This invention relates generally to multi-layer surface coatings for use with articles of manufacture and products requiring low friction, low wear, and protective exterior surfaces. More particularly, the invention is related to articles having mutually sliding components, such as valve components for water mixing valves, having surface protective layers comprising a strengthening layer and an outer amorphous diamond coating.
In certain applications, such as for example, valve plates for fluid control valves, there is a need for mutually sliding surfaces to be wear resistant, abrasion resistant, scratch resistant, and to have a low coefficient of friction. The elements of one type of control valve for mixing of hot and cold water streams typically comprise a stationary disk and a moveable sliding disk, although the plate elements may be of any shape or geometry having a sealing surface, including e.g., flat, spherical, and cylindrical surfaces. The term “disk” herein therefore refers to valve plates of any shape and geometry having mating surfaces which engage and slide against each other to form a fluid-tight seal. The stationary disk typically has a hot water inlet, a cold water inlet, and a mixed water discharge outlet, while the moveable disk contains similar features and a mixing chamber. It is to be understood that the mixing chamber need not be in the disk but could part of an adjacent structure. The moveable disk overlaps the stationary disk and may be slid and/or rotated on the stationary disk so that mixed water at a desired temperature and flowrate is obtained in the mixing chamber by regulating the flowrate and proportions of hot water and cold water admitted from the hot water inlet and the cold water inlet and discharged through the mixed water discharge outlet. The disks mating sealing surfaces should be fabricated with sufficient precision to allow the two sealing surfaces to mate together and form a fluid tight seal (i.e. they must be co-conformal and smooth enough to prevent fluid from passing between the sealing surfaces). The degree of flatness (for a flat plate shape), or co-conformity (for non-flat surfaces) and smoothness required depend somewhat on the valve construction and fluids involved, and are generally well known in the industry. Other types of disk valves, while still using mating sealing surfaces in sliding contact with each other, may control only one fluid stream or may provide mixing by means of a different structure or port configuration. The stationary disk may for example be an integral part of the valve body.
Previous experience with this type of control valve has demonstrated there is a problem of wear of the mating surfaces of the disks due to the fact that the stationary and moveable disks are in contact and slide against each other (see for example U.S. Pat. Nos. 4,935,313 and 4,966,789). In order to minimize the wear problem, these valve disks are usually made of a sintered ceramic such as alumina (aluminum oxide). While alumina disks have good wear resistance, they have undesirable frictional characteristics in that operating force increases, and they tend to become “sticky” after the lubricant grease originally applied to the disks wears and washes away. The scratch and abrasion resistance of alumina plates to large and small particles (respectively) in the water stream is good; however, they are still susceptible to damage from contaminated water streams containing abrasive particles such as sand; and improvement in this regard would be beneficial. Additionally, the porous nature of the sintered ceramic disks makes them prone to “lockup” during long periods of non-use, due to minerals dissolved in the water supply that precipitate and crystallize between coincident pores in the mating surfaces. One objective of the present invention is to provide disks having reduced wear, improved scratch and abrasion resistance and reduced frictional characteristics. Another objective is to provide non-porous or reduced-porosity valve disks to reduce the number of locations where precipitated crystals may form between the mating surfaces.
Sintered ceramics in particular are relatively difficult and expensive (due to their hardness) to grind and polish to a degree of co-conformity and smoothness adequate for sealing. It would be advantageous to use a material for the disks, such as metal, which is less expensive, easier to grind and polish and which is not porous. However, the wear resistance and frictional behavior of bare metallic disks is generally not acceptable for sliding seal applications. A further objective of the present invention is to provide disks made of metal a base material and having improved wear, scratch, and abrasion resistance and improved frictional characteristics as compared to uncoated ceramic disks.
It is disclosed in the prior art (e.g., U.S. Pat. No. 4,707,384 and U.S. Pat. No. 4,734,339, which are incorporated herein by reference) that polycrystalline diamond coatings deposited by chemical vapor deposition (CVD) at substrate temperatures around 800-1000° C. can be used in combination with adhesion layers of various materials in order to provide scratch and wear resistant components. Polycrystalline diamond films, however, are known to have rough surfaces due to the crystal facets of the individual diamond grains, as is apparent in the photographs of FIGS. 2 and 3 in the '384 patent. It is known in the art to polish such surfaces in order to minimize the coefficient of friction in sliding applications, or even to deposit the polycrystalline diamond on a smooth substrate and then remove the film from the substrate and use the smooth side of the film (which was previously against the substrate) rather than the original surface as the bearing surface. The present invention overcomes prior art problems by providing a number of advantageous features, including without limitation providing a smooth and very hard surface for sliding applications, while avoiding difficult and expensive post-processing of a polycrystalline diamond surface layer. The methodology also advantageously employs substrate materials (such as, suitable metals, glasses, and composite and organic materials) that cannot be processed at the elevated temperatures necessary for CVD deposition of polycrystalline diamond.
