential for these particles was measured at −10 mV. These nanoparticles could be coated with charged polymer-dye and colorless charged polymer as indicated in the specification.
EXAMPLE 8
Lightfastness Study of Nanoparticles Containing a Subphthalocyanine Dye with and without a Porphine Colorant Stabilizer
An examination of the lightfast properties of poly(α-methylstyrene) nanoparticles containing the subphthalocyanine dye KCSUBP in the presence of a range of concentrations of the colorant stabilizer copper-meso-perfluorotetraphenylporphine (abbreviated CuF 20 TPP) was undertaken. Thus, the CuF 20 TPP colorant stabilizer and the subphthalocyanine dye KCSUBP were admixed. Data from this study are provided in Table 1, where absorptions are reported at λ MAX before and after exposure to the Atlas Suntest CPS+xenon lamp (R.B. Atlas Inc., Toronto, Canada) radiation over time. As these data indicate, the lightfast properties of the subphthalocyanine dye are greatly improved to archival levels by the presence of CuF 20 TPP.
TABLE 1
Absorption Values at Times T MIN for Poly(α-methylstyrene)
Nanoparticles Containing a Subphthalocyanine Dye with and without a
Porphine Colorant Stabilizer
Sample (in poly-α-methylstyrene)
T 0
T 120
T 330
T 450
T 570
KCSUBP
2.60
2.60
2.00
1.96
1.71
KCSUBP + CuF 20 TPP
2.04
2.04
2.04
2.04
2.01
(low concentration)
KCSUBP + CuF 20 TPP
2.93
2.93
2.93
2.93
2.93
(high concentration)
CuF 20 TPP
0.57
0.57
0.53
0.50
0.47
EXAMPLE 9
Nanoparticles Containing a Subphthalocyanine Dye Covalently Attached to a Porphine Colorant Stabilizer
The covalent attachment of a porphine colorant stabilizer to the subphthalocyanine would result in a dye with truly archival properties. Thus, the following compound can be synthesized by reacting the bromo subphthalocyanine with the amino derivative of the perfluoroporphine, to obtain the structure shown below, where Z is —NHCuF 19 TPP. In addition, the substituent Z in the following structure can also represent —NXCuF 19 TPP, —PXCuF 19 TPP, —AsXCuF 19 TPP, —BXCuF 19 TPP, —OCuF 19 TPP, —SCuF 19 TPP, —CX 2 CuF 19 TPP, —SiX 2 CuF 19 TPP, —GeX 2 CuF 19 TPP, —SnX 2 CuF 19 TPP, and the like, where X can independently represent H, alkyl, aryl, halide, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxide, phenoxide, substituted derivatives thereof, and so forth.
EXAMPLE 10
Stability of Styrene Nanoparticles
The stability of a suspension of styrene nanoparticles on standing in 1 mM aqueous KCl was examined by light scattering size measurements. These measurements were made using a Zetapals Instrument (Brookhaven Instrument Corporation, Holtsville, N.Y.), by adding 1–3 drops of sample into a cuvet containing 1 mM KCl solution, using standard procedures. Data are reported for poly(α-methylstyrene) nanoparticles containing the subphthalocyanine dye KCSUBP, with and without the colorant stabilizer CuF 20 TPP, and are compared to a polystyrene nanoparticle containing neither colorant nor stabilizer. These results are provided in Table 2.
TABLE 2
Nanoparticle Size on standing in 1 mM aqueous KCl for 2 Hours
Size (nm),
Size (nm),
Sample
0 min
120 min
KCSUBP
98.8
98.8
KCSUBP + CuF 20 TPP
247.3
54.4
poly(α-methylstyrene)
102.3
63.3
control
The decrease in particle size of the KCSUBP +CuF 20 TPP and the poly(α-methylstyrene) control samples reflects the system adjusting itself toward a minimal interfacial area between the dispersed phase and the dispersion medium. The conditions of surfactant/solvents allow the particles to adjust themselves to the optimum interfacial area which, for this system, would appear to be around 54–98 nm. This phenomenon is called “Ostwald ripening”.
EXAMPLE 11
Colored Styrene Nanoparticle Lightfastness on Uncoated Cotton Fabric
Suspensions of styrene nanoparticles from Examples 1 (containing KCSUBP) and 6 (containing KCSUBP+CuF 20 TPP) were prepared, and swatches of uncoated cotton fabric (ca. 1 inch×2 inches) were dipped into each suspension. Each swatch was dried in a vacuum oven under gentle heating, and then exposed to a Atlas Suntest CPS+ xenon lamp radiation, method 13 (R.B. Atlas Inc., Toronto, Canada). Over time, the samples that were treated with the subphthalocyanine dye KCSUBP without colorant stabilizer faded considerably faster than the sample treated with the subphthalocyanine dye KCSUBP with colorant stabilizer CuF 20 TPP present.
It should be understood that the foregoing relates only to certain disclosed embodiments of the present invention and that numerous modifications or alterations may be made therein without departing from the spirit and scope of the invention as set forth in the appended claims.
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The present invention provides recording media comprising nanoparticles, methods of stabilizing recording media against electromagnetic radiation (including ultraviolet radiation and radiation in the visible wavelength range), methods for enhancing the substrate independent durability performance of recording media, and methods for color density and hue control. The recording media deliver improved color, better color density control, improved printability, enhanced durability, and increased lightfastness, but also are capable of being printed on all substrates including woven and non-woven fabrics and paper products, without special treatment or other limitations.
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FIELD OF THE INVENTION
This invention is generally directed to residential and commercial alarm systems which are selectively armed and disarmed by a user. More specifically, the security alarm system of the present invention utilizes a modified deadbolt lock assembly that arms (or turns ON) an alarm system when the bolt is engaged, and disarms (or shuts OFF) the alarm system when the bolt is retracted. The alarm system of the present invention is capable of distinguishing which specific sensors should be bypassed when the bolt is engaged with no authorized person inside the premises, as opposed to when the bolt is engaged with an authorized person inside the premises.
