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Patent US20040102780 - Protective devices for use with angled interference screws - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA protective device for use with an interference screw used to attach a soft tissue graft within a bone tunnel reduces the tendency of the interference screw to undesirably snag a soft tissue graft and/or sutures when screwed into a bone tunnel. The protective device has an angled face that corresponds...http://www.google.com/patents/US20040102780?utm_source=gb-gplus-sharePatent US20040102780 - Protective devices for use with angled interference screwsAdvanced Patent SearchPublication numberUS20040102780 A1Publication typeApplicationApplication numberUS 10/304,719Publication dateMay 27, 2004Filing dateNov 26, 2002Priority dateNov 26, 2002Also published asUS7235078Publication number10304719, 304719, US 2004/0102780 A1, US 2004/102780 A1, US 20040102780 A1, US 20040102780A1, US 2004102780 A1, US 2004102780A1, US-A1-20040102780, US-A1-2004102780, US2004/0102780A1, US2004/102780A1, US20040102780 A1, US20040102780A1, US2004102780 A1, US2004102780A1InventorsHugh WestOriginal AssigneeWest Hugh S.Export CitationBiBTeX, EndNote, RefManReferenced by (11), Classifications (18), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetProtective devices for use with angled interference screwsUS 20040102780 A1Abstract A protective device for use with an interference screw used to attach a soft tissue graft within a bone tunnel reduces the tendency of the interference screw to undesirably snag a soft tissue graft and/or sutures when screwed into a bone tunnel. The protective device has an angled face that corresponds to an angled face of the interference screw and threads that correspond to the threads of the interference screw. When used together, the protective device effectively completes the part of the interference screw that is removed to form the angled face. This, in turn, reduces or eliminates any sharp edges that would otherwise catch or snag the tissue graft and/or sutures as the interference screw is screwed into a bone tunnel during a joint repair procedure. The protective device may be included within a kit together with a correspondingly sized and shaped interference screw, and optionally with a driver. Images(4) Claims(20)
What is claimed is: 1. A protective device for use with an interference screw that is configured in size and shape for securing a tissue graft to a bone, the protective device comprising: a body extending from a proximal end to a distal end along a central axis, the body including: an angled face having an angle relative to the central axis, the angled face being configured to engage a correspondingly angled face on an end of an interference screw, and a threaded portion having threads that are configured to align with corresponding threads disposed on the interference screw when the protective device is concentrically aligned with the interference screw and the face of the protective device engages the face of the interference screw. 2. A protective device as defined in claim 1, the angled face of the protective device corresponding to an angled face of an interference screw so that when the protective device is mated with the interference screw, the protective device and interference screw are substantially concentrically aligned about the central axis. 3. A protective device as defined in claim 2, the angled faces of the protective device and the interference screw having normalized angles relative to the central axis that together add up to about 90�. 4. A protective device as defined in claim 1, the angled face of the protective device having a normalized angle relative to the central axis in a range of about 30� to about 70�. 5. A protective device as defined in claim 1, the angled face of the protective device having a normalized angle relative to the central axis in a range of about 50� to about 60�. 6. A protective device as defined in claim 1, the threads of the protective device having a pitch and spacing that are substantially similar to the pitch and spacing of threads of the interference screw. 7. A protective device as defined in claim 1, the threaded portion having a diameter that is substantially equal to the diameter of the interference screw. 8. A protective device as defined in claim 1, the threaded portion having an external diameter of at least about 10 mm. 9. A protective device as defined in claim 1, further comprising a non-threaded portion adjacent to the threaded portion distal to the angled face. 10. A protective device as defined in claim 1, further comprising a passageway through the body along the central axis, the passageway sized and configured so as to permit a shaft of a driver that is configured to mechanically engage the interference screw to pass through the passageway. 11. A protective device as defined in claim 10, the passageway being sized and configured so that the protective device can freely rotate relative to driver when the shaft is disposed through the passageway. 12. A protective device as defined in claim 10, the passageway being sized and configured so as to mechanically engage the driver when the shaft is disposed through the passageway. 13. A protective device as defined in claim 1, the protective device being mechanically adjustable so as selectively accommodate two or more differently-sized interference screws. 14. A kit for use in securing a tissue graft to a bone, comprising: one or more interference screws, each interference screw comprising: a threaded body extending along a central axis and including threads for threadable insertion into a bone tunnel, the threaded body including an angled face disposed at an end of the threaded body, and one or more protective devices, each protective device comprising: a body having an angled face that is configured to engage the angled face of at least one of the interference screws within the kit when the protective device is concentrically aligned with the interference screw about the central axis. 15. A kit as defined in claim 14, at least one of the protective devices further comprising a threaded portion having threads that are configured to align with corresponding threads disposed on the interference screw when the protective device is concentrically aligned with the interference screw and the face of the protective device engages the face of the interference screw. 16. A kit as defined in claim 14, the kit comprising: a plurality of interference screws, at least two of which are differently-sized; and a plurality of protective devices sized and configured so that there is at least one protective device that corresponds to each interference screw. 17. A kit as defined in claim 14, further comprising at least one driver that is configured to mechanically engage a corresponding hole in one or more of the interference screws. 18. A kit as defined in claim 17, each protective device further comprising a passageway through the body that is sized and configured so as to permit a shaft of the driver to pass through the passageway when the protective device is mated with a corresponding interference screw. 19. A kit as defined in claim 18, the passageway being sized and configured so as to mechanically engage the driver when the shaft is disposed through the passageway. 20. A method of introducing an interference screw into a bone tunnel, comprising: (a) obtaining an interference screw that is sized and configured so as to engage bone tissue surrounding the bone tunnel with a desired level of pressure, the interference screw having a threaded body disposed along a central axis, an angled face disposed at an end of the threaded body, and a hole configured to mechanically engage a shaft of a driver; (b) obtaining a protective device comprising a body having a passageway through which a shaft of a driver can pass and an angled face that is configured to engage the angled face of the interference screw when the protective device is concentrically aligned with the interference screw; (c) inserting a shaft of a driver through the passageway of the protective device and into the hole of the interference screw in order for the driver to mechanically engage the interference screw and concentrically align it with the protective device; and (d) introducing the interference screw into a bone tunnel by rotating the driver and causing the interference screw to rotate about the central axis. Description
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0021] The invention relates to protective devices for use with angled interference screws used to affix soft tissue grafts within angled bone tunnels during reconstructive surgery. The invention also relates to methods and kits that comprise one or more protective devices in combination with one or more angled interference screws. [0022] Reference will now be made to figures wherein like structures will be provided with like reference designations. [0023] Reference is first made to FIG. 1, which is an exploded view of an exemplary interference screw 100, an exemplary protective device 200, and an exemplary driver 300. FIG. 2 depicts the interference screw 100, exemplary protective device 200, and exemplary driver 300 in use to secure a soft tissue graft 440 within a bone tunnel 410. Before discussing how the various components work together to reduce the tendency of the interference screw to snag the graft and/or sutures when screwed into the bone tunnel, various features and embodiments relating to the interference screw will now be given. [0024] Angled interference screws that may be used in combination with protective devices according to the invention are described in co-pending U.S. application Ser. No. 09/977,154, filed Oct. 12, 2001 in the name of Hugh S. West, Jr., M.D., and entitled IMPROVED INTERFERENCE SCREW HAVING INCREASED UPPER DIAMETER. For purposes of disclosing angled interference screws, the foregoing U.S. application is incorporated by reference. [0025] In general, angled interference screws comprise a threaded body that extends between a proximal end and a distal end along a central axis. Virtually any interference screw known in the art can be modified so as to have an angled trailing end. In one embodiment, the threaded body may include proximal and distal threaded sections having differing diameters, with the proximal section having a larger average diameter than the distal section. The proximal and distal threaded sections may comprise constant diameters, such that the outer diameter of each section is substantially cylindrical, or they may have varying diameters such that at least part of each section includes a taper (i.e., is angled rather than parallel to the central axis). One threaded section may be cylindrical and the other section at least partially tapered. [0026] The proximal threaded section includes an angled face, preferably corresponding to the angle of the bone tunnel into which the interference screw is to be inserted. In this way, the angled face will be able to lie approximately flush with the bone surface surrounding the bone tunnel, or at least lie parallel thereto. This reduces or eliminates any significant protrusion by the interference screw above the bone surface when completely inserted within the bone tunnel during fixation of a soft tissue graft, while maintaining contact with substantially all of the cortical bone defining the bone tunnel wall. [0027] Angled interference screws can have any thread pattern. In one embodiment, the thread pattern will comprise a single continuous thread having a uniform pitch wrapping around the outer perimeter of the threaded body. The distal