It is also disclosed in the prior art (e.g., U.S. Pat. No. 6,165,616, which is incorporated herein by reference) that engineered interface layers may be employed to relieve thermally-induced stress in a polycrystalline diamond layer. These thermally induced stresses arise during cooling of the substrate after coating deposition at relatively high temperatures, and are due to the difference in thermal expansion coefficient between the substrate and the diamond coating. Rather complicated engineering calculations are specified in the '616 patent to predetermine the desired interface layer composition and thickness. The interface layer thickness' disclosed in the '616 patent to minimize the thermally-induced stress in the diamond layer are of the order 20 to 25 microns according to
It is further disclosed in the prior art (e.g., U.S. Pat. No. 4,935,313 and U.S. Pat. No. 4,966,789, which are incorporated herein by reference) that cubic crystallographic lattice carbon (polycrystalline diamond) and other hard materials may be used as surface coatings on valve disks, and that pairs of mutually sliding valves discs which differ from each other in either surface composition or surface finish are preferable to those which are the same in these characteristics, with respect to minimizing friction between the plates. The present invention provides mating valve disk surfaces having a lower friction coefficient than the disclosed materials in water-lubricated or fluid wetted surface applications such as water valves, and to allow identical processing of both mating surfaces in order to avoid the need to purchase and operate different types of processing equipment. The present invention further provides, without limitation, mating valve disk surfaces having a lower friction coefficient than the disclosed materials in water-lubricated or fluid wetted surface applications such as water valves. Furthermore, both mated sliding surfaces of the disks can be hard and have an abrasion resistance to contaminated water streams and to allow identical processing of both mating surfaces in order to avoid the need to purchase and operate different types of processing equipment.
An exemplary embodiment relates to a component for a faucet that includes a substrate comprising alumina. A first material is provided over at least a portion of the substrate, the first material comprising titanium and carbon. A second material is provided over the first material, the second material comprising carbon and having carbon sp3 bonding of at least 40 percent.
Another exemplary embodiment relates to a component for a faucet that includes a ceramic substrate and a first material on a surface of the substrate where the first material includes titanium. A second material is on the first layer of material and includes at least 40 percent tetrahedrally-bonded carbon.
Another exemplary embodiment relates to a component for a faucet that includes an alumina substrate. A material comprising carbon is provided over at least a portion of the substrate, the material comprising carbon having at least 40 percent tetrahedrally-bonded carbon. A material comprising titanium is provided between the material comprising carbon and the substrate.
Another exemplary embodiment relates to a component for a fluid control valve that includes a valve disk comprising a substrate comprising alumina, a titanium carbide material provided on a surface of the substrate, and a carbon layer on the titanium carbide material, the carbon layer comprising at least 40 percent tetrahedrally-bonded carbon.
Another exemplary embodiment relates to a fluid control valve that includes a first disk in contact with a second disk where a surface of the first disk is configured to slide against a surface of the second disk. A coating is provided on the surface of the first disk, the coating comprising a first layer of material comprising titanium and a second layer of material provided over the first layer of material, the second layer of material being amorphous and comprising at least 40 percent tetrahedrally-bonded carbon.
According to an exemplary embodiment, a component includes a wear resistant, scratch resistant, abrasion resistant, and low-friction surface. More particularly, it the component includes a multi-layer structure comprising a thin strengthening layer having higher hardness than the substrate material, and a thin amorphous diamond wear-resistant and friction-reducing layer deposited on the strengthening layer. The amorphous diamond layer provides a low-friction, wear and abrasion resistant sealing surface with particular advantages in water-lubricated or fluid wetted applications. The incorporation of a strengthening layer to support the top amorphous diamond layer, provides better scratch and abrasion resistance than an amorphous diamond layer alone, and allows a thinner amorphous diamond layer to be used. The strengthening layer is particularly useful to avoid problems with large particles caught between the mating surfaces, which can break through a thin diamond coating because of plastic deformation of the softer substrate beneath.
Embodiments of the invention are illustrated generally in the figures, where
As shown in
Another material suitable for the strengthening layer 23 is conventional DLC (Diamond-Like Carbon), which is a form of non-crystalline carbon well known in the art and distinct from amorphous diamond. DLC coatings are described for example in U.S. Pat. No. 6,165,616 (in which they are called (a-C) coatings). DLC can be deposited by sputtering or by conventional CVD. DLC is an amorphous material with mostly sp2 carbon bonding and little of the tetrahedral sp3 bonding that characterizes amorphous diamond. The hardness of DLC is substantially lower than that of amorphous diamond and is more similar to the hardness of conventional hard coating materials such as titanium nitride and chromium nitride. The internal stresses in DLC coatings are also lower than those in amorphous diamond coatings, allowing DLC to be deposited in thicker layers than amorphous diamond without loss of adhesion. The term DLC as used herein includes hydrogenated forms of the material.
The strengthening layer 23 functions primarily to improve scratch and abrasion resistance of the multilayer coating. The hardness of the strengthening layer 23 should be at least greater than that of the substrate 18 in order to perform its intended function of improving the scratch resistance of the coated disk. The thickness of the strengthening layer 23 is at least a thickness sufficient to improve the scratch resistance of the substrate 18. For materials typically used as hard coatings, such as those disclosed above, this thickness is generally from around 500 nm to around 10 microns, and preferably from about 2000 nm to around 5000 nm. In testing of faucet water valves it has been found that a chromium nitride strengthening layer having a thickness of about 5 microns provides adequate scratch and abrasion resistance (in conjunction with a thin amorphous diamond top layer) for types and sizes of contaminants considered to be typical in municipal and well water sources.