BACKGROUND OF THE INVENTION
Burglaries, and the perceived risk thereof, have continually increased, particularly in crowded urban areas. Thus, more and more businesses and homes are protected by alarm systems. Most alarm systems comprise an alarm control panel; a series of detectors, sensors and/or door/perimeter contacts; and a user-controlled keypad. An alarm control panel typically includes all the necessary wiring and processing capability to determine whether signal information received from the detectors, sensors, contacts, etc. is indicative of an intruder. In more modern systems, the alarm control panel also provides the means for securing the telephone line in the house and dialing out to a central monitoring station if the processed signals are indicative of an intruder. A central monitoring station will then typically call the owner of the premises and, unless a proper secret code is provided, dispatch the police. The initial telephone call to the owner is not required but is usually done to confirm that the signal indicative of an alarm condition is not, instead, a false alarm. In certain municipalities, signals from the control panel may be sent directly to the police department or other municipal branch.
In the past, the provided keypad was often utilized for both installation and operational programming functions, and to permit a user to arm or disarm the alarm system. However, the programming of an installed alarm system is increasingly conducted via downloading directly to the alarm control panel from a hand-held device or from a remote location using a telephone connection. Thus, the keypad has become little more than a complicated and expensive “ON/OFF” switch.
In conventional alarm systems, when a user is ready to exit the premises and desires the alarm system to be turned ON (i.e., armed), a unique user code will be punched into the keypad. Typically, a delay is set that allows sufficient time for the user to exit the premises through the access door without setting off a false alarm. Conversely, when entering the premises, the user again must punch in a preselected code, utilizing the keypad, to disarm the alarm system. Again, a delay time is typically provided. If a user forgets or incorrectly inputs the preselected code and the delay time expires, an alarm condition will be initiated. Typically, an alarm condition will result in both an audio indication (such as a buzzer) and notification (via the telephone lines) to a central monitoring station.
Conventional keypad security systems are viewed unfavorably by users for a multiplicity of reasons. First, users need to remember their specific code and keep it secret. In order to permit authorized visitors access for a limited period of time (such as a house guest), a home or business owner must provide the access code yet would later need to change it to maintain security. Additionally, users often experience anxiety with the delay time permitted to enter a proper authorization code when either entering or exiting the premises. Many users, particularly elderly users, often lack the manual dexterity or the ability to view the keypad required to properly enter a code which allows them to enter the pre-established code. All of these shortcomings result in unnecessary false alarms which occur during the simple process of entering or exiting the premises.
It seems almost obvious to note that a very large majority of business and residential consumers who are concerned enough about security issues to purchase an alarm system, also utilize a deadbolt lock assembly on their access doors. While an alarm system is an effective deterrent against burglaries and indicates when an unauthorized individual (e.g., an intruder) has entered the premises, a reliable deadbolt lock assembly can prevent break-ins in the first place. Thus, the prior art does show some examples of an alarm utilized in conjunction with a deadbolt.
Droz U.S. Pat. No. 4,370,644 utilizes a deadbolt as a cut-off switch. The system presumes that when the deadbolt is retracted and in its unlocked position, an alarm condition signal should never be issued. The main advantage of this system is that it permits a user to leave the alarm system ON (or never shut the system OFF) while in the protected premises for an extended period of time. Although this system, under such circumstances, would normally detect the presence of an individual inside the premises and thus “see” an alarm condition, since the retracted deadbolt functions as an open switch, no actual alarm condition signal would be issued. The Droz device, however, provides no means for arming the alarm system by utilizing the deadbolt or insuring that both the deadbolt is engaged and the alarm system is ON when the user leaves the premises. Instead, false alarms are simply somewhat minimized due to the fact that no alarm condition can be initiated if the deadbolt is retracted. Furthermore, a user is permitted to set the alarm system well prior to leaving the premises as long as the deadbolt is not engaged. However, if the user leaves the premises without engaging the deadbolt, no alarm condition can ever be issued—whether the alarm system is armed or not.
Nourmand U.S. Pat. No. 4,937,560 provides an electromechanical interlock device that prevents a deadbolt from being moved from an unlocked position to a locked position until the security system is armed. Conversely, the provided electromechanical interlock also prevents the deadbolt from being moved from the locked position to the unlocked position until the security system is disarmed. The main function of the Nourmand device is to prevent false alarms and is accomplished by not allowing the user to enter the premises (since the deadbolt remains engaged) until the alarm system is turned OFF. The deadbolt is not utilized in any manner to arm or disarm the alarm system; instead, the permissible functioning of the deadbolt is modified depending on whether the alarm system is ON or OFF. The Nourmand device is, in effect, a deadbolt control. A glaring problem with the Nourmand device is that it is not adaptable to a door which an authorized person uses to enter the premises when the alarm is armed. The Nourmand system absolutely prevents the building from being entered prior to the security system being disarmed. However, most conventional alarm systems provide means for disarming an alarm inside the premises by setting an appropriate delay time.
Fromberg U.S. Pat. No. 5,925,861 provides a security door lock which is capable of issuing an alarm signal when an unauthorized user attempts to open a secured door. A cylindrical magnet contained within the latch permits the generation of an information signal which indicates that an attempt to open the secured door has been made. While the Fromberg device provides a separate door latch alarm, it is unrelated to any process of arming or disarming a home or business alarm system.
It is therefore a primary object of the present invention to provide a new and improved security alarm system.
It is another object of the present invention to provide a new and improved security alarm system which is less expensive and cumbersome than alarm systems using a keypad.
It is yet a further object of the present invention to provide a new and improved security alarm system that can be armed and disarmed based on the position of a deadbolt.
It is yet still a further object of the present invention to provide a new and improved security alarm system that can be armed and disarmed based on the position of a deadbolt and wherein the deadbolt's position is accurately detected by means of a Reed switch, a microswitch, or other means.