tip, particularly if tapered, may or may not be entirely threaded. The thread or threads may have a constant thread depth (i.e., the radial distance between the outer edge and root of the thread) throughout at least a portion of the screw, although the thread depth may vary at the distal end if tapered, and it may vary, if desired, at the transition between the distal and proximal threaded sections. [0028] It is also within the invention to provide interference screws that include no threads along a particular length of screw about the circumference (e.g., discontinuous threads), such as a non-threaded transition section between the proximal and distal threaded sections, a non-threaded distal tip, or a non-threaded section at the proximal end. It is also within the scope of the invention to provide interference screws of varying thread pitch. [0029] As shown in FIGS. 1 and 2, the exemplary interference screw 100 comprises a threaded body 110 axially extending between an angled face 120 and a tip 130 along a central axis 140. The tip 130 may advantageously be tapered as illustrated in order to facilitate entry of the interference screw 100 into a bone tunnel. [0030] Inasmuch as the interference screw 100 is inserted into a patient's body, the interference screw preferably comprises a material composition that is biodegradable, biocompatible and/or biointegratable. According to one preferred embodiment, the interference screw comprises polyl-l-lactic acid (PLLA). It will be appreciated, however, that the interference screw may alternatively comprise other suitable materials, such as bio-compatible plastics and bio-compatible metals, including but not limited to titanium or stainless steel. [0031] According to one embodiment, the angled face 120 of the interference screw 100 is preferably angled or aligned relative to the central axis 140 in order to correspond or be compatible with the angle of the bone tunnel relative to the bone surface. This will enable the angled face 120 of the interference screw 100 to lay substantially flush with the bone surface surrounding a bone tunnel when the screw 100 is completely inserted into the bone tunnel and oriented at an appropriate rotational angle. In the case of ACL repair surgery, the bone tunnel will usually have an angle in a range of about 20� to about 60� relative to the bone surface, preferably in a range of about 30� to about 40�, and more preferably, in an angle of about 35�. The angled face 120 of the interference screw 100 will have an angle that matches or corresponds to this angle in order to lie substantially flush, or at least parallel, to the bone surface when inserted into a bone tunnel. In general, the angle of the angled face 120 will have an angle relative to the central axis 140 that has the same magnitude as the angle of the bone tunnel relative to the bone surface. [0032] The exemplary threaded body 110 of the interference screw 100 comprises a distal threaded cylindrical section 150 and a proximal threaded cylindrical section 160. As shown in FIGS. 1 and 2, the threads of the distal and proximal cylindrical sections 150 and 160 have the same pitch, although this is not required. The threads of the distal and proximal cylindrical sections 150 and 160 are also shown as being joined as a single continuous thread, although this is not required. [0033] The diameter of the distal threaded cylindrical section 150 next to the tapered tip 130 is smaller than the diameter of the proximal threaded cylindrical section 160. The term �diameter� as used herein will generally refer to the outer diameter defined by the outer edge of the threads, although it will also refer to twice the radius in the case where a portion of the screw has been removed or omitted, such as in the case of an obliquely angled face. According to one embodiment, the diameter of the distal threaded cylindrical section 150 is within a range of about 9 mm to about 11 mm, and the diameter of the proximal threaded cylindrical section 160 is within a range of about 10 mm to about 12 mm. In one embodiment, the diameter of the distal cylindrical section 150 is approximately 1 mm less than the diameter of the proximal cylindrical section 160. A tapered transition section may be provided to join the distal cylindrical section 150 with the proximal cylindrical section 160 with a smooth transition. [0034] The variation in diameter between the distal threaded section 150 and the proximal threaded section 160 enables the interference screw 100 of the invention to securely compress a soft tissue graft against the cortical bone region of a bone tunnel while, at the same time, applying less pressure against the soft tissue graft within the cancellous bone region of the bone tunnel. This is beneficial for enabling the soft tissue graft to more quickly heal and bond with the bone in the cancellous bone region, while providing increased holding strength of the soft tissue graft by the interference screw against the hard cortical bone region. [0035] It will be appreciated that the length of the interference screw 100 may comprise any desired length for accommodating various needs and preferences. [0036] As shown, the interference screw 100 also includes an exemplary drive socket 170. The drive socket 170 is advantageously configured for receiving the shaft 310 of a driver 300 that can rotatably screw the interference screw 100 into a bone tunnel. As shown, the exemplary drive socket 170 comprises a shape that is configured for receiving the shaft 310 of a typical interference screw driver 300 that includes three radially extending protrusions. [0037] The drive socket 170 is preferably aligned with the central axis 140 of the interference screw 100 and may extend to any desired depth within the interference screw 100. In particular, the drive socket 170 may be configured to extend only partially into the interference screw 100 or, alternatively, to extend all the way through the proximal section 160 and into the distal section 150 of the interference screw 100. The drive socket 170 may also extend all the way through the proximal and distal sections 150 and 160. An axial bore (not shown) may be provided for a guide wire, as will be understood by those skilled in the art. [0038] The exemplary protective device 200 is configured for use with the exemplary interference screw 100. In particular, the protective device 200 is configured to concentrically align with the interference screw 100 along central axis 140 and to engage the interference screw 100 along its angled face 120. In one embodiment, the protective device 200 includes an angled face 220 that is sized and shaped so as to planarly engage the angled face 120 of the interference screw 100, as shown and described below in more detail in reference to FIG. 2. In the alternative, the angled faces 120 and 220 may be nonplanar, such as having complementary shapes or curvatures that are able to mate or otherwise interact in a desired fashion. [0039] To accommodate the angle of the angled face 120 of the interference screw 100, the protective device 200 includes an angled face 220 that has an angle relative to the central axis 140 that corresponds to or complements the angle of the angled face 120 of the interference screw 100. For example, the angles of the angled faces 120 and 220 may be selected so that they add up to 90� when using angles that have been normalized to between 0-90� (e.g., angles between 90-180� are �normalized� by subtracting the angle from 180�). Thus, if the angle of angled face 120 of the interference screw 100 were 30� relative to the central axis, the corresponding angle of the angled face 220 of the protective device 200 would be 60�. In this way, the angled faces 120 and 220 will lie flush together and the interference screw 100 and protective device 200 will be concentrically aligned. [0040] With respect to the preferred angles mentioned above relating to interference screws suitable for use in ACL repair procedures, the angled face 220 of the protective device 200 will have a normalized angle that is preferably in a range of about 30� to about 70� relative to the central axis 140, more preferably in a range of about 50� to about 60�, and most preferably about 55� relative to the central axis 140. [0041] Because the protective devices according to the invention are used for inserting an interference screw 100 within the body, they may comprises any material that is safe when temporarily contacted with a person's body. Because it is not intended for the protective devices to remain embedded within a patient's body, it is not necessary for them to have the same level of biocompatibility as the interference screw. Nevertheless, it is within the scope of the invention for the protective device to comprise (PLLA), Teflon (polytetrafluoroethylene (PTFE)), stainless steel, titanium or other materials used to make the interference screw. [0042] The length of the protective device may vary to accommodate the size of various interference screws and driving instruments. The protective device is preferably long enough that it can mate with the face of the interference screw at the same time that both are being engaged by the driving instrument. To accommodate various lengths of protective device 200, however, a driving instrument 300 may be configured with an adjustable collar 320 that can be selectively positioned and repositioned as desired at various locations along the shaft 310 of the driving instrument 300. The collar 320 can be configured, for example, with an allan wrench locking/releasing screw (not shown), or any other suitable locking means. [0043] The diameter of the protective device 200 may also vary. In one embodiment, the diameter of the protective device 200 is at least as large as the diameter of the proximal threaded cylindrical section 160 of the interference screw 100. Accordingly, the diameter of the protective device 200 has a diameter of at least about 10 mm. [0044] As shown in FIG. 1, the body 210 of the protective device 200 includes a passageway 250 through the body 210 of the protective device 200 along the central axis 140. This passageway 250 is preferably large enough to allow the shaft 310 of the driving instrument 300 to pass through it. The passageway 250 may be configured so as to enable the driving instrument to slidably engage the protective device 200 or to pass through the protective device 200 without engaging it. The embodiment in which the passageway 250 does not engage the shaft 310 allows the protective device 200 to freely rotate about the shaft 310 of the driving instrument 300. This can be useful for allowing the protective device 200 to be rotated about the shaft 310 until it is properly aligned with the interference screw 100 so that it can mate with or otherwise engage the angled face 120 of the interference screw 100. [0045] In one embodiment, the passageway 250 through the protective device 200 is sized and shaped so as to mechanically engage the shaft 310 of the driving instrument 300 in a limited number of alignments. This embodiment helps ensure that the protective device 200 is properly aligned with the interference screw 100. For example, the passageway 250 may have the same cross-sectional shape as the drive socket 170 of the interference screw 100. [0046] According to one aspect of the invention, the protective device 200 may include a threaded portion 230 and an extension 240. The extension 240 may be non-threaded, as shown, or threaded if desired. It is generally configured to receive the compressive forces applied by a driving instrument 300, as described above, particularly the collar 320. [0047] The threaded portion 230 of the protective device 200 