In some embodiments of the present invention as shown in
PVD processes are well known and conventional and include cathodic arc evaporation (CAE), sputtering, and other conventional deposition processes. CVD processes can include low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), and thermal decomposition methods. PVD and CVD techniques and equipment are disclosed, inter alia, in J. Vossen and W. Kern “Thin Film Processes II”, Academic Press, 1991; R. Boxman et al, “Handbook of Vacuum Arc Science and Technology”, Noyes, 1995; and U.S. Pat. Nos. 4,162,954 and 4,591,418, with the patents incorporated herein by reference.
In the case of sintered ceramic materials, although the individual granules forming the sintered material may have high hardness, the scratch resistance of the overall sintered structure as measured by scratch testing is much lower than that of the material forming the granules (e.g., alumina). This is due to the fact that the materials typically used to sinter or bond the alumina granules together, typically silicates, are not as hard as the granules themselves. The hardness of the strengthening layer 23 can be similar to or even less than the hardness of the individual granules comprising the ceramic disk, and still being harder than the overall sintered ceramic structure. It has been found by experiment, for example, that the depth of the scratch caused by a stylus (radius=100 microns) sliding under a load of 30 Newtons is approximately 4-6 microns on an uncoated sintered alumina substrate, while the scratch depth on an identical substrate coated with a 3 micron thick chromium nitride strengthening layer is only 2-3 microns.
The strengthening layer 23 can be formed by conventional vapor deposition techniques including, but not limited to sputtering, cathodic arc evaporation (CAE), and CVD. The most preferred methods are sputtering, CAE, or other means which may be carried out at a relatively low temperature, thereby minimizing thermally-induced stresses in the coating stack upon cooling. If the strengthening layer 23 is deposited by CAE, it is also desirable to use macroparticle filtering in order to control and to preserve the smoothness of the surface of the substrate 18. The strengthening layer 23 can also be formed by other well-known methods for forming hard coatings such as spray pyrolysis, sol-gel techniques, liquid-dipping with subsequent thermal treatment, nano-fabrication methods, atomic-layer deposition methods, and molecular-layer deposition methods.
The strengthening layer 23 can alternatively be formed by a process that produces a hardened surface layer on the substrate base material. Such processes include, for example, thermal oxidation, plasma nitriding, ion implantation, chemical and electrochemical surface treatments such as chemical conversion coatings, anodizing including hard anodizing and conventional post-treatments, micro-arc oxidation and case hardening. The strengthening layer 23 can also include multiple layers 24 and 25 as shown in
In the multi-layer structure of
The thickness of the amorphous diamond layer 30 is at least a value effective to provide improved wear and abrasion resistance of the sliding component. This thickness is generally at least about 100 nm, preferably at least about 200 nm and more preferably at least about 300 nm. The upper thickness range of the layer 30 is determined by material characteristics, economic considerations and the need to minimize thickness-dependent intrinsic stresses in the layer 30 as discussed below. Also amorphous diamond layer 30 advantageously exhibits an extremely smooth surface topology as can be seen by reference to the photo of
One characteristic of amorphous diamond is that it develops high intrinsic (non-thermally-induced) internal stresses, which increase as the coating thickness increases and which are predominately related to atomic bonding distortions and not to thermal expansion/contraction. While this intrinsic stress is believed to contribute to the high hardness of the material, it also limits the coating thickness since stress-induced forces tend to cause delamination of the coating from the substrate 18 (or the strengthening layer 23) above a certain thickness. Although amorphous diamond can be deposited directly on a metal, glass or iron aluminide disk (optionally with an adhesion layer), it is difficult to deposit a thick enough layer to provide adequate scratch resistance for water valve applications. Scratch resistance is important because water supplies sometimes contain abrasive contaminants due to pipeline breaks, construction, etc. The additional strengthening layer 23 of the present invention provides better support of the amorphous diamond layer 30 than does the softer substrate material, advantageously allowing a thinner layer of amorphous diamond to be used, while still obtaining improved scratch and abrasion resistance. The strengthening layer 23 can also be chosen to be a material that has a greater deposition rate and/or is less expensive to deposit than the amorphous diamond layer 30, in order to minimize overall coating cost while maintaining performance. In the most preferred embodiment, an upper thickness limit for the amorphous diamond layer 30 of around 1-2 microns can be used to avoid stress-induced delamination, while an upper thickness of around 800 nm, and more preferably around 300-500 nm, can be desirable for economic reasons while still achieving the desired performances characteristics.