It is another object of the present invention to provide a new and improved security alarm system that can distinguish whether an authorized user is locking the deadbolt when leaving the protected premises or is locking the deadbolt while an authorized person remains inside the protected premises.
It is still another object of the present invention to provide a new and improved security alarm system that can be easily deactivated during a false alarm.
It is yet a further object of the present invention to provide a new and improved security alarm system that can easily be deactivated by a standard telephone utilizing its keypad.
It is yet still another object of the present invention to provide a new and improved security alarm system that is totally programmable without the utilization of a keypad.
It is still another object of the present invention to provide a new and improved security alarm system which is armed and disarmed dependent upon the position of a deadbolt, and which is further tamper proof.
It is yet another object of the present invention to provide a new and improved security alarm system that provides ease of installation.
It is still another object of the present invention to provide a new and improved security alarm system that can automatically determine whether to arm both perimeter and interior components when no authorized person remains in the protected premises or whether to arm only perimeter components when an authorized person remains in the premises.
Other objects and advantages of the present invention will become apparent from the specification and the drawings.
SUMMARY OF THE INVENTION
Briefly stated and in accordance with the preferred embodiments of the present invention, a security alarm system which may be selectively armed or disarmed when monitoring a protected premises is described which utilizes the position of a deadbolt to determine whether the security system should be armed or disarmed. The security system comprises (i) an entry door for permitting ingress to the protected premises from the outside of the entry door and egress from the protected premises from the inside of the entry door; (ii) a lock for selectively locking and unlocking the entry door; and (iii) a switch having a first state indicative of the lock being in a locked position and a second state indicative of the lock being in an unlocked position wherein, when the switch is in its first state, the security system is armed and, when the switch is in its second state, the security system is disarmed. Sensing means are also provided to determine if the lock was engaged from inside or outside the protected premises. In the case where the lock was engaged from outside the premises and no authorized individual remains inside, sensors inside the premises would become activated. Conversely, in the case where the lock was engaged from inside the premises or from outside the premises and an authorized individual remains inside, the inside sensors would remain deactivated. The disabling of an inadvertent (false) alarm is easily, yet securely, achieved by activating a first user-controlled disarming means and returning the lock to its unlocked position.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter regarded as the invention herein, it is believed that the present invention will be more readily understood upon consideration of the description, taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic illustration of the outside of a secured door incorporating a security alarm system in accordance with the present invention;
FIG. 2 is a schematic illustration of the inside of the secured door incorporating the security alarm system in accordance with the present invention;
FIG. 3 is a schematic illustration of a preferred deadbolt sensor command unit utilized in conjunction with the security alarm system in accordance with the present invention;
FIG. 4 is a first embodiment of a deadbolt position indicator switch of the security alarm system in accordance with the present invention;
FIG. 5 is an electrical circuit diagram of the deadbolt position indicator switch of FIG. 5 in accordance with the present invention;
FIG. 6 is a second embodiment of a deadbolt position indicator switch of the security alarm system in accordance with the present invention;
FIG. 7 is an electrical circuit diagram of the deadbolt position indicator switch of FIG. 6; and
FIG. 8 is a schematic illustration of a control panel and telephone interconnection utilized in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIG. 1, a standard door 10 is shown which is hinged-mounted in a doorframe 12 . A door handle 14 (depicted as a door knob) is on door 10 as well as a deadbolt lock assembly 16 . Deadbolt lock assembly 16 includes a key chamber 18 which receives a key 19 and is operably connected to a bolt 20 . Bolt 20 is operable to either retract within door 10 in its unlocked position or to extend from door 10 through a deadbolt hole of doorframe 12 in its locked position. FIG. 1 visually appears no different than the outside of any door incorporating a deadbolt lock assembly. However, the present invention may be utilized not only in conjunction with standard type mechanical deadbolts operated at least on one side by a key, but also with deadbolts that may be electronically controlled by a swipe card, a wireless keyfob, a keypad, etc.
Turning next to FIG. 2, the inside (or secured side) of door 10 and doorframe 12 is illustrated. The left side of doorframe 12 is shown exploded outwardly in the direction of directional arrows 22 in order to more clearly view bolt 20 . Door 10 can be either opened or closed by a user by utilizing a door handle 24 when bolt 20 is in its retracted position. Bolt 20 can be placed in either its locked (extended) position or its unlocked (retracted) position by means of a thumb turn 26 . Again, up to this point, FIG. 2 visually appears no different than a standard door utilizing a deadbolt lock assembly. In fact, it is preferred that most of the mechanical components of the present invention appear, and be able to be installed, as already known by installers. This easy adaptation will permit for easy retrofit applications.
A left panel 28 of doorframe 12 includes a deadbolt sensor command unit 30 which is hard wired to a power source by means of wires 32 . Deadbolt sensor command unit 30 is more easily viewed in FIG. 3 . In the preferred embodiment of the present invention, deadbolt sensor command unit 30 will include a light emitting diode (LED) display 34 , a bypass icon 36 which can be visible on LED display 34 , a panic button 38 , a red “ARMED” LED 40 , a green “READY” LED, a bypass toggle button 44 , a zone bypass button 46 , and an optional “EXIT/HOME” button 48 . The use of each of the components of deadbolt sensor command unit 30 will be more readily understood when considered in connection with the description of the functionality of the present invention. However, proper utilization of the deadbolt sensor command unit 30 is dependent upon having an effective means for determining whether bolt 20 is in its locked (extended) or unlocked (retracted) position. Furthermore, when bolt 20 is in its locked position, it is essential to effectively determine whether the user has totally exited the premises (with no other authorized persons home) or simply secured the premises from within.