is configured with threads having the same pitch and general configuration as the threads disposed on the proximal portion 160 of the interference screw 100. This allows the discontinuous threads that are exposed along the face 120 of the interference screw 100 to align with the discontinuous threads that are disposed along the face 220 of the protective device 200. Having the threads of the two devices mate better shields the edges of the threads of the interference screw 100, which would otherwise be exposed in the absence of the protective device 200. [0048] The protective devices according to the invention may be manufactured independently of the interference screws or they may be manufactured integrally with the interference screws. If manufactured integrally with a corresponding interference screw, the interference screw and protective device can simply be cut apart, thereby ensuring that the angled face of the interference screw will match the angled face of the protective device. In this embodiment, the thickness of the cutting blade or other device used to separate the protective device from the interference screw is preferably not so great as to remove too much material (kerf), thereby creating a discontinuity in the threads at the point of contact between the interference screw and the protective device. [0049] Turning specifically now to FIG. 2, the use of the protective device 200 in combination with an interference screw 100 is illustrated. By way of background, FIG. 2 shows a partial cross-sectional view of a knee joint 400. A bone tunnel 410 is formed at an angle into or through the femur 420 and through the tibia 430 of the knee joint 400. The bone tunnel 410 formed through the tibia 430 is preferably formed at an angle within a range of about 30� to about 40� relative to the bone surface. [0050] During ACL reconstructive surgery, according to one embodiment, a soft tissue graft 440 is inserted through the bone tunnel 410 of the femur 420 and the tibia 430. According to the one embodiment, the soft tissue graft 440 comprises a hamstring graft. Hamstring grafts typically comprise multiple strands (e.g. four strands) and are well known in the art for ACL repair operations. Although a multi-strand hamstring graft may be used in the present example as one suitable soft tissue graft, it will be appreciated that the interference screws of the invention may be used to affix other appropriate soft tissue grafts comprising any number of strands (e.g., one or more strands taken from the patellar tendon). In appropriate circumstances an interference screw may be used to affix bone-tendon-bone or other grafts. [0051] The soft tissue graft 440 is initially passed through the tibial portion of the bone tunnel 410 and secured within the bone tunnel 410 of the femur 420 with an interference screw or other device. Next, the soft tissue graft 440 is pulled through the bone tunnel 410 within the tibia 430 and then properly tensioned to ensure that the graft 440 is ultimately secured with the correct amount of tension. Any suitable graft tensioning device may be employed. An example of a tensioning device that is especially suitable for independently tensioning multiple stranded tissue grafts is described in U.S. application Ser. No. 09/711,4440, filed Nov. 13, 2000 in the name of Hugh S. West, Jr., M.D., and entitled APPARATUS AND METHODS FOR INDEPENDENTLY CONDITIONING AND PRE-TENSIONING A PLURALITY OF LIGAMENT GRAFTS DURING JOINT REPAIR. For purposes of disclosing soft tissue graft tensioning devices, the foregoing U.S. application is incorporated herein by reference. [0052] Once the soft tissue graft 440 has been properly tensioned, the soft tissue graft 440 can be secured to the tibia 430. An interference screw according to the present invention may be used to secure the soft tissue graft 440 within the bone tunnel 410 of the tibia 430, thereby reducing the effective length and elasticity of the soft tissue graft 440. [0053] In one embodiment, the ends 460 of the soft tissue graft 440 are tied, such as with a whip stitch, and pulled apart so that an interference screw, such as interference screw 100, may be inserted within the bone tunnel 410 between the separate strands of the soft tissue graft 440. Alternatively, the graft 440 may be positioned eccentrically within the bone tunnel 410. Once the interference screw 100 has been properly positioned, a driving instrument, such as driving instrument 300, can be used to screw the interference screw 100 into the bone tunnel 410 within the tibia 430. The driving instrument 300 can be rotated, in order to screw the interference screw 100 into the bone tunnel 410, by rotating the driving engagement portion 330 (FIG. 1) of the driving instrument 300 with a handle, motorized drive, or other suitable driving device. [0054] The interference screw 100 is used in combination with the protective device 200 in order to shield the discontinuous threads disposed along the edges of the face 120 of the interference screw 100. This, in turn, reduces or eliminates the tendency of the thread of the interference screw 100 to snag or engage the tissue graft 440 or sutures in an undesirable fashion. As shown in FIG. 2, the face 210 of the protective device 200 is planarly engaged with the face 120 of the interference screw 100. The threads of protective device 200 are also aligned with the threads of the interference screw 100. Accordingly, as the interference screw 100 is screwed into the bone tunnel 410, the edges of the angled face 120 are shielded by the face 220 of the protective device 200 so that they will not catch on the ends 460 of the tissue graft 440 and/or sutures connected to the graft 440. [0055] Although the protective device 200 depicted in FIGS. 1 and 2 is sized and configured to mate with interference screw 100 having a corresponding size and shape, it is within the scope of the invention to provide protective devices (not shown) that can be adjusted so as to accommodate a plurality of interference screws of various sizes and/or shapes. For example, protective devices within the scope of the invention may be spring loaded or otherwise able to expand or contract depending on the size of the interference screw. A locking device may be provided that locks the protective device into a desired size or configuration. [0056] It is also within the scope of the invention to provide unthreaded protective devices. FIG. 3 illustrates the use of an unthreaded protective device 500 that is able to mate with the interference screw 100 in much the same way as the threaded protective device 200 described above (i.e., by abutting the angled face 120 of the interference screw 100). The main difference is that the unthreaded protective device 500 does not complete the thread pattern of the inference screw 100. Instead, the unthreaded protective device 500 substantially completes the shape of the interference screw in order to occupy the otherwise open space extending from the angled face 120. In this way, the unthreaded protective device 500 will help to prevent or inhibit a soft tissue graft or sutures from becoming snagged by the exposed edge of the inference screw 100 in the vicinity of the angled face 120. [0057] Depending on the tightness of the fight between the inference screw 100 and a bone tunnel into which it is to be placed, it may be beneficial in same cases for the unthreaded protective device 500 to have a diameter that is less than the diameter of the inference screw 100 in order to facilitate the temporary entry of the protective device 500 into the bone tunnel during placement of the interference screw. Aside from lacking threads, the unthreaded protective device 500 is in other respects the same or similar to the threaded protective device 200 described above. [0058] It is within the scope of the invention to singly provide one or more of the protective devices as needed to facilitate insertion of an angled interference screw into a bone tunnel. In addition, one or more protective devices may be included together with one or more interference screws within a kit, optionally in combination with one or more driver devices. Kits that comprise differently sized and/or shaped interference screws may comprise a plurality of correspondingly sized and shaped protective devices in order to provide a protective device that is able to mate with each interference screw. Alternatively, kits may comprise differently sized and/or shaped interference screws together with one or more protective devices that are adjustable so as to accommodate various interference screws within the kit. [0059] In summary, the protective devices of the invention are configured help place interference screws into bone tunnels and, more particularly, to help place angled interference screws into bone tunnels in a way as to prevent the edges of the interference screw face from catching or snagging a tissue graft and/or sutures attached to the graft and/or other tissues or structures present at the surgical site. [0060] The protective devices may be configured with various diameters, lengths, thread pitch, and face angles to accommodate variations in the corresponding interference screws. The protective devices may be sold separately from the interference screws or sold as part of a kit comprising an interference screw and a corresponding protective device. The kit may also include a driving instrument configured for use with the interference screw and protective device. [0061] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope. BRIEF DESCRIPTION OF THE DRAWINGS [0017] To further clarify the above and other advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. The invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which: [0018]FIG. 1 is an exploded view of an angled interference screw, an exemplary protective device according to the invention, and a driving instrument used to screw the interference screw into a bone tunnel; [0019]FIG. 2 is a perspective view of a knee joint that includes a femur, a tibia, and an angled bone tunnel fashioned through the tibia and femur, together with a soft tissue graft inserted through the bone tunnel and an interference screw being inserted into the bone tunnel while mated with a protective device according to the invention; and [0020]FIG. 3 is a perspective view of an unthreaded protective device according to the invention in a mating configuration relative to an interference screw. BACKGROUND OF THE INVENTION [0001] 1. The Field of the Invention [0002] The present invention generally relates to the field of joint repair surgery, such as reconstruction of the anterior cruciate ligament (ACL). More particularly, the invention relates to the field of interference screws used generally for fixation of soft tissue grafts, such as tibial affixation of soft tissue ACL grafts. [0003] 2. The Relevant Technology [0004] Injuries to joints, specifically the knee, are quite common, particularly when one engages in vigorous sporting activities. A common injury is a rupture or tear of the anterior cruciate ligament (ACL), which is the primary ligament responsible for holding the knee joint together and which keeps it from slipping out of joint or dislocating. An unrepaired ruptured or torn ACL can cripple, and would most certainly limit physical activity of, the person suffering a ruptured or torn ACL. [0005] One method for performing an ACL reconstruction procedure involves taking a tissue graft from another part of the body, such as a soft tissue graft (e.g., from the hamstrings), and attaching it at both ends through bone tunnels drilled through the two bones that make up the knee joint: the femur and the tibia. When secured