Amorphous diamond is well suited to wet sliding applications in water valve applications. In particular it has been shown to have a very low coefficient of friction and also extremely low abrasion wear in water-lubricated sliding tests in which both sliding surfaces are coated with amorphous diamond. In contrast, DLC coatings are known to have higher friction coefficients higher wear rates, and to deteriorate in frictional performance with increasing humidity. A further advantage of amorphous diamond is that the relatively low deposition temperature allows a wider choice of substrate materials and minimizes or eliminates permanent thermally induced distortion of the substrate.
Regarding the low coefficient of friction reported for amorphous diamond coatings in water-lubricated sliding tests, it is thought that this may be due at least in part to graphitic inclusions (commonly called macroparticles) that are incorporated in amorphous diamond coatings made by some methods. Such graphitic inclusions can be numerous in carbon coatings deposited by cathodic arc evaporation, depending on the choice target materials and use of macroparticle filtering means as discussed below. These graphitic inclusions do not degrade the performance of the amorphous diamond coating due their softness and the small fraction of the total surface area they occupy. Rather, it is thought that they may improve performance by increasing lubricant retention between the sliding plates.
It is disclosed in U.S. Pat. No. 5,401,543 (incorporated herein by reference) that amorphous diamond coatings which are essentially free of macroparticles can be deposited by cathodic arc evaporation from a vitreous carbon or pyrolytic graphite cathode. The maximum density of macroparticles (graphitic inclusions) in such coatings, as calculated from the areal dimensions of the photographic figures and the macroparticle counts disclosed, is around 200 macroparticles per square millimeter. Such macroparticle-free amorphous diamond coatings can be used as layer 30 in the present invention, but are less-preferred than those deposited from an ordinary graphite cathode and containing substantial numbers of graphitic inclusions, such as, for example, at least about 500 per square millimeter. They are also less preferred because the required vitreous carbon or pyrolytic graphite cathodes are quite expensive compared to ordinary graphite.
The number of graphitic inclusions 40 incorporated into coatings (see
The adhesion of the amorphous diamond layer 30 to a nitride form of the strengthening layer 23 can in some cases be improved by the introduction of a carbon-containing gas, such as methane, during a short period at the end of the deposition of the strengthening layer 23. This results in a thin transition zone of carbo-nitride and/or carbide material between the strengthening layer 23 and the amorphous diamond layer 30. In other cases the adhesion can be improved by turning off all reactive gasses during a short period at the end of the deposition of the strengthening layer 23. This results in a thin metal layer between the strengthening layer 23 and the amorphous diamond layer 30. It has also been noted that the introduction of methane during the filtered-arc deposition of the amorphous diamond layer 30 increases the coating deposition rate, and can also improve the coating hardness and scratch resistance. In still other cases, for example the case in which the amorphous diamond layer 30 is to be deposited on a thermally oxidized metal surface, it can be desirable to deposit the separate adhesion-promoting layer 21 between the strengthening layer 23 and the amorphous diamond layer 30. Suitable materials for the adhesion layer 21 can include for example refractory carbide-forming metals, such as, Ti and W, and various transition metals such as Cr, and can also include carbides of those metals.
In order that the invention may be more readily understood the following examples are provided. The examples are illustrative and do not limit the invention to the particular features described.
Clean stainless steel valve disks are placed in a vacuum deposition chamber incorporating an arc evaporation cathode and a sputtering cathode. The arc source is fitted with filtering means to reduce macroparticle incorporation in the coating, as described for example in U.S. Pat. Nos. 5,480,527 and 5,840,163, incorporated herein by reference. Sources of argon and nitrogen are connected to the chamber through a manifold with adjustable valves for controlling the flowrate of each gas into the chamber. The sputtering cathode is connected to the negative output of a DC power supply. The positive side of the power supply is connected to the chamber wall. The cathode material is chromium. The valve disks are disposed in front of the cathode, and may be rotated or otherwise moved during deposition to ensure uniform coating thickness. The disks are electrically isolated from the chamber and are connected through their mounting rack to the negative output of a power supply so that a bias voltage may be applied to the substrates during coating.
Prior to deposition the vacuum chamber is evacuated to a pressure of 2×10e−5 Torr or less. Argon gas is then introduced at a rate sufficient to maintain a pressure of about 25 milliTorr. The valve disks are then subjected to a glow discharge plasma cleaning in which a negative bias voltage of about 500 volts is applied to the rack and valve disks. The duration of the cleaning is approximately 5 minutes.
A layer of chromium having a thickness of about 20 nm is then deposited on the valve disks by sputtering. After the chromium adhesion layer is deposited, a strengthening layer of chromium nitride having a thickness of about 3 microns is deposited by reactive sputtering.
After the chromium nitride layer is deposited, the valve disks are disposed facing the arc source, and a top amorphous diamond layer having a thickness of about 300 nm is deposited by striking an arc on the carbon electrode and exposing the substrates to the carbon plasma exiting the source outlet. A negative DC bias of about 500 volts is initially applied to the substrates to provide high-energy ion bombardment for surface cleaning and bonding improvement. After about 5 minutes at high bias voltage, the bias voltage is reduced to about 50 volts for the remainder of the deposition process. An argon pressure of about 0.5 milliTorr is maintained in the chamber during deposition. Pulsed or AC bias voltages may alternatively be employed, and a higher or lower argon may also be maintained in order to stabilize the arc source operation and optimize coating properties.