FIG. 4 represents a first embodiment of an electromagnetic deadbolt position indicator switch 49 which can be utilized in conjunction with the present invention to determine whether bolt 20 is in its locked (extended) or unlocked (retracted) position. A bolt cup 50 is provided on the edge of door 10 and is shaped to receive bolt 20 when bolt 20 is in its locked position. A magnet 52 and a vertical Reed switch 54 are secured on opposite sides of bolt cup 50 . When bolt 20 is in its locked position (i.e., it is within bolt cup 50 ), the magnetic flux between magnet 52 and vertical Reed switch 54 is interrupted. Under such conditions, the normally open Reed switch 54 will be in the position of FIG. 5 such that ON/OFF toggle switch 56 remains opened and the alarm system becomes armed. When bolt 20 is placed in its unlocked position (i.e., as depicted in FIG. 4 ), a magnetic flux is generated between magnet 52 and vertical Reed switch 54 . Under such conditions, ON/OFF toggle switch 56 becomes closed and the alarm system becomes disarmed. Utilizing deadbolt position indicator switch 49 shown schematically in FIG. 4 and electrically in FIG. 5, a signal can be generated indicative of whether deadbolt 20 is in its locked or unlocked position.
The deadbolt position indicator switch (or at least vertical Reed switch 54 ) of FIG. 4 and FIG. 5 must be sufficiently isolated so that deadbolt position indicator switch 49 cannot be tampered with by an intruder utilizing a large magnet. It will also be noted that deadbolt position indicator switch 49 of FIG. 4 advantageously includes no separately moving parts. Instead, the only actuation means is whether bolt 20 is in its locked or unlocked position. Furthermore, since the operation of deadbolt position indicator switch 49 of FIG. 4 is not dependent on any physical contact between bolt 20 and bolt cup 50 , vertical Reed switch 54 will become closed even in the situation where bolt 20 is only partially inserted into bolt cup 50 and the key removed. This overcomes the common flaw associated with most deadbolt lock assemblies whereby a key can be removed even if the bolt is not completely extended in a locked position.
FIG. 6 and FIG. 7 depict, respectively, a schematic and electrical circuit diagram of a second embodiment of a deadbolt position indicator switch 55 which may be utilized in accordance with the present invention. A bolt cup 57 is provided having a sufficient space in which bolt 20 can be inserted when in a locked position. A plastic holder 58 includes a magnet 60 which is movable based upon the pressure applied to a foam spacer 62 . Deadbolt position indicator switch 55 of FIG. 6 includes both a normally open vertical Reed switch 64 and a normally open anti-tamper horizontal Reed switch 66 . When bolt 20 is in its retracted (or unlocked) position (as shown in FIG. 6 ), both vertical Reed switch 64 and anti-tamper horizontal Reed switch 66 are in their open position, and thus, ON/OFF toggle switch 68 is also open as shown in FIG. 7 and the alarm system will be disarmed. When the deadbolt is put in its locked position by a key, a thumb turn, or other means, plastic holder 60 will compress foam spaces 62 and a magnetic flux between magnet 60 and vertical Reed switch 64 will be created. Under such circumstances, ON/OFF toggle switch 68 will become closed and the alarm system will become armed.
While the embodiment of deadbolt position indicator switch 55 shown in FIG. 6 and FIG. 7 is not as effective as deadbolt position indicator switch 49 of FIG. 4 and FIG. 5 in dealing with the situation whereby bolt 20 is only partially inserted within the bolt cup, it does not require the electromagnetic isolation required by deadbolt position indicator switch 49 . Based on the parallel arrangement of vertical Reed switch 64 and anti-tamper horizontal Reed switch 66 , any attempt by a would-be intruder to disarm the alarm by means of a large magnet would instead open vertical Reed switch 64 but close anti-tamper horizontal Reed switch 66 thereby still creating an armed system. In effect, any attempt to tamper with deadbolt position indicator switch 55 to disarm the alarm system would simply reverse the orientation of vertical Reed switch 64 and anti-tamper switch 66 ; the result is that ON/OFF toggle switch 68 remains closed and the alarm system remains armed.
Although the two deadbolt position indicator switches represented in FIGS. 4-7 represent the preferred means for determining the position of the lock, many alternative designs can be incorporated. For instance, any of a number of well-known microswitches could be utilized. Alternatively, an interrupted beam across the bolt cup could indicate a lock in its locked position whereas, conversely, an uninterrupted beam across the bolt cup would indicate a lock in its unlocked position.
Turning next to FIG. 8, an alarm control panel 70 is shown which has been coupled to a standard telephone 72 having a keypad 73 . Wires 32 are shown as the interconnection between panel 70 and deadbolt sensor command unit 30 for the example where they will share a common power source. A dual tone, multi-frequency (DTMF) decoder 74 has also been provided for purposes that will become apparent upon consideration of the functionality of the present invention, as described below.
In actual operation, a security alarm system should be armed and no separate zones faulted when no one is present in the protected premises. However, there are instances when users desire to arm the security alarm system even though certain zones will remain bypassed. Similarly, many users set their alarm system with bypass zones when present within the premises. Many various uses can be made; the present invention provides the user all the same options as conventional security alarm systems—without the use of the cumbersome and expensive keypad. A security alarm system typically includes numerous sensors comprising components that provide perimeter protection and components that provide interior protection. The interior protection components are often bypassed when the user is home.
The description of several functional uses of the present invention will effectively describe the components shown on deadbolt sensor command unit 30 of FIG. 3 . The first example will be when a user wishes to exit the residence while the security alarm system is disarmed and certain zones are faulted. The user would approach door 10 and notice that neither the red “ARMED” LED 40 nor the green “READY” LED 42 is lit. The faulted zones will be scrolling slowly in the dual seven segment LED display 34 . Any bypassed zones would be signified by the appearance of bypass icon 36 along with the appropriate zone number which indeed is bypassed. At this point, the user can check for faulted zones and take corrective actions such as closing windows, securing doors, etc. However, the user will not be forced to close bypass zones in order to arm the security alarm system. Once the user has addressed faulted zones as desired, the green “READY” LED 42 will be lit. At this point, the user can exit the door and lock the deadbolt from the outside. The system preferably will beep three distinct times signifying that the perimeter sensors have been armed. However, the interior sensors will preferably not be immediately activated. Instead, upon the locking of a deadbolt, the interior sensors will look to detect an individual in the premises for a predetermined delay time. If the interior sensors do not detect motion within the preselected delay time, the interior sensors will then arm. Alternatively, if the interior sensors do indeed detect motion within the preselected delay time, the interior sensor will be bypassed; the system will assume that the deadbolt had been engaged by a user inside the premises or that another authorized person remains in the premises.