in place, the tissue graft mimics and, hence, takes the place of, the ACL itself. This tissue graft holds the femur and tibia together to make the joint more stable, while simultaneously allowing for normal joint movements (i.e., flexion and extension). [0006] One way to attach the graft to the bone is with an interference screw. An interference screw is screwed into a bone tunnel through which the soft tissue graft passes, thereby causing the graft to be compressed against the surface of the bone tunnel with sufficient force for holding the graft in place. The interference screw shortens the effective length of the graft and minimizes the �bungee effect� by affixing the soft tissue graft and preventing the graft from stretching inside of the bone tunnels. [0007] One type of interference screw includes a threaded body and a trailing end, or head, that is substantially flat and perpendicular relative to the threaded body. This can create a problem whenever the bone tunnel is formed at an angle relative to the bone surface. Because an angled bone tunnel is not perpendicular to the bone surface, the surface of the trailing end of the interference screw will not lie flush with the bone surface. As a result, either a corner of the trailing end will protrude from the bone, requiring an extra cutting step to remove the protrusion, or a substantial portion of the screw will be recessed within the bone tunnel surface, which reduces the amount of surface contact between the screw and the hard cortical bone at the bone surface, thereby potentially comprising the holding strength of the screw against the graft. [0008] In order for the interference screw to make complete circumferential contact against the cortical bone region of the bone tunnel, an improved screw has been developed by the inventor having an obliquely angled trailing end that matches or corresponds to the angle of the bone tunnel. In this way, the trailing end can lie flush with the bone tunnel surface, while also making complete circumferential contact at the cortical bone region of the bone tunnel, when the screw has been inserted properly into the bone tunnel. [0009] Interference screws of the inventor having obliquely angled trailing ends have proven to be an excellent solution to the problems inherent whenever a bone tunnel is angled so as to not be perpendicular to the bone tunnel surface. Nevertheless, forming an oblique angle in the trailing end of the interference screw can create relatively sharp edges, particularly where the threads are exposed, which can potentially snag the tissue graft and/or sutures attached to the graft when the screw is screwed into the bone tunnel. Accordingly, there is a present need to provide interference screws with angled trailing ends while minimizing the risk that the interference screw will snag the tissue graft and/or sutures as the screw is screwed into the bone tunnel. SUMMARY OF THE INVENTION [0010] The present invention is directed to protective devices for use with angled interference screws used to affix soft tissue grafts within angled bone tunnels during reconstructive surgery. The protective devices reduce or eliminate the tendency of angled interference screws from snagging the tissue graft and/or sutures as the interference screw is screwed into the bone tunnel. The invention also encompasses methods and kits that employ or include one or more protective devices in combination with one or more angled interference screws. [0011] According to one embodiment, the protective devices of the invention are configured to engage interference screws that have angled faces or trailing ends while the interference screws are inserted into obliquely aligned bone tunnels. Each protective device generally comprises a threaded body having a central passage through which a drive shaft can be inserted and an angled surface that mates with the angled surface of the interference screw. In this way, the protective device essentially completes the interference screw (i.e., it fills in the portion of the screw that is removed to form the angled trailing end). [0012] The protective device temporarily forms an interference screw/mating device combination that virtually eliminates any sharp edges associated with the angled trailing end of the interference screw. This, in turn, reduces the risk that the interference screw will snag the tissue graft and/or sutures when screwed into the bone tunnel to secure a tissue graft in place. [0013] According to one aspect of the invention, the protective device includes threads having the same pitch and spacing as the threads on the interference screw. Accordingly, when the protective device is aligned with the interference screw, and when the angled faces of the mating device and the interference screw are in mating engagement, the threads of the protective device will be substantially aligned with the threads of the interference screw. In this way, the protective device will temporarily complete the thread pattern of the portion of the interference screw that is removed to form the angled trailing end. Completing the thread pattern allows the interference screw to be threadably inserted into the bone tunnel without unnecessarily exposing the discontinuous threads that are disposed along the angled face of the interference screw to the surrounding tissues. This, in turn, facilitates placement of the interference screw within the bone tunnel, particularly when pressing the tissue graft against the bone tunnel wall. Notwithstanding the foregoing, it is also within the scope of the invention to provide protective devices that are unthreaded although this embodiment is not presently preferred. [0014] In many cases, the surgeon may have interference screws of varying size and/or shape at his or her disposal to accommodate differences in the size and/or angle of different bone tunnels formed within different patients. In such cases, it may be advantageous to provide a variety of protective devices that correspond to the variously sized and/or shaped interference screws. In this way, the surgeon will be able to select a protective device that best fits or mates with a particular interference screw being used. [0015] In an alternative embodiment, it may be desirable to provide one or more protective devices that are adjustable so as to accommodate interference screws of various size and/or shape. For example, a protective device within the scope of the invention may be spring loaded or otherwise able to expand or contract depending on the size of the interference screw. A locking device may be provided that locks the protective device into a desired size or configuration. [0016] These and other advantages and features of the present invention will more fully apparent from the following description and appended claims, or learned by the practice of the invention as set forth hereinafter. Referenced byCiting PatentFiling datePublication dateApplicantTitleUS7727278 *Jun 30, 2006Jun 1, 2010Rti Biologics, Inc.Self fixing assembled bone-tendon-bone graftUS7744635Mar 3, 2005Jun 29, 2010Spinal Generations, LlcSpinal fixation systemUS8021398Aug 2, 2006Sep 20, 2011Life Spine, Inc.Spinal fixation systemUS8257407 *Apr 23, 2009Sep 4, 2012Aryan Henry EBone plate system and methodUS8617227 *May 25, 2011Dec 31, 2013Acumed LlcBone connector with pivotable jointUS20100082071 *Sep 26, 2008Apr 1, 2010Missoum MoumeneComposite Screw Having A Metallic Pin and a Polymeric ThreadUS20100121448 *Jan 14, 2010May 13, 2010Depuy Mitek, Inc.Method and apparatus for fixing a graft in a bone tunnelUS20110224738 *May 25, 2011Sep 15, 2011Acumed LlcBone connector with pivotable jointEP1797845A1 *Dec 18, 2006Jun 20, 2007Ethicon Inc.Arthroscopic implants with integral fixation devicesWO2009123791A1 *Feb 10, 2009Oct 8, 2009Lonnie PaulosInterference screw driver assembly and method of useWO2013159760A1 *Apr 11, 2013Oct 31, 2013Primed Halberstadt Medizintechnik GmbhBone screw arrangement for fixing a tendon (transplant shuttle system tss)* Cited by examinerClassifications U.S. Classification606/916, 606/323, 606/304, 606/321, 606/312International ClassificationA61B17/86, A61F2/08, A61B17/88Cooperative ClassificationA61F2002/0882, A61F2002/0841, A61F2002/0858, A61F2/0805, A61B17/861, A61B17/8875, A61F2002/0829, A61F2/0811European ClassificationA61F2/08F, A61B17/88SLegal EventsDateCodeEventDescriptionNov 24, 2010FPAYFee paymentYear of fee payment: 4Dec 4, 2007CCCertificate of correctionNov 26, 2002ASAssignmentOwner name: HS WEST INVESTMENTS LLC, UTAHFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WEST, HUGH S. JR., M.D.;REEL/FRAME:013527/0272Effective date: 20021126RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google

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text:
13 questions linked to/from How to use and style new AlertDialog from appCompat 22.1 and above
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I'm using ActionBarActivity from the Android 5 SDK and here is my theme.xml for v21 <style name="AppTheme_Light" parent="Theme.AppCompat.Light.DarkActionBar"> <item name="android:...
I'm trying to change the text color in dialog boxes, most commonly AlertDialog. I've tried every solution at these pages: AlertDialog styling - how to change style (color) of title, message, etc ...
asked Feb 10 '15 at 18:05
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I'm trying to style all my dialog fragments to look the same in my app. The dialogs coming from my settings fragment are styled exactly the way I want it. For my custom dialog fragments, the style ...
I have a fragment in which I need to show a custom dialog. Please check out my code below. public class MyFragment extends Fragment{ @Override public void onCreate(Bundle savedInstanceState) { ...
Been fighting for hours about changing the alignment of the buttons inside AlertDialog (support.v7 one), since they won't align themselves according to the locale view direction, despite the whole app ...
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How to make custom style for example for green buttons and background of message using AlertDialog. ??? Definition of AlertDialog: AlertDialog.Builder alert = new AlertDialog.Builder(About.this, R....
I am using UserDialogs library in my MVVMCross project. The following code has been tested and works perfectly fine, I could able to see Loading Dialog. The issue that I have, how could I able to ...
asked Jun 30 '16 at 19:58
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There is problem with my styles. I would like prepare AlertDialog totaly colered in yellow without shadow. Here is code below: AlertDialog.Builder alert = new AlertDialog.Builder(About.this, R.style....
asked May 15 '15 at 12:45
I'm applying this theme from manifest : <activity android:name=".ui.rate.MyActivity" android:theme="@android:style/Theme.Dialog"> </activity> With this the ...
java android view crash android-theme
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Title showing 2 times in AlertDialog
I am trying to show an AlertDialog in android. The problem is that the title of the dialog appears 2 times. I want it to show only one title? How can I do it? That is how the dialog looks like And ...
I am creating some AlertDialog using the v7 support library 22.1.1 (as I want to support Android 2.3 as well): import android.support.v7.app.AlertDialog; //import android.app.AlertDialog; ...
android android-layout android-support-library android-dialog android-tablelayout
asked May 7 '15 at 9:38
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Why the accent color in the popup dialogue view(created dynamically i.e by java code) is green whereas I have different color in my application theme?