It has been found by experiment that valve disks made of stainless steel and coated according to the above example were able to withstand more than 15,000 test cycles in circulating water carrying 20 micron silica sand, while standard uncoated alumina valve disks failed under the same conditions in less than 2500 cycles.
Clean zirconium valve disks are placed into an air oven, heated to a temperature of 560 C, held at this temperature for about 6 hours, and cooled. A strengthening layer of zirconium oxide is thereby formed on the substrate surface, having a thickness of 5-10 microns. The disks are then placed in a vacuum deposition chamber incorporating a filtered arc evaporation cathode and a sputtering cathode. An adhesion layer of chromium having a thickness of about 20 nm is deposited on the valve disks by sputtering as described in example 1. After the chromium adhesion layer is deposited, an amorphous diamond layer is deposited as described in Example 1.
Valve disks made of zirconium and treated as described to form a multilayer structure on their surfaces were tested for scratch resistance, using a scratch tester with variable loading. The scratch depths generated on the treated Zr disks by a stylus tip having 100 micron radius under a load of 3 Newtons were around 4.7 microns deep, while those on untreated Zr disks were about 9.5 microns or more than twice as deep. Scratch test performance is believed to be a relevant predictor of scratch and abrasion resistance in field applications.
Clean molded-glass valve disks are placed in a vacuum deposition chamber incorporating a laser ablation source, a PECVD source, and a sputtering cathode. The valve disks are subjected to a RF (radio-frequency) discharge plasma cleaning by known means. An adhesion layer of titanium having a thickness of about 20 nm is then deposited on the valve disks by sputtering. A strengthening layer of DLC having thickness of about 3 microns is then deposited on top of the adhesion layer by PECVD using known deposition parameters. An amorphous diamond layer having thickness of about 300 nm is then deposited on top of the DLC layer by laser ablation using typical deposition parameters.
Clean stainless steel valve disks are placed in a vacuum chamber containing a filtered arc evaporation source and a sputtering cathode. The chamber is evacuated, nitrogen gas is introduced, a plasma discharge is established between the disks and the chamber walls, and the disk surface is plasma-nitrided according to known parameters. Nitrogen diffuses into the stainless substrates to form a surface layer harder than the bulk substrate, and the process is continued for a period of time sufficient for the layer depth to reach about 2 microns. A superlattice consisting of multiple alternating layers of carbon nitride and zirconium nitride is then deposited on the nitrided stainless steel surface by filtered arc evaporation and sputtering respectively. The alternating individual layers are about 10 nm thick, and about 100 layers of each material is deposited for a total superlattice thickness of about 2 microns. The ratio of nitrogen to carbon in the carbon nitride layers is preferably around 1.3, since carbon nitride+zirconium nitride superlattices having this N:C ratio have been shown to have primarily sp3-bonded carbon and hardness in the range of 50 gigaPascals. Carbon nitride as used herein refers to a material having a N:C ratio between about 0.1 and 1.5.
The large number of thin layers may conveniently be deposited by mounting the substrate on a rotating cylinder such that the substrates pass first in front of one deposition source and then the other, such that one pair of layers is deposited during each revolution of the cylinder. The total strengthening layer thickness is about 4 microns including the plasma-nitrided stainless steel layer. An amorphous diamond layer having thickness of about 200 nm is then deposited on top of the superlattice layer by filtered arc evaporation as described in Example 1.
The construction and arrangement of the elements shown in the preferred and other exemplary embodiments is illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, use of materials, etc.) without materially departing from the novel teachings and advantages of the subject matter recited herein. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the preferred and other exemplary embodiments without departing from the scope of the present invention.
The present application is a Continuation of U.S. patent application Ser. No. 12/641,008, filed Dec. 17, 2009 which is a Continuation-In-Part of U.S. patent application Ser. No. 12/141,848, filed Jun. 18, 2008, which is a Continuation-in-Part of U.S. patent application Ser. No. 11/732,948 filed Apr. 5, 2007 (now U.S. Pat. No. 7,445,026), which is a Continuation of U.S. patent application Ser. No. 11/201,395 filed Aug. 10, 2005 (now U.S. Pat. No. 7,216,661), which is a Continuation of U.S. patent application Ser. No. 10/741,848 filed Dec. 18, 2003 (now U.S. Pat. No. 6,935,618), which is a Continuation of U.S. patent application Ser. No. 10/322,871 filed Dec. 18, 2002 (now U.S. Pat. No. 6,904,935). This application (as well as U.S. patent application Ser. No. 12/641,008 and U.S. patent application Ser. No. 12/141,848) is also a Continuation-in-Part of U.S. patent application Ser. No. 11/784,765 filed Apr. 9, 2007, which is a Continuation-In-Part of U.S. patent application Ser. No. 11/201,395 filed Aug. 10, 2005 (now U.S. Pat. No. 7,216,661), which is a Continuation of U.S. patent application Ser. No. 10/741,848 filed Dec. 18, 2003 (now U.S. Pat. No. 6,935,618), which is a Continuation of U.S. patent application Ser. No. 10/322,871, filed Dec. 18, 2002 (now U.S. Pat. No. 6,904,935). The entire disclosures for each of the following U.S. patent applications (and any patents granted thereon) are incorporated herein by reference in their entirety: U.S. patent application Ser. No. 10/322,871; U.S. patent application Ser. No. 10/741,848; U.S. patent application Ser. No. 11/201,395; U.S. patent application Ser. No. 11/732,948; U.S. patent application Ser. No. 11/784,765; and U.S. patent application Ser. No. 12/141,848.