While the aforementioned delay time is utilized to help the security alarm system of the present invention to determine whether bolt 20 had been engaged from inside or outside the premises, optional EXIT/HOME button 48 might also be implemented. If the user is engaging bolt 20 from inside the premises, he/she can first depress button 48 before engaging bolt 20 . The system will be programmed to interpret such a scenario as being indicative of a locking from inside the premises, and therefore not arm the interior sensors. In the same way, EXIT/HOME button should be depressed when the person leaving the premises is indeed exiting, but another authorized person remains in the premises. Of course, optional EXIT/HOME button 48 can be programmed to work in reverse (i.e., wherein depression of the button is indicative of the locking of bolt 20 from outside the premises with no one remaining home).
The next example to be considered is when a user is exiting the residence, the security alarm system is armed, and certain zones are bypassed. Under such a scenario, the user will approach door 10 and notice that “ARMED” LED 40 is lit with the bypassed zones scrolling by slowly on LED display 34 . Upon unlocking bolt 20 by means of thumb turn 26 , the “READY” LED 42 would light. If zones are then faulted, the “READY” LED 42 would unlight and corrective action would have to be taken. After all corrective action is taken, the user would then exit door 10 and lock deadbolt assembly 16 by means of key 19 from outside door 10 to arm the system as described above.
When the user returns to the residence and desires to disarm the system, he/she would simply approach the front door, and unlock the deadbolt. The security alarm system would thus be disarmed. When the user actually opens door 10 and enters the premises “READY” LED 42 on deadbolt sensor command unit 30 would be lit.
A security alarm system must also be able to be armed when the user is at home or when he/she retires for the evening. Under such a scenario, the user would approach the door of the residence and if the “READY” LED 42 is lit, lock the deadbolt from the inside to arm the system. The system, under such circumstances, would monitor the interior for a preselected delay to determine if anyone is home or any pets are present. When properly functioning, the security alarm system would indeed detect the presence of the user inside the premises and the interior sensors would automatically be bypassed.
In conventional keypad security alarm systems, the keypad can also be utilized by a user to select bypass zones. The present invention can readily accomplish the same function without the need of a keypad. The user first would depress bypass toggle button 44 . At that point, the security alarm system would present each faulted zone sequentially on LED display 34 . If the user desired to bypass a particular zone, a user would hold down zone bypass button 46 for three seconds and the displayed zone would be bypassed. A chirping buzzer can be utilized to indicate that zone bypass button 46 has been depressed for a sufficient length of time (i.e., three seconds) to bypass the indicated zone. LED display 34 would then display the next faulted zone. If the user desired to skip the faulted zone and not bypass it, he/she would quickly depress zone bypass button 46 and the system would scroll to the next zone. Bypass toggle button 44 could then be pushed again to take the system out of bypass programming mode. If all faulted zones are bypassed or physically remedied, the system would automatically revert out of this bypass programming mode.
In any security alarm system, even an extremely passive one such as described herein, users will on occasion trip the alarm, thus causing a false alarm. An alarm condition signal would be indicated although in actuality the cause of this alarm condition was a false alarm. As stated above, control panel 70 would seize the telephone line and dial the central monitoring station. The central monitoring station would contact the user requesting the secret code developed by that user. Thus, the police would not be notified. However, until the alarm is disengaged, the actual siren at the location can be disturbing and embarrassing to the user. Even if the central monitoring station is equipped to deactivate the alarm, the overall security alarm system would then be out of synch since the alarm would be disarmed while bolt 20 was in a locked position.
The present invention is adaptable to provide numerous ways for a user to silence an inadvertent alarm. One way of accomplishing this task is by providing a disarm code similar to that established with keypad alarm security systems except that the code can be entered through the more familiar means of standard telephone 72 utilizing its keypad 73 . The DTMF decoder is 74 can interpret these touchtone signals to disarm the system. However, in the preferred embodiment, the alarm still should not be completely silenced until the user also approached door 10 and unlocked bolt 20 . Thus, the system would be disarmed and the bolt retracted, as is desired. Instead of utilizing standard telephone 72 using its keypad 73 , a hidden kill switch, a keypad, a fingerprint reader, a retinal scanner, a wireless keyfob, etc. could also be provided when the user desires to disarm the system. In either of these instances, it would still be desirable to require the user to also retract the deadbolt before the alarm is silenced. This second step will ensure that the alarm system remains in “synch.”
Whether utilizing a standard telephone using its keypad, a kill switch, a wireless keyfob, or other means, the security alarm system of the present invention could not be disarmed by an intruder simply by retracting the deadbolt once inside the premises. This system thus helps prevent “break and grab” burglaries wherein an intruder rapidly breaks into a secured premises, disables the audio alarm, quickly grabs desired items, and exits the premises prior to the time the police can respond to the alarm.
The one feature provided for on deadbolt sensor command unit 30 which, to this point, has not been described is panic button 38 . Many users desire a simple means for immediately advising the central monitoring station that an emergency exists. Panic button 38 provides this feature. It should be noted by those skilled in the art that panic button 38 can be replaced with separate fire, police and emergency medical buttons (bearing appropriate icons) to dial the specific desired assistance.
It will be apparent from the foregoing description that the present invention provides a new and improved security alarm system which is easily installed and provides all the functions and features of keypad-activated security alarm systems. While a specific layout of various visual indicia, etc. has been provided, many variations may be utilized. For instance, the LEDs may be of various colors and, in fact, could be combined as a tri-color LED indicative of varying status. Moreover, any of the LEDs described herein can be replaced, or supplemented, by other indicator means including a voice annunciator and the like.