So I have set the colors i.e primary, primaryDark, accentColor in the style.xml manually and I can see whole application is taking the colors properly such as toolbar is having the appropriate colors, ...
java android android-fragments colors dialog

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Patent US5600680 - High frequency receiving apparatus - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsA high frequency television signal receiving apparatus providing excellent linear detection of output characteristics by improving the phase characteristic of the picture synchronous detector. A variable capacitive element is equivalently connected in parallel to a reference solid-state oscillation element....http://www.google.com/patents/US5600680?utm_source=gb-gplus-sharePatent US5600680 - High frequency receiving apparatusAdvanced Patent SearchPublication numberUS5600680 APublication typeGrantApplication numberUS 08/525,247Publication dateFeb 4, 1997Filing dateSep 8, 1995Priority dateJun 1, 1993Fee statusLapsedAlso published asCN1065395C, CN1097915APublication number08525247, 525247, US 5600680 A, US 5600680A, US-A-5600680, US5600680 A, US5600680AInventorsAkira Mishima, Hiroshi Nagai, Akio IwaseOriginal AssigneeMatsushita Electric Industrial Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (10), Referenced by (8), Classifications (20), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetHigh frequency receiving apparatusUS 5600680 AAbstract A high frequency television signal receiving apparatus providing excellent linear detection of output characteristics by improving the phase characteristic of the picture synchronous detector. A variable capacitive element is equivalently connected in parallel to a reference solid-state oscillation element. The reference solid-state oscillation element controls the frequency of a local oscillation device including a PLL circuit for feeding a local oscillation signal to a mixer for converting a high frequency signal into an intermediate frequency signal. A first low pass filter is connected between a phase comparator for detecting a phase difference of the intermediate frequency signal and the output of a detection oscillator for generating a detection oscillation signal with a specific phase difference. A second low pass filter having a larger time constant than the first low pass filter is connected to the variable capacitive element. The capacitance of the variable capacitive element is varied by the output voltage of the phase comparator. The signal frequency of the local oscillation device is shifted, and is controlled to converge the frequency of the intermediate frequency signal within the frequency range of the detection oscillation signal.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3784917 *Dec 15, 1972Jan 8, 1974Philco Ford CorpConstant lock-in range automatic frequency controlUS4642573 *Oct 3, 1985Feb 10, 1987Hitachi, Ltd.Phase locked loop circuit for demodulating suppressed carrier signalsUS4871973 *May 12, 1988Oct 3, 1989Nec CorporationDemodulator including sweep controller for controlling synchronization capture rangeUS5128626 *May 28, 1991Jul 7, 1992Nec CorporationCoherently demodulating arrangement including quasi-coherent demodulator for PSK signalsUS5179729 *Feb 20, 1990Jan 12, 1993Matsushita Electric Industrial Co., Ltd.Tuner station selecting apparatusUS5325401 *Mar 13, 1992Jun 28, 1994Comstream CorporationL-band tuner with quadrature downconverter for PSK data applicationsUS5335354 *Nov 26, 1991Aug 2, 1994Kabushiki Kaisha ToshibaDemodulation circuit having automatic frequency control functionUS5396521 *Oct 18, 1993Mar 7, 1995Nec CorporationReceiver capable of reducing power consumption in a PLL circuitUS5483687 *Nov 10, 1993Jan 9, 1996Motorola, Inc.Operational transconductance amplifier track and hold systemUS5499392 *Jul 19, 1994Mar 12, 1996Matsushita Communication Industrial Corporation Of AmericaFilter having a variable response time for filtering an input signal* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5930697 *Jun 10, 1996Jul 27, 1999Temic Telefunken Microelectronic GmbhHeterodyne receiver with synchronous demodulation for receiving time signalsUS6046781 *Mar 24, 1997Apr 4, 2000Samsung Electronics Co., Ltd.Automatic fine tuning of TV receiver for receiving both digital and analog TV signalsUS6094236 *Apr 28, 1997Jul 25, 2000Kabushiki Kaisha ToshibaTuner circuitUS6748220May 5, 2000Jun 8, 2004Nortel Networks LimitedResource allocation in wireless networksUS7079591Aug 1, 2001Jul 18, 2006Radiodetection LimitedMethod and system for recovering information from a magnetic field signal usable for locating an underground objectUS7209725 *Jan 3, 2000Apr 24, 2007Parkervision, IncAnalog zero if FM decoder and embodiments thereof, such as the family radio serviceWO2003012478A2 *Aug 1, 2002Feb 13, 2003Fling Richard WilliamSystem for recovering information from a magnetic field signal usable for locating an underground object and methodWO2003071673A2 *Feb 25, 2003Aug 28, 2003Manku TajinderFrequency down converter using a multitone local oscillator* Cited by examinerClassifications U.S. Classification375/327, 375/344, 348/536, 455/265, 329/360, 329/325, 455/260, 455/262, 348/735International ClassificationH04N5/44, H03D1/22, H04N7/10, H03D9/00, H03J7/08, H03D7/16Cooperative ClassificationH03D1/2254, H03J7/08, H03D7/163European ClassificationH03J7/08, H03D1/22E1Legal EventsDateCodeEventDescriptionMar 24, 2009FPExpired due to failure to pay maintenance feeEffective date: 20090204Feb 4, 2009LAPSLapse for failure to pay maintenance feesAug 11, 2008REMIMaintenance fee reminder mailedJul 7, 2004FPAYFee paymentYear of fee payment: 8Jul 24, 2000FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google


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Cliff Lodge - Guest House (De Kelders, ZAF) | Expedia
1-800-238-0767 Cliff Lodge - Guest House
6 Cliff Street De Kelders Gansbaai
Kayak Junkies - 1.9 miles
Grootbos Nature Reserve - 2.3 miles
Situated by the ocean, this romantic guesthouse is 2.2 mi (3.5 km) from Kayak Junkies and within 6 mi (10 km) of Danger Point Lighthouse and Gansbaai Harbor. Grootbos Nature Reserve and Kleinbaai Harbour are also within 6 mi (10 km). Property Features
Along with an outdoor pool, this guesthouse has massage/treatment rooms and a library. Free full breakfast, free WiFi in public areas, and free self parking are also provided. Other amenities include tour/ticket assistance. Room Amenities
All 5 rooms offer free WiFi, premium bedding, and satellite TV. Other amenities available to guests include hair dryers, safes, and desks. Information missing or incorrect? Tell us!Opens in a new window Select to view moreAbout the Guest house Tab 1 of 2 selectedSelect to viewGuest Reviews Tab 2 of 2 Cliff Lodge - Guest House
A complimentary breakfast is offered each morning. High-speed wireless Internet access is complimentary. This romantic guesthouse also offers an outdoor pool, a library, and tour/ticket assistance. Complimentary self parking is available on site. Total number of rooms - 5 Free breakfast Tours/ticket assistance Free WiFi Library Spa treatment room(s) Free self parking Beach umbrellas Beach towels Outdoor pool Show all guest house amenities
Premium bedding Free toiletries Hair dryer In-room safe Desk Satellite TV service Free WiFi Where to Eat

value: This website is an online travel agency owned by Expedia Group, an American online travel shopping company based in Seattle.


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The 6 Best Kerkini Lake Hotels - Where To Stay in Kerkini Lake, Greece
Hotels & places to stay in Kerkini Lake, Greece
Featured hotels in Kerkini Lake
11 properties in Kerkini Lake
Description Set on the foothills of Belles Mountain, Villa Belles offers traditional-style accommodation with modern amenities, overlooking the magnificent Kerkini Lake and surrounded by the countryside landscape...
"This was a birdwatching week alone. The location is stunning, the birds on Kerkini Lake remarkable and the hotel could not be better placed for that. The staff were super. Very friendly, considerate and..."
Description Built of local stone and wood, Oikoperiigitis Hotel is set amidst lush greenery within 500 metres from Lake Kerkini in Serres.
"Very cozy, comfortable, lovely and stylishly furnished, clean, quiet. Еverything was wonderful."
I.Tsch.. Bulgaria
Hotel Erodios This is a Preferred Partner property. It is committed to providing guests with a positive experience thanks to its commendable service and good value. This property may pay Booking.com a bit more to be in this Programme.
Description Enjoying panoramic views of Kerkini Lake in Lithotopos village and just 100 metres from its shore, Erodios hotel is surrounded by a green-covered area of 22,000 m2.
KALCHO. Bulgaria
Ihnilatis This is a Preferred Partner property. It is committed to providing guests with a positive experience thanks to its commendable service and good value. This property may pay Booking.com a bit more to be in this Programme.
Description Ihnilatis is located amidst a well-tended garden in Korifoudi village. It offers traditionally decorated, air conditioned studios opening out to a terrace. Lake Kerkini is 400 metres away.
Mr ZaYaC. Ukraine
Description The traditionally built Guesthouse To Fragma is located in Lithotopos Village of Serres, within 300 metres from Lake Kerkini.
"Lovely room with a balcony watching over the lake. Vary nice host, helped us with everything we needed. Has a great resturant with fresh fishes."
Hillel. Georgia
Description Guesthouse Alkioni offers air-conditioned rooms opening out to a balcony with Kerkini Lake and mountain views.
"Very nice and quiet location above the whole village, with superb panorama to the lake and dam below. Spotless clean, stylish and spacious property and very welcoming staff. We felt like in our own personal..."
Eugen Mitu. Romania
Description Located 100 metres from Kerkini Lake, Guesthouse Kerkinitis in Lithotopos Village, features a garden and free WiFi throughout. Other facilities include a communal kitchen and lounge area.
"Roomy comfortable accommodation, good breakfast and very friendly and helpful hosts. We will be back"
Description Offering a restaurant, the traditional and stone-built Morfi Hotel is in the centre of Kerkini Village. It features self-catered accommodation with a fireplace.
"I spent here 2 separate nights with my family within a longer journey to and back. Hosts are highly friendly. Meal is optional, but good and cost effective. Kerkini Lake is 1 km far, it is good to walk..."
Description Featuring free WiFi throughout the property, Guesthouse Georgia offers accommodation in Lithótopos. Free private parking is available on site.
Limnaio This is a Preferred Partner property. It is committed to providing guests with a positive experience thanks to its commendable service and good value. This property may pay Booking.com a bit more to be in this Programme.
Description Enjoying a quiet location in Chrysohorafa Village, the traditionally built Limnaio guest house lies within a short walk from the eastern shore of Lake Kerkini.