Number | Name | Date | Kind |
---|---|---|---|
2020286 | Bittle | Nov 1935 | A |
2411867 | Brenner | Dec 1946 | A |
2639116 | Green | May 1953 | A |
2793282 | Steigerwald | May 1957 | A |
2861166 | Cargill | Nov 1958 | A |
2947610 | Hall et al. | Aug 1960 | A |
2968723 | Steigerwald | Jan 1961 | A |
RE25105 | Cargill, Jr. | Dec 1961 | E |
3141746 | De Lai | Jul 1964 | A |
3173175 | Lemelson | Mar 1965 | A |
3207582 | Inoue | Sep 1965 | A |
3346458 | Schmidt | Oct 1967 | A |
3371404 | Lemelson | Mar 1968 | A |
3384119 | Manoogian | May 1968 | A |
3504063 | Lemelson | Mar 1970 | A |
3607061 | Angus | Sep 1971 | A |
3615208 | Byron | Oct 1971 | A |
3630677 | Angus | Dec 1971 | A |
3630678 | Gardner | Dec 1971 | A |
3630679 | Angus | Dec 1971 | A |
3635811 | Lane | Jan 1972 | A |
3667503 | Farrell et al. | Jun 1972 | A |
3702573 | Nemeth | Nov 1972 | A |
3714332 | Estes et al. | Jan 1973 | A |
3747638 | Manoogian et al. | Jul 1973 | A |
3766914 | Jacobs | Oct 1973 | A |
3794026 | Jacobs | Feb 1974 | A |
3813296 | Mcstrack et al. | May 1974 | A |
3829969 | Fischbein et al. | Aug 1974 | A |
3840451 | Golyanov et al. | Oct 1974 | A |
3854493 | Farrell | Dec 1974 | A |
3879175 | Levitt | Apr 1975 | A |
3912500 | Vereschagin et al. | Oct 1975 | A |
3913280 | Hall | Oct 1975 | A |
3916506 | Wolf | Nov 1975 | A |
3929432 | Caveney | Dec 1975 | A |
3934612 | Kast | Jan 1976 | A |
3941903 | Tucker | Mar 1976 | A |
3953178 | Engel | Apr 1976 | A |
3959557 | Berry | May 1976 | A |
3965935 | Morisseau | Jun 1976 | A |
4006540 | Lemelson | Feb 1977 | A |
4018241 | Sodal et al. | Apr 1977 | A |
4029368 | Tschirky et al. | Jun 1977 | A |
4054426 | White | Oct 1977 | A |
4084942 | Villalobos | Apr 1978 | A |
4104441 | Fedoseev et al. | Aug 1978 | A |
4115156 | Straumann | Sep 1978 | A |
4162954 | Morrison | Jul 1979 | A |
4173522 | Pulker et al. | Nov 1979 | A |
4183377 | Bernat | Jan 1980 | A |
4190301 | Lachonius et al. | Feb 1980 | A |
4228142 | Holcombe et al. | Oct 1980 | A |
4241135 | Lee et al. | Dec 1980 | A |
4260203 | Garner | Apr 1981 | A |
4325403 | Uhlmann | Apr 1982 | A |
4327758 | Uhlmann | May 1982 | A |
4345798 | Cortes | Aug 1982 | A |
4367130 | Lemelson | Jan 1983 | A |
4378029 | Parkison | Mar 1983 | A |
4385880 | Lemelson | May 1983 | A |
4387287 | Marazzi | Jun 1983 | A |
4394400 | Green et al. | Jul 1983 | A |
4410054 | Nagel et al. | Oct 1983 | A |
4434188 | Kamo et al. | Feb 1984 | A |
4457491 | Dudman | Jul 1984 | A |
4468138 | Nagel | Aug 1984 | A |
4490229 | Mirtich et al. | Dec 1984 | A |
4492845 | Kljuchko et al. | Jan 1985 | A |
4504519 | Zelez | Mar 1985 | A |
4509519 | Detsch | Apr 1985 | A |
4524106 | Flasck | Jun 1985 | A |
4531273 | Smith et al. | Jul 1985 | A |
4532149 | McHargue | Jul 1985 | A |
4540636 | Iver et al. | Sep 1985 | A |
4554208 | MacIver et al. | Nov 1985 | A |
RE32106 | Lemelson | Apr 1986 | E |
4591418 | Snyder | May 1986 | A |
4594294 | Eichen et al. | Jun 1986 | A |
4597844 | Hiraki et al. | Jul 1986 | A |
4610577 | Spensberger | Sep 1986 | A |
4618505 | MacIver et al. | Oct 1986 | A |
4620601 | Nagel | Nov 1986 | A |
4621031 | Scruggs | Nov 1986 | A |
4661213 | Dorsett et al. | Apr 1987 | A |
4663183 | Ovshinsky et al. | May 1987 | A |
4666318 | Harrison | May 1987 | A |