While there has been shown and described what is presently considered to be the preferred embodiments of this invention, it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the broader aspects of this invention. For instance, although a deadbolt lock assembly has been shown, the invention could also be adapted to a latch which is key activated. Furthermore, while a standard door has been depicted, the subject invention can be incorporated on a window, garage door, or any other egress/ingress apparatus. Moreover, the subject invention can be utilized in either hardwired or wireless security alarm systems. Additionally, although a horizontally moving deadbolt has been depicted, a vertical deadbolt can also be utilized.
It is, therefore, aimed in the appended claims to cover all such changes and modifications as fall within the true scope and spirit of the invention.
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A security alarm system which may be selectively armed or disarmed when monitoring a protected premises is described which utilizes the position of a deadbolt to determine whether the security system should be armed or disarmed. The security system comprises (i) an entry door for permitting ingress to the protected premises from the outside of the entry door and egress from the protected premises from the inside of the entry door; (ii) a lock for selectively locking and unlocking the entry door; and (iii) a switch having a first state indicative of the lock being in a locked position and a second state indicative of the lock being in an unlocked position wherein, when the switch is in its first state, the security system is armed and, when the switch is in its second state, the security system is disarmed. Sensing means are also provided to determine if the lock was engaged from inside or outside the protected premises. In the case where the lock was engaged from outside the premises and no authorized individual remains inside, sensors inside the premises would become activated. Conversely, in the case where the lock was engaged from inside the premises or from outside the premises and an authorized individual remains inside, the inside sensors would remain deactivated. The disabling of an inadvertent (false) alarm is easily, yet securely, achieved by activating a first user-controlled disarming means and returning the lock to its unlocked position.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to, and claims priority from U.S. patent application Ser. No. 10/938,868 “Process for Creating Spun Yarn” filed May 10, 2005, and hereby incorporates by reference this application as set forth in its entirety herein.
1. FIELD OF THE INVENTION
[0002] The present invention relates to an antimicrobial, absorbent yarn textile matrix fostering a moist wound-healing environment which minimizes or eliminates the possibility of infection, and is especially useful as a component of a wound dressing.
BACKGROUND OF THE INVENTION
[0003] Silver has been used as an antimicrobial since ancient times. It has been used to stop bacterial infections. Recent years have seen a renewed interest in silver. This renewed interest is driven in part by the development of antibiotic resistant bacteria, such as methicillin-resistant Staphylococcus aureus (MRSA). Conventional antibiotics have little or no effect on these resistant bacteria. Resistant bacteria are especially problematic in wounds, causing infections, destroying tissue, delaying the healing process and causing unpleasant odors. Silver is a broad-spectrum antibiotic that is effective against such resistant bacteria. Even though these bacteria develop resistance to antibiotics, they do not develop resistance to silver. There is a current need for an antibiotic wound care product that uses silver to treat and/or prevent MRSA and other infections caused by resistant bacteria.
[0004] Silver is also known to exhibit wound-healing properties. Expeditious wound healing benefits the patient by providing increased comfort and decreased susceptibility to further infection and secondary injury. There is a current need for wound care products that utilize silver to increase the rate of wound healing.
[0005] Many presently existing antimicrobial wound care products have been used to treat infections, however, these lose their effectiveness in a short period of time. This is especially true for wound care products that contain silver in an ionic form. Ionic silver is readily dissolved in an aqueous environment and dissipated. Such dressings must be replaced frequently often resulting in extreme pain or discomfort and inconvenience for the patient as the dressing is removed and a new dressing is applied.
[0006] Similarly, silver creams (including silver sulfadiazine) must be consistently reapplied to the injured area, and the dressing must be removed for reapplication of the cream. There is currently a need for a wound care product that releases silver ions over an extended period of time and which alleviates the need for frequent removal or replacement of the dressing or application of silver creams.
[0007] Silver may be commonly applied in ionic form as a silver salt. Such salts can be irritating to the skin. Moreover, prolonged contact with silver salts can cause argyria, which is characterized by a pronounced, permanent ashen-gray skin discoloration, which can be localized or universal. There currently is a need for a non-irritating silver wound care product that does not rely on silver salts for the delivery of silver ions. There is also a current need for an ionic silver wound care product that does not cause argyria.
[0008] Metallic silver is a costly substance. Silver wound care products that use too much silver would be unduly expensive and wasteful. On the other hand, silver wound care products that use too little silver would be ineffective. There currently is a need for a silver wound care product that enables the delivery of an optimal dosage of silver to the wound area.
[0009] Silver is known to affect the operation of matrix metalloproteinases (MMPs). Excessive MMPs are known to interfere with and slow the wound healing process. Existing silver-based wound care products inhibit MMPs too much, and also interfere with the wound healing process. There is currently a need for a silver wound care product that delivers a proper amount of silver, which limits the activity of MMPs without unduly restricting MMPs activity.
[0010] Other existing silver-based wound care products are made from silver-plated films with limited flexibility. These dramatically reduce the flexibility and comfort of the bandages. Textile bandages are much more flexible and hence, much more comfortable for patients. There is currently a need for a silver-based wound care product that is more flexible and comfortable.
SUMMARY OF THE INVENTION
[0000]
The present invention may be embodied as a method of manufacturing a textile matrix having improved anti-microbial properties comprising the steps of:
a) preparing input fibers [ 110 ], the preparation includes the following substeps:
i. providing input fibers [ 113 ] with a predetermined length range, and ii. metallizing the input fibers [ 115 ];
b) carding the metallized fibers [ 120 ] by the following sub-steps:
i. opening the metallized fibers [ 121 ] to separate the individual fibers from each other, ii. blending the metallized fibers [ 123 ] with other fibers, iii. orienting the blended fibers [ 127 ] in generally the same direction to create a web, and iv. cross-lapping the fibers [ 128 ] of the web.