"Thew owners was super friendly and helpful! we loved the rooms and enjoyed all facilities, even if for one night."
See all 11 properties in Kerkini Lake
Browse our 'Best of' lists to find the top rated properties in Kerkini Lake, based on 1149 reviews from real guests
Best hotels in Kerkini Lake
#1 of 3 Hotels in Kerkini Lake
“On the way back from Lefkada, one night stop in Eroduos...”
#2 of 3 Hotels in Kerkini Lake
“Great location close to the shore of Lake Kirkini, with...”
#3 of 3 Hotels in Kerkini Lake
“What a warm welcome and caring attitude!”
“Stunning views, fantastic location.”
See complete list of Kerkini Lake hotel reviews
Best B&Bs and inns in Kerkini Lake
#1 of 4 B&Bs and Inns in Kerkini Lake
“Quiet, nice location, excellent breakfast and Maria most...”
#2 of 4 B&Bs and Inns in Kerkini Lake
“Clean room, good breakfast, nice view.”
“Nice experience ar an surreal lake in Grece”
#3 of 4 B&Bs and Inns in Kerkini Lake
“location, friendly peraonal”
“We had a cosy room with a large, corner balcony.”
See complete list of Kerkini Lake B&B and inn reviews
Best holiday rentals in Kerkini Lake
#1 of 2 Holiday Rentals in Kerkini Lake
“Very nice hotel, the apartment had a fireplace and was...”
#2 of 2 Holiday Rentals in Kerkini Lake
“Good place to stay for a quick trip to Kerkini”
“We were there first time to watch birds, and found out our stay was too shot.”
See complete list of Kerkini Lake holiday rental reviews
People are talking about Kerkini Lake! Explore guest hotel reviews featuring "Kerkini Lake"
“Very nice location, amazing view of the Kerkini Lake, our suite was very pleasant, especially the main bedroom, had several windows and the balcony that you could open and make a breeze. All windows and both balconies had mosquito nets. No need for A/C. Very quiet, in the middle of the countryside. Nice staff. Crispy clean bed linen, nice towels, clean room. ”
“we arrived at 2am local time and the owner was waiting for us with keys. Room was perfect with aircondition and large balcony overlooking the lake. Breakfast was very tasty with local traditional food. Vangelis (the owner) was very helpful where to buy local products. He also organised for us boat ride on a Kerkini lake. it was very pleasant stay and for sure we will be back again.”
“I spent here 2 separate nights with my family within a longer journey to and back. Hosts are highly friendly. Meal is optional, but good and cost effective. Kerkini Lake is 1 km far, it is good to walk to and aside.”
“Fine place to stay for nature and relaxing. Kerkini Lake is near and you can watch a lot of birds in their habitat.”
Popular hotels in Kerkini Lake
In and around Kerkini Lake
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value: This website is a Dutch online travel agency for lodging reservations & other travel products, and a subsidiary of Booking Holdings. It is headquartered in Amsterdam.The website has over 28 million listings.


text:
Patent US5013581 - Method of making a polymer-metal compound having a predetermined electrical ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsThe method of making an electrically conductive polymer-metal compound having a predetermined electrical conductivity on a substrate includes the steps of preparing a reaction mixture of a gaseous metallo-organic compound, a metal-free gaseous organic compound and a carrier gas such as argon or mixtures...http://www.google.com/patents/US5013581?utm_source=gb-gplus-sharePatent US5013581 - Method of making a polymer-metal compound having a predetermined electrical conductivity by depositing on a substrate from a glow discharge zoneAdvanced Patent SearchPublication numberUS5013581 APublication typeGrantApplication numberUS 07/561,934Publication dateMay 7, 1991Filing dateAug 2, 1990Priority dateMay 12, 1987Fee statusLapsedAlso published asCA1332720C, DE3716235A1, DE3716235C2, EP0291444A1, EP0291444B1Publication number07561934, 561934, US 5013581 A, US 5013581A, US-A-5013581, US5013581 A, US5013581AInventorsHarald Suhr, Angelika Etspuler, Ernst Feurer, Christian OehrOriginal AssigneeSchering AktiengesellschaftExport CitationBiBTeX, EndNote, RefManReferenced by (5), Classifications (23), Legal Events (7) External Links: USPTO, USPTO Assignment, EspacenetMethod of making a polymer-metal compound having a predetermined electrical conductivity by depositing on a substrate from a glow discharge zoneUS 5013581 AAbstract The method of making an electrically conductive polymer-metal compound having a predetermined electrical conductivity on a substrate includes the steps of preparing a reaction mixture of a gaseous metallo-organic compound, a metal-free gaseous organic compound and a carrier gas such as argon or mixtures of argon and hydrogen, producing a glow discharge zone in the reaction mixture and exposing the substrate to action of the gaseous metallo-organic compound and the metal-free gaseous organic compound in the glow discharge zone in such a way as to produce a film or layer of the polymer-metal compound with a predetermined electrical conductivity. The selection of the electrical conductivity can be made by setting at least one of a number of parameters of the process including the pressure and temperature of the glow discharge zone, the power density in the glow discharge and particularly the ratio of the amount of metal-free gaseous organic compound to carrier gas. The substrate may be a plastic such as polyimide, an aluminum or silicon oxide ceramics or glass.
We claim: 1. A method of making an electrically conductive polymer-metal compound on a substrate comprising the steps of preparing a reaction mixture of a gaseous metallo-organic compound and a metal-free gaseous organic compound, producing a glow discharge zone in said reaction mixture and exposing the substrate to action of the gaseous metallo-organic compound and the metal-free gaseous organic compound in the glow discharge zone so as to produce the electrically conductive polymer-metal compound with a predetermined electrical conductivity.
2. A method according to claim 1, wherein the metallo-organic compound is volatile and sublimable under operation conditions during the exposing.
3. A method according to claim 1, further comprising a step of additionally heating the metallo-organic compound in a supply container.
4. A method according to claim 1, further comprising a step of admixing a carrier gas with the reaction mixture prior to the exposing.
5. A method according to claim 4, wherein said carrier gas is selected from the group consisting of argon, helium, hydrogen and mixtures of argon and hydrogen.
6. A method according to claim 4, further comprising a step of preselecting a ratio of amounts of said metal-free gaseous organic compound and said carrier gas to produce said polymer-metal compound having said predetermined electrical conductivity.
7. A method according to claim 1, wherein said glow discharge is characterized by a plurality of parameters including a pressure, a temperature and a power density in the glow discharge zone and further comprising preselecting and controlling at least one of said parameters to predetermine the polymer-metal compound electrical conductivity.
8. A method according to claim 1, wherein said substrate is an inorganic substrate selected from the group consisting of aluminum oxide ceramics, silicon oxide ceramics, glass and metals with oxide and nitrite layers.
9. A method according to claim 1, wherein said metallo-organic compound is selected from the group consisting of dimethylgold(III)-acetylacetonate, copper hexafluoroacetylacetonate, nickel hexafluoroacetylacetonate, allylcyclopentadienylpalladium(II), tin tetramethyl, tin tetraethyl, nickel tetracarbonyl, molybdenum hexacarbonyl and dicobaltocatocarbonyl.
10. A method according to claim 1, wherein said metal-free gaseous organic compound is selected from the group consisting of methane, ethane, propane, butane, acrylonitrile, ethylene, propene, butenes, pyridine, piperdine and morpholine.
11. A method according to claim 1, wherein said substrate is a plastic.
12. A method according to claim 11, wherein said plastic is polyimide.
This application is a continuation-in-part application of the application Ser. No. 07/193,589 having a filing date of May 12, 1988.
BACKGROUND OF THE INVENTION The present invention relates to a method of making a polymer-metal compound whose electrical conductivity varies within large limits and can be adjusted to a desired value and, more particularly, to a method of making an electrically-conductive polymer-metal compound of a predetermined conductivity on a substrate made of inorganic or organic material.
Methods of making an electrically conductive polymer-metal compound are known, in which methods volatile metallo-organic compounds are decomposed in a glow discharge zone in a reactor and are polymerized into the polymer-metal compound containing the metallic components. These methods are known as plasma polymerization methods.
A method of plasma polymerization of iron carbonyl and related iron metallo-organic compounds has been investigated by Sadhir and Saunders. This method is described in the article "Deposition of conducting thin films of organometallic monomers by plasma polymerization" by R. K. Sadhir and H. E. Saunders in J.Vac.Sci. Technol. A 3(6), 1985, pp. 2093-2097. In this method no additional metal-free organic compounds are used in the reactant mixture in which the glow discharge is formed so that an additional parameter effecting the ratio of metal to carbon in the discharge is not available. There is no teaching of a way to control the deposition so that a coating with a predetermined electrical conductivity can be obtained. The value of the conductivity of the conductive film which is produced depends on the geometry of the apparatus used to produce the film, especially the distance between the supply location of the metallo-organic compound and the substrate. It is understandable that a polymer-metal film with a predetermined desired resistance value cannot be produced by this method.