4696829 | Legg | Sep 1987 | A |
4698256 | Giglia et al. | Oct 1987 | A |
4702808 | Lemelson | Oct 1987 | A |
4707384 | Schachner et al. | Nov 1987 | A |
4708496 | McPherson | Nov 1987 | A |
4708888 | Mitchell et al. | Nov 1987 | A |
4714660 | Gates | Dec 1987 | A |
4720199 | Geczy et al. | Jan 1988 | A |
4720349 | Kobayashi et al. | Jan 1988 | A |
4720918 | Curry et al. | Jan 1988 | A |
4724058 | Morrison | Feb 1988 | A |
4725345 | Sakamoto et al. | Feb 1988 | A |
4729440 | Hall | Mar 1988 | A |
4732364 | Seger et al. | Mar 1988 | A |
4732491 | Geczy | Mar 1988 | A |
4734339 | Schachner et al. | Mar 1988 | A |
4755237 | Lemelson | Jul 1988 | A |
4756631 | Jones | Jul 1988 | A |
4761217 | Dorsett et al. | Aug 1988 | A |
4764036 | McPherson | Aug 1988 | A |
4764434 | Aronsson et al. | Aug 1988 | A |
4767608 | Matsumoto et al. | Aug 1988 | A |
4776862 | Wiand | Oct 1988 | A |
4778730 | Zucker | Oct 1988 | A |
4783368 | Yamamoto et al. | Nov 1988 | A |
4797009 | Yamazaki | Jan 1989 | A |
4810584 | Yu-Zhong | Mar 1989 | A |
4816286 | Hirose | Mar 1989 | A |
4816291 | Desphandey et al. | Mar 1989 | A |
4816682 | Levitt et al. | Mar 1989 | A |
4822355 | Bhuvaneshwar | Apr 1989 | A |
4822466 | Rabalais et al. | Apr 1989 | A |
4824262 | Kamigaito et al. | Apr 1989 | A |
4832075 | Dubach | May 1989 | A |
4832993 | Coulon | May 1989 | A |
4837089 | Araki et al. | Jun 1989 | A |
4842937 | Meyer et al. | Jun 1989 | A |
4842945 | Ito et al. | Jun 1989 | A |
4848199 | Kelm | Jul 1989 | A |
4849199 | Pinneo | Jul 1989 | A |
4849290 | Fujimori et al. | Jul 1989 | A |
4858556 | Siebert | Aug 1989 | A |
4859493 | Lemelson | Aug 1989 | A |
4871581 | Yamazaki | Oct 1989 | A |
4874596 | Lemelson | Oct 1989 | A |
4882138 | Pinneo | Nov 1989 | A |
4889195 | Kruger et al. | Dec 1989 | A |
4892420 | Kruger | Jan 1990 | A |
4900628 | Ikegaya et al. | Feb 1990 | A |
4902535 | Garg et al. | Feb 1990 | A |
4904542 | Mroczkowski | Feb 1990 | A |
4919974 | McCune et al. | Apr 1990 | A |
4933058 | Bache et al. | Jun 1990 | A |
4935303 | Ikoma et al. | Jun 1990 | A |
4935313 | Knapp et al. | Jun 1990 | A |
4938940 | Hirose et al. | Jul 1990 | A |
4940015 | Kobashi et al. | Jul 1990 | A |
4948629 | Hacker et al. | Aug 1990 | A |
4950543 | Winter et al. | Aug 1990 | A |
4960643 | Lemelson | Oct 1990 | A |
4961958 | Desphandey et al. | Oct 1990 | A |
4966789 | Knapp et al. | Oct 1990 | A |
4968326 | Wiand | Nov 1990 | A |
4973494 | Yamazaki | Nov 1990 | A |
4974498 | Lemelson | Dec 1990 | A |
4985229 | Obitsu et al. | Jan 1991 | A |
4987007 | Wagal et al. | Jan 1991 | A |
4991822 | Enke | Feb 1991 | A |
4992298 | Deutchman et al. | Feb 1991 | A |
4997636 | Prins | Mar 1991 | A |
5006203 | Purdes | Apr 1991 | A |
5009923 | Ogata et al. | Apr 1991 | A |
5021628 | Lemelson | Jun 1991 | A |
5024977 | Friederich et al. | Jun 1991 | A |
5032243 | Bache et al. | Jul 1991 | A |
5036733 | Tiholiz et al. | Aug 1991 | A |
5037212 | Justman et al. | Aug 1991 | A |
5037522 | Vergason | Aug 1991 | A |
5040501 | Lemelson | Aug 1991 | A |
5046703 | Kamiyama et al. | Sep 1991 | A |
5055318 | Deutchman et al. | Oct 1991 | A |
5064682 | Kiyama et al. | Nov 1991 | A |
5067826 | Lemelson | Nov 1991 | A |
5068148 | Nakahara et al. | Nov 1991 | A |