[0020] The present invention may also be embodied as a method of manufacturing textile components from an input fiber having improved anti-microbial properties comprising the steps of:
a) preparing input fibers [ 110 ], the preparation includes the following substeps:
i. providing input fibers [ 113 ] with a predetermined length range, and ii. metallizing the input fibers [ 115 ];
b) carding the metallized fibers [ 120 ] by the following sub-steps:
i. opening the metallized fibers [ 121 ] to separate the individual fibers from each other, ii. blending the metallized fibers [ 123 ] with other fibers, iii. orienting the blended fibers [ 127 ] in generally the same direction to create a web, and iv. drawing the web [ 129 ] to create a sliver having fibers with antimicrobial properties.
OBJECTS OF THE INVENTION
[0029] It is another object of the present invention to provide a wound care product which employs silver metallized yarn capable of releasing ionic silver to inhibit infections and facilitate wound healing.
[0030] It is another object of the present invention to provide a wound care product which is capable of releasing ionic silver, copper and zinc ions over an extended period of time without the use of irritating metal salts.
[0031] It is another object of the present invention to provide a wound care product which is capable of releasing ionic silver which does not cause argyria.
[0032] It is another object of the present invention to provide a wound care product which maintains a moist wound-healing environment while preventing the growth of bacteria and fungi.
[0033] It is another object of the present invention to provide a wound care product which retains a moist wound environment, but eliminates unpleasant odors.
[0034] It is another object of the present invention to provide an anti-bacterial, and anti-fungal metallized yarn which employs a large surface area for discharge of metal ions.
[0035] It is another object of the present invention to provide an anti-bacterial, and anti-fungal metallized yarn in which the metal ions do not become detached from the yarn substrate.
[0036] It is another object of the present invention to provide a wound care product which enables the delivery of an optimal dosage of silver ion.
[0037] It is another object of the present invention to provide a wound care product which delivers a predetermined rate of silver release, which limits MMP activity to a level roughly associated with optimum wound healing.
[0038] It is another object of the present invention to provide an anti-bacterial, and anti-fungal metallized yarn which can be used in applications including hosiery and other knit-wear.
[0039] It is another object of the present invention to provide an anti-bacterial, and anti-fungal metallized yarn which is easy and inexpensive to manufacture.
[0040] It is another object of the present invention to provide a combination of silver metallized and copper metallized yarn to create wound care products which treat and/or prevent resistant bacterial infections such as MRSA and fungal infections.
BRIEF DESCRIPTION OF THE DRAWINGS
[0041] A complete understanding of the present invention may be obtained by reference to the accompanying drawing, when considered in conjunction with the subsequent detailed description, in which:
[0042] FIG. 1 is a flowchart showing one embodiment of a process for creating textile components according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0043] One embodiment of the present invention is a novel antibiotic textile matrix made of a metallized yarn having absorptive properties that are especially useful in wound care products, such as wound dressings.
Metallized Fibers
[0044] The textile matrix of the invention includes silver coated fibers. The silver coated fibers may be manufactured as described in U.S. Pat. No. 4,042,737, entitled “Process For Producing Crimped Metal-Coated Filamentary Materials, And Yarns And Fabrics Obtained Therefrom,” issued to Rohm and Haas Company (Philadelphia, Pa.), on Aug. 16, 1977, hereby incorporated by reference as if set forth in its entirety herein. Similar fibers are commercially available from Noble Fiber Technologies sold under the tradename X-static®.
[0045] Copper has been known and proven to be a very effective anti-fungal agent and also has other anti-microbial properties. It is also very ductile and can be used to metallize a surface of a textile substrate. The combination of silver with copper is very effective in providing not only anti-bacterial, but also anti-fungal properties.
[0046] Silver-coated fibers, such as the X-Static® product, can be copper coated using conventional electrodeless copper chemistry. Zinc-coated fibers can also be incorporated into the textile matrix.
[0047] In addition to providing an antimicrobial effect, the addition of the metallized fibers also reduce physical adherence of the dressing to the wound site.
[0048] This reduced physical adherence reduces the amount that a wound dressing sticks to, and pulls on the wound and making the dressing more comfortable to wear. The reduced adherence also decreases pain and discomfort when the dressing is removed or replaced.
[0049] The preferred substrate of the silver-coated fiber is nylon. The following table describes the preferred characteristics of the metallized fibers:
[0000]
Length
Denier
(cm)
(dpf)
Silver/Copper (% w/w)
Outside range
½-8
0.5-50
3%-75%
Intermediate range
¼-6
0.7-30
9%-60%
Optimal range
1-3
1-10
12%-30%
Ideal
~2
~3
~21
[0050] Using fibers having the length, denier per fiber and silver to copper ratio, the optimum ion release is obtained to prevent infections and optimizes healing.
Composition of the Textile Matrix
[0051] The textile matrix of the present invention is spun yarn using fibers of the length, denier per fiber and silver to copper ratio as specified in the table above.
[0052] The desirable antimicrobial properties and efficacy of the textile matrix are determined using the Dow Corning Shake Flask Test over 24 hours of the New NY State 63 Test for Bacteriostatic Activity. Other tests included, but are not limited to ASTM E-2149 for a time period ranging from 10 minutes to 7 days. Preferably the kill rate is not less than about 70%. More preferably the kill rate is not less than about 85%, and ideally the kill rate is not less than about 95%.
[0053] The present invention can also be used for other applications such as being woven into material for odor prevention, socks for athlete's foot prevention and into bedding liners to kill dust mites, etc.
Method of Making
[0054] Manufacturing the textile matrix involves preparing the input fiber, carding the fiber (includes sub-steps: opening the silver-coated fiber, blending and orienting the fiber, cross-lapping the fiber) and optionally, needle punching the web.
[0055] Manufacturing a sliver involves preparing the input fiber, carding the fiber (includes sub-steps: opening the silver-coated fiber, blending and orienting the fiber, drawing the fiber) and optionally roving to further condense the fiber.
[0056] Each of these steps is described in the ensuing text.