A method of producing conductive metal-fluorocarbon polymer films has been described by Perrin, Despax, Hanchett and Kay in the article, "Microstructure and electrical conductivity of plasma deposited gold/fluorocarbon composite film" by J. Perrin, B. Despax, V. Hanchett and E. Kay, J.Vac.Sci.Technol. A 4(1), 1986, pp. 46 to 51. The substrate is exposed to a plasma discharge in a fluorocarbon and argon gas mixture in this method. Instead of using a gaseous metallo-organic compound as a source of metal atoms for the plasma produced in the fluorocarbons gold or other metal atoms are added to the composite film produced on the substrate by RF sputtering methods using a gold coated electrode. The method produces an organic polymer film, in which metallic particles in the form of numerous small spots spaced from each other are embedded. These films must contain at least about 50% metal atoms to be conductive. Typical properties of the films produced are the limited values of "spot density" and the 50% threshold for film conductivity. Thus, it is almost impossible to obtain a film with an electrical conductivity above a certain value.
Morosoff and Haque have studied the plasma polymerization of volatile transition metal compounds and C2 hydrocarbons. A coating was formed by exposing a substrate to a plasma made in a reactant gas containing an iron carbonyl and a C2 hydrocarbon. The nature of the products and chemical processes occurring during film formation was determined. No measurements of electrical conductivity were made however and there was no study of the effect of varying process parameters on the electrical conductivity of the film formed, so that there is no way to know if an electrically conductive polymer layer would form under the conditions used in their experiments. Similarly there is no suggestion that their method could be used to produce an electrically conductive layer. This work was described in the article "Transition metal containing plasma polymers" by N. Morosoff and R. Haque and S. D. Clymer and A. L. Crumbliss in J.Vac.Sci.Technol. A 3(6), 1985, pp.2096 to 2101.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of producing a polymer-metal compound by a vapor deposition and reaction process in a glow discharge, which utilizes a volatile metallo-organic compound and a metal-free gaseous organic compound as starting materials.
This and other objects of the present invention are attained by a method of making an electrically conductive polymer-metal compound on an organic or inorganic substrate, comprising the steps of preparing a reaction mixture of a gaseous metallo-organic compound and a metal-free gaseous organic compound, producing a glow discharge zone in said reaction mixture and exposing the substrate to action of the gaseous metallo-organic compound and the metal-free gaseous organic compound in the glow discharge zone to produce a film of an electrically conductive polymer-metal compound of a predetermined electrical conductivity.
By gaseous metallo-organic and metal-free organic compounds used in our process we mean those compounds which are sufficiently volatile and sublimable so that they can be used under the operational conditions of a plasma reactor in our process.
The method may also include a step of additionally heating the metallo-organic compound in a supply container to produce the gaseous metallo-organic compound need for the reaction mixture.
The method may additionally include a step of supplying a carrier gas which is admixed with the metal-free gaseous organic compounds and gaseous metallo-organic compounds before plasma polymerization in the reactor.
The carrier gas may be an inert gas selected from the group consisting of argon and helium and the carrier gas may be admixed with a reducing gas such as hydrogen.
To make a polymer-metal compound having a predetermined resistance and/or conductivity, particularly the ratio between the amounts of the metal-free gaseous organic compound used and the carrier gas in the reaction mixture should be pre-selected.
However other parameters such as the total pressure in the glow discharge, the temperature of the electrodes of the reactor used to produce the discharge zone and the temperature in the glow discharge and the power density in the glow discharge zone may be preselected and controlled to predetermine the polymer-metal compound electrical conductivity or resistance.
The invention is especially applicable to a manufacturing process for production of resistors on inorganic or organic nonconducting substrates and integrated circuits containing these resistors. Antistatic layers and radiation-shielding layers for sensitive electronic circuits can be produced using the methods of our invention. Almost any shape substrate may be coated by these methods including film, plate, disc and large surface area substrates.
The polymer-metal compounds produced by the method of our invention have properties which are entirely different from the films and coatings which have been made in the prior art. It is possible to produce electrical conductivities over a wide range of orders of magnitude. The conductivities of the films produced by the method of our invention have an approximately simple linear dependence on film composition. Predetermined conductivities can be simply obtained by an exact metering of the gaseous metallo-organic compound and the metal-free gaseous organic compound supplied to the reactant mixture in which the glow discharge is generated. The control of the composition of the film can be improved particularly when the inert carrier gas, especially argon, is used.
The specific advantages of the method of our invention are based on the mechanism of the film formation on the substrate.
In contradistinction to conventional methods a metal-carrying metallo-organic molecule is first absorbed on an outer surface of the substrate and then, due to reaction with the plasma and its ions, electrons and protons, is converted a free metal-containing fragment. Thus, not only is the substrate etched by the plasma, but also the metallo-organic molecule, depending on the intensity and duration of the operation, is decomposed into greater or smaller metallic fragments. When the organic component of the fragments is not entirely removed the films are produced by combination of the gaseous organic molecules and metallo-organic fragments. Organic monomers are then embedded in a polymeric matrix in the produced films. Because of this mechanism the film formed does not include the metal in the form of crystals or localized spots or aggregates.
These features of the mechanism operating in the glow discharge zone, when taken together with the simple control of film properties by adjustment of certain operational parameters of our method, make possible a "custom-made" production of resistors, for example for sensors, integrated circuits and other applications.
A further advantage of the process according to our invention is that the substrate is extraordinarily well preserved and is exposed to only a very small energy density. Thus, sensitive plastics which are strongly damaged during the cathode sputtering can also be used as an organic substrate in our process and coated with films.
The methods of our invention can take place in a conventional plasma reactor. The plasma reactor, in which the glow discharge zone is produced in the reaction mixture, can be a pipe reactor, tunnel reactor or parallel plate reactor. The plasma may be produced by D.C. current or alternating current. High frequency alternating current may be used. The pressure in the plasma reactor is advantageously 5 to 100 Pa, which is also advantageous compared to the high vacuum conditions required in cathode sputtering or vapor-deposition. No high vacuum with pressure less than 3 Pa is required.
The substrates used in our process can be inorganic substrates, particularly inorganic nonconducting substrates such as aluminum oxide ceramics, silicon oxide ceramics and glass. Metals with oxide and nitrite layers may also be used as substrates. Organic substrates can also be used. The organic substrates which can used include especially plastics, which can be particularly sensitive. Polyimide can be used as one of the organic substrates of the invention.
All metallo-organic compounds, which are volatile or sublimable under the proposed vacuum conditions, are suitable as the gaseous metallo-organic compounds of the invention. The transport of both the metal-free gaseous organic compounds and metallo-organic compounds of the invention into the glow discharge occurs by generation of a pressure differential by vacuum techniques so that a uniform gas reactant mixture is provided in the glow discharge zone. The supply containers for either or both the metallo-organic compound and the gaseous metal-free organic compound can be provided with a heating device for conveying compounds, which are more difficult to vaporize in sufficient amounts into the gas flow to the glow discharge zone.
The following metallo-organic compounds may be used as the gaseous metallo-organic compounds of our invention:
Dimethylgold(III)-acetylacetonate
Copper hexafluoroacetylacetonate
Nickel hexafluoroacetylacetonate
Allylcyclopentadienylpalladium (II)
Tin tetramethyl
Tin tetraethyl
Dicobaltoctocarbonyl
Saturated and unsaturated hydrocarbons can be used as the gaseous metal-free organic compounds of the invention. These compounds enter into polymerization reactions under the action of the glow discharge. The following are examples of the gaseous metal-free organic compounds of the method of our invention: methane, ethane, propane, butane, ethylene, propene, butenes, pyridine, piperidine and morpholine.
The following examples, which are all performed in a parallel plate reaction well known in the prior art, are set forth below to clarify the invention.
EXAMPLES Example I. Polymeric Palladium Layer Allylcyclopentadienyl palladium (II), the metallo-organic compound, and propene, the metal-free gaseous organic compound, are admitted to a parallel plate reactor in an argon carrier gas. An aluminum oxide ceramic substrate is exposed to a glow discharge zone formed in this reaction mixture between the electrodes of the parallel plate reactor. A voltage of 400 D.C. volts is applied to the electrodes. The electrodes are maintained at a temperature of 30� C. The power density at the electrodes is 0.1 watt/cm2. The pressure in the reactor in the glow discharge is 20 Pa. The substrate is exposed to the glow discharge in this reaction mixture for 100 minutes to form an 0.5 micrometer thick film.
Different ceramic plates were coated one after the other under the above operational conditions. Each time a plate was coated the ratio between the amount of propene and argon in the gas mixture was changed. The proportion of gaseous metal, palladium, is maintained constant, because it is provided by the vapor pressure, since the supply container for the palladium compound is not heated in this example.
Electrical resistance of the deposited polymeric palladium layer has been measured according to a four-point method in the apparatus of Kulicke and Soffa, Model 331. These resistances are shown in Table I.
TABLE I______________________________________Resistance of PolymericPalladium Layer vs % Propene in the Gas Phase% Propene in      Gas Flow Rate,                  Pd in the Film,                              Resistance,Reaction Mixture      sccm        % by weight μΩ cm______________________________________ 0         20          75          5.8.10433         20          71          1.6.10750         20          59          1.1.10867         20          43          1.0.108100        20           0          1.0.108______________________________________ where "sccm" means standard cm. min-1 As the table shows the resistance of the polymeric palladium films formed in this example is variable over a wide range of order of magnitudes.
Example II. Polymeric Palladium Layer on Inorganic Substrate Allylcyclopentadienyl palladium (II), the metallo-organic compound, and acrylonitrile, the metal-free gaseous organic compound, are admitted to a parallel plate reactor with an argon carrier gas. An aluminum oxide ceramic substrate is exposed to a glow discharge zone formed in this reaction mixture between the electrodes of the parallel plate reactor. A voltage of 400 D.C. volts is applied to the electrodes. The electrodes are maintained at a temperature of 120� C. The power density at the electrodes is 0.1 watt/cm2. The pressure in the reactor in the glow discharge is 20 Pa. The substrate is exposed to the glow discharge in this reaction mixture for 100 minutes to form an 0.5 micrometer thick film.
Different ceramic plates were coated one after the other under the above operational conditions. Each time a plate was coated the ratio between the amount of acrylonitrile and argon in the gas mixture was changed. The proportion of gaseous metal, palladium, is maintained constant, because it is provided by the vapor pressure, since the supply container for the palladium compound is not heated in this example.
Electrical resistance of the deposited polymeric palladium layer has been measured according to a four-point method in the apparatus of Kulicke and Soffa, Model 331. These resistances are shown in Table II and are generally several orders of magnitude less than those of Example I.
TABLE II______________________________________Resistance of Polymeric PalladiumLayer vs % Acrylonitrile in the Gas Phase% Acrylonitrilein Reaction      Gas Flow Rate,                  Pd in the Film,                              Resistance,Mixture    sccm        % by weight μΩ cm______________________________________ 0         100         94          4.3.10220         100         49          5.2.10725         100         47          9.1.10750         100         42          >1.0.108______________________________________ where "sccm" means standard cm. min-1.
Example III. Polymeric Gold Layer on Polyimide Dimethylgold(III)-acetylacetonate, the metallo-organic compound, and propene, the metal-free gaseous organic compound, are admitted to a parallel plate reactor with an argon carrier gas. A polyimide organic substrate is exposed to a glow discharge zone formed in this reaction mixture between the electrodes of the parallel plate reactor. A 13.56 Mhz alternating voltage is applied to the electrodes. The electrodes are maintained at a temperature of 25� C. The power density at the electrodes is 0.05 watt/cm2. The pressure in the reactor in the glow discharge is 20 Pa. The substrate is exposed to the glow discharge in this reaction mixture for 90 minutes to form an 0.5 micrometer thick film. The supply container for the organo-metallic was heated at 60� C.
Different ceramic plates were coated one after the other under the above operational conditions. Each time a plate was coated the ratio between the amount of propene and argon in the gas mixture was changed.
Electrical resistance of the deposited polymeric gold layer has been measured according to a four-point method in the apparatus of Kulicke and Soffa, Model 331. These resistances are shown in Table III.
TABLE III______________________________________Resistance of PolymericGold Layer vs % Propene in the Gas Phase% Propene in      Gas Flow Rate,                  Au in the Film,                              Resistance,Reaction Mixture      sccm        % by weight μΩ cm______________________________________0           0          73          2.0.1033           5          59          1.3.1077          10          50          2.5.10710         15          40          >1.0.108______________________________________ where "sccm" means standard cm. min-1.
Example IV. Polymeric Tin Layer on Silicate Glass Tin tetramethyl, the metallo-organic compound, and propene, the metal-free gaseous organic compound, are admitted to a parallel plate reactor with an argon carrier gas. A silicate glass substrate is exposed to a glow discharge zone formed in this reaction mixture between the electrodes of the parallel plate reactor. A 13.56 Mhz alternating voltage is applied to the electrodes. The power density at the electrodes is 0.4 watt/cm2. The pressure in the reactor in the glow discharge is 25 Pa. The inorganic substrate is exposed to the glow discharge in this reaction mixture for 60 minutes to form a 2 micrometer thick film. The electrodes were maintained at a temperature of 100� C. The supply container for the organo-metallic was not heated.
Electrical resistance of the deposited polymeric tin layer has been measured according to a four-point method in the apparatus of Kulicke and Soffa, Model 331. These resistances are shown in Table IV.
TABLE IV______________________________________Resistance of Polymeric TinLayer vs % Propene in the Gas Phase% Propene in      Gas Flow Rate,                  Sn in the Film,                              Resistance,Reaction Mixture      sccm        % by weight μΩ cm______________________________________0          0           95           903          1           94          5005          2           92          80010         4           78          >1.0.108______________________________________ where "sccm" means standard cm. min-1.
Example V. Polymeric Cobalt Layer on Silicon Oxide Ceramic Dicobaltoctacarbonyl, the metallo-organic compound, and propene, the metal-free gaseous organic compound, are admitted to a parallel plate reactor with an argon-hydrogen carrier gas. A silicon oxide ceramic substrate is exposed to a glow discharge zone formed in this reaction mixture between the electrodes of the parallel plate reactor. A 13.56 Mhz alternating voltage is applied to the electrodes. The power density at the electrodes is 0.6 watt/cm2. The pressure in the reactor in the glow discharge is 22.5 Pa. The inorganic substrate is exposed to the glow discharge in this reaction mixture for 90 minutes to form a 0.5 micrometer thick film. The electrode temperature was 80� C.
Electrical resistance of the deposited polymeric tin layer has been measured according to a four-point method in the apparatus of Kulicke and Soffa, Model 331. These resistances are shown in Table V.
TABLE V______________________________________Resistance of Polymeric CobaltLayer vs % Propene in the Gas Phase% Propene in      Gas Flow Rate,                  Co in the Film,                              Resistance,Reaction Mixture      sccm        % by weight μΩ cm______________________________________1.5        1           78          2.5.1033.         2           76          3.8.1034.4        3           72          5.2.1039.0        4           62          3.7.10313.        6           43          >1.0.108______________________________________ where "sccm" means standard cm. min-1 Example VI. Polymeric Tin Layer on Silicate Glass Tetramethyl tin, the metallo-organic compound, and butane, the metal-free gaseous organic compound, are admitted to a parallel plate reactor in an argon carrier gas. A silicate glass substrate is exposed to a glow discharge zone formed in this reaction mixture between the electrodes of the parallel plate reactor. An alternating voltage at 13.56 Mhz was applied to the electrodes. The electrodes are maintained at a temperature of 100� C. The power density at the electrodes is 0.4 watt/cm2. The pressure in the reactor in the glow discharge is 25 Pa. The substrate is exposed to the glow discharge in this reaction mixture for 60 minutes to form an 2 micrometer thick film.
Different ceramic plates were coated one after the other under the above operational conditions. Each time a plate was coated the ratio between the amount of butane and argon in the gas mixture was changed. The proportion of gaseous metal, tin, is maintained constant, because it is provided by the vapor pressure, since the supply container for the tin compound is not heated in this example.
Electrical resistance of the deposited polymeric tin layer has been measured according to a four-point method in the apparatus of Kulicke and Soffa, Model 331. These resistances are shown in Table VI.
TABLE VI______________________________________Resistance of Polymeric TinLayer vs % Butane in the Gas Phase% Butane in      Gas Flow Rate,                  Sn in the Film,                              Resistance,Reaction Mixture      sccm        % by weight μΩ cm______________________________________ 0         0           95          90 5         2           91          2000-500010         4           82          (19-22).10415         6           80          (65-97).10420         8           70          (4-5).106______________________________________ where "sccm" means standard cm. min-1 It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of constructions differing from the types described above.
While the invention has been illustrated and described as embodied in a method of making a polymer-metal compound having a predetermined electrical conductivity by depositing on a substrate from a glow discharge zone, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Referenced byCiting PatentFiling datePublication dateApplicantTitleUS5395642 *Dec 17, 1993Mar 7, 1995Solvay Deutschland GmbhProcess for depositing layers having high specific electrical conductivityUS5516458 *May 11, 1995May 14, 1996Eastman Kodak CompanyCoating composition used to prepare an electrically-conductive layer formed by a glow discharge process containing tin carboxylate, antimony alkoxide and film-forming binderUS5681687 *Feb 2, 1996Oct 28, 1997Eastman Kodak CompanyContaining organometallic compound and binderUS5853819 *Oct 24, 1996Dec 29, 1998Eastman Kodak CompanyImaging element comprising an electrically conductive layer formed by a glow discharge processUS6888465 *Oct 28, 2002May 3, 2005Preh-Werke Gmbh & Co. KgSensor unit for detecting the wetting of a window* Cited by examinerClassifications U.S. Classification427/569, 427/109, 427/125, 427/124, 427/253, 427/252International ClassificationC23C16/18, C04B41/49, C04B41/51, C03C17/34, C08G85/00, C08F2/52, H05K3/14Cooperative ClassificationC04B41/49, H05K3/146, C04B41/5188, C23C16/18, C03C17/3417European ClassificationC04B41/51V, H05K3/14C, C23C16/18, C04B41/49, C03C17/34D2Legal EventsDateCodeEventDescriptionJul 1, 2003FPExpired due to failure to pay maintenance feeEffective date: 20030507May 7, 2003LAPSLapse for failure to pay maintenance feesNov 20, 2002REMIMaintenance fee reminder mailedOct 8, 1998FPAYFee paymentYear of fee payment: 8Oct 13, 1994FPAYFee paymentYear of fee payment: 4Jan 26, 1994ASAssignmentOwner name: ATOTECH DEUTSCHLAND GMH, GERMANYFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SCHERING AG;REEL/FRAME:006839/0511Effective date: 19931210Aug 2, 1990ASAssignmentOwner name: SCHERING AG, GERMANYFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SUHR, HARALD;ETSPULER, ANGELIKA;FEURER, ERNST;AND OTHERS;REEL/FRAME:005406/0589Effective date: 19900723RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google


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