Manufacturing
[0057] Referring now to FIG. 1 , the steps of the manufacturing process according to one embodiment of the present invention are shown.
1. Preparing the Input Fiber
[0058] In step 110 , the metal coated fiber is prepared. One such method is that described in U.S. Pat. No. 4,042,737, referenced above.
[0059] In step 113 , the metallized fiber is preferably manufactured in the form of a continuous filament and then cut into short segments having lengths as described above. The inventors have surprisingly discovered that by using cut yarn, rather than staple fiber, the properties of the final product are dramatically improved. In step 115 the fibers are significantly easier to metallize in the manufacturing process because there is less clumping (adhesion to itself) of fibers. The inventors believe that this improvement is facilitated by the general axial alignment of the fibers after they are cut, relative to the random orientation of the fibers that result from coating staple product. Another factor that helps prevent clumping is the manufacture of the short fibers from long fibers after aqueous processing, as opposed to processing short (staple) fibers and allowing them to dry together.
[0060] Copper-coated yarn is prepared by using commercially available copper chemistry applied to silver-coated fibers.
2. Carding
[0061] In step 120 , carding is accomplished using a traditional carding process. A preferred carding machine is the Bematic card, manufactured by Bettarinj & Serafirij Sarl. (Prato, Italy).
[0062] Carding blends the fibers together and orients them in generally the same direction, i.e., generally parallel. Carding includes the following sub-steps:
[0063] 2a. Opening the Silver-Coated Fiber with or without Copper-Coated Fibers
[0064] In step 121 , the metallized fibers are opened. When the silver-coated fiber is processed wet and subsequently dried, it clumps together (though not to the same extent as staple fiber that is processed and then dried). The fiber is opened, to separate the individual staple fibers from each other to enable it to be blended with the alginate.
[0065] 2b. Blending and Orienting the Fibers
[0066] The silver-coated fiber and the absorbent fiber are then blended in step 123 and oriented in step 127 to create a web.
[0067] Optionally, the blended fibers may be opened in step 125 .
[0068] 2c. Drawing the Fiber
[0069] In step 129 , the output of above steps is drawn to create a sliver having absorbent and antimicrobial properties.
3. Roving to Further Condense the Fiber (Optional)
[0070] To further condense the fiber, the sliver may optionally be put through a roving process in step 140 .
4. Spinning
[0071] In step 150 the manufactured sliver is spun onto a bobbin to be knit, woven, etc. in a traditional textile operation.
[0072] Optionally, the step of cross-lapping the fiber, step 128 and needle punching the web, step 130 may be employed as is known in the prior art to result in a textile matrix.
Method of Using
[0073] The end result will result in textile components used in making clothing and wound care products with optimum metal ion release and superior anti-odor, anti-static, anti-microbial, hydrodynamic, thermodynamic properties.
[0074] The percentage of metallized fiber, such as the X-Static® product used in the textiles typically range from 2% to 25% by weight, but overall from 1% to 75% of the spun yarn by weight.
Example
[0075] Three textile matrix samples were manufactured according to the foregoing procedure with varying amounts of silver thread and cotton blend (10/90, and 50/50).
[0076] The matrix was tested for antimicrobial activity and absorbance using the NY State 63 Test for Bacteriostatic Activity. Five (5) 1″ inch squares of the textile matrix were used as samples.
[0077] Ten bottom sections of 35×10 mm disposable tissue culture dishes were placed in standard petri dishes containing 10 ml of sterile distilled water. 0.2 μl of a 24 hour broth culture containing 10 5 organisms was placed in the center of each disposable tissue culture dish. The test and control squares were then placed in the disposable tissue culture dishes, with one side in contact with the inoculum. The covers were than rep laced on the standard petri dishes. The petri dishes were then placed on a level shelf of an incubator at 37° C. and incubated for 24 hours. After 24 hours, the samples were removed from the petri dishes by means of a flamed forceps and placed into 100 ml of Letheen broth in an 8 oz. wide mouth jar. The jar was shaken vigorously for about 1 minute. Serial dilutions were made and placed on AATCC bacteriostasis agar. Plates containing the agar were then incubated for 24-48 hours at 37° C. The percentage reduction of inoculum by samples and controls was calculated.
[0000]
Antimicrobial Activity
% Silver
% Cotton
Kill Rate
10
90
>99.9%
50
50
>99.9%
Other Fibers
[0078] As descried in more detail below, the textile matrix may include additional fibers other than the silver-coated fibers and absorptive fibers. Examples include cotton, cellulose, polyester, acrylic and nylon.
Other Therapeutic Agents
[0079] The textile matrix of the invention may also include other antibiotics, such as doxycycline or other topical antibiotics. The textile matrix may also include hormone treatments, such as estrogen, to facilitate wound healing. For example, antibiotics and hormones may be used in conjunction with the textile matrix as described in U.S. Pat. No. 5,914,124.
[0080] The textile matrix may also include fibers, particles or similar substrates coated with antibiotic (e.g., anti-microbial, anti-bacterial, and/or anti-fungal) metals, such as copper and/or zinc. A preferred combination textile matrix product includes silver-coated fibers and copper-coated fibers.
[0081] Another preferred combination textile matrix product includes silver-coated fibers and zinc-coated fibers.
[0082] While several presently preferred embodiments of the novel invention have been described in detail herein, many modifications and variations will now become apparent to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and variations as fall within the true spirit of the invention.
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Input fibers to be used for the manufacture of textile components are cut to a proper length [ 113] . The fibers are metallized [ 115] with silver and copper. The metallized fibers are opened [ 121] and blended [ 123] with other fibers. The blended fibers are preferably opened again [ 125] . Then the blended fibers are oriented [ 127] and drawn [ 129] into a sliver. Roving [ 140] may be applied to the sliver to condense the fibers. The length of the fibers, the denier of the fibers, the amount of metal coating and composition of the metal coating are selected to provide an optimum amount of metal ion discharge to have the proper antimicrobial properties, while optimizing wound healing properties, and minimizing manufacturing costs.
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