5070274 | Yoshikawa et al. | Dec 1991 | A |
5075094 | Morrish et al. | Dec 1991 | A |
5082359 | Kirkpatrick | Jan 1992 | A |
5088202 | Boland et al. | Feb 1992 | A |
5094915 | Subramaniam | Mar 1992 | A |
5096352 | Lemelson | Mar 1992 | A |
5098737 | Collins et al. | Mar 1992 | A |
5100565 | Fujiwara et al. | Mar 1992 | A |
5104634 | Calcote | Apr 1992 | A |
5114696 | Purdes | May 1992 | A |
5114745 | Jones | May 1992 | A |
5124179 | Garg et al. | Jun 1992 | A |
5126274 | McIver et al. | Jun 1992 | A |
5127983 | Imai et al. | Jul 1992 | A |
5129289 | Boland et al. | Jul 1992 | A |
5131941 | Lemelson | Jul 1992 | A |
5132105 | Remo | Jul 1992 | A |
5132587 | Lemelson | Jul 1992 | A |
5135808 | Kimock et al. | Aug 1992 | A |
5135941 | Djuric et al. | Aug 1992 | A |
5137398 | Omori et al. | Aug 1992 | A |
5139621 | Alexander et al. | Aug 1992 | A |
5142785 | Grewal et al. | Sep 1992 | A |
5158695 | Yashchenko et al. | Oct 1992 | A |
5161728 | Li | Nov 1992 | A |
5164051 | Komaki et al. | Nov 1992 | A |
5165955 | Gentle | Nov 1992 | A |
5170993 | Bonetti | Dec 1992 | A |
5171607 | Cumbo | Dec 1992 | A |
5185179 | Yamazaki et al. | Feb 1993 | A |
5190823 | Anthony et al. | Mar 1993 | A |
5205188 | Repenning et al. | Apr 1993 | A |
5224969 | Chen et al. | Jul 1993 | A |
5225366 | Yoder | Jul 1993 | A |
5227196 | Itoh | Jul 1993 | A |
5232568 | Parent et al. | Aug 1993 | A |
5237967 | Willermet et al. | Aug 1993 | A |
5239746 | Goldman | Aug 1993 | A |
5242741 | Sugiyama et al. | Sep 1993 | A |
5245104 | Cullick | Sep 1993 | A |
5246035 | Skyllingstad et al. | Sep 1993 | A |
5249554 | Tamor et al. | Oct 1993 | A |
5255929 | Lemelson | Oct 1993 | A |
5257558 | Farzin-Nia et al. | Nov 1993 | A |
5260141 | Tsai et al. | Nov 1993 | A |
5279723 | Falabella et al. | Jan 1994 | A |
5281274 | Yoder | Jan 1994 | A |
5284394 | Lemelson | Feb 1994 | A |
5288556 | Lemelson | Feb 1994 | A |
5295305 | Hahn et al. | Mar 1994 | A |
5296274 | Movchan et al. | Mar 1994 | A |
5300942 | Dolgoff | Apr 1994 | A |
5314652 | Simpson et al. | May 1994 | A |
5322735 | Fridez et al. | Jun 1994 | A |
5332348 | Lemelson | Jul 1994 | A |
5338027 | Rehkemper et al. | Aug 1994 | A |
5349265 | Lemelson | Sep 1994 | A |
5352493 | Dorfman et al. | Oct 1994 | A |
5360227 | Lemelson | Nov 1994 | A |
5364192 | Damm et al. | Nov 1994 | A |
5366556 | Prince et al. | Nov 1994 | A |
5370195 | Keshavan et al. | Dec 1994 | A |
5382293 | Kawarada et al. | Jan 1995 | A |
5388027 | Pollock et al. | Feb 1995 | A |
5391407 | Dearnaley | Feb 1995 | A |
5391409 | Shibata et al. | Feb 1995 | A |
5392982 | Li | Feb 1995 | A |
5393572 | Dearnaley | Feb 1995 | A |
5395221 | Tucker et al. | Mar 1995 | A |
5397347 | Cuilleron et al. | Mar 1995 | A |
5401543 | Storer | Mar 1995 | A |
5403399 | Kurihara et al. | Apr 1995 | A |
5405645 | Sevillano et al. | Apr 1995 | A |
5411797 | Davanloo et al. | May 1995 | A |
5415704 | Davidson | May 1995 | A |
5437243 | Pike-Biegunski | Aug 1995 | A |
5441013 | Jeng et al. | Aug 1995 | A |
5449569 | Schumm | Sep 1995 | A |
5451307 | Bennett et al. | Sep 1995 | A |
5456406 | Lemelson | Oct 1995 | A |
5462722 | Liu et al. | Oct 1995 | A |
5462772 | Lemelson | Oct 1995 | A |
5462776 | Gruen | Oct 1995 | A |
5474816 | Falabella | Dec 1995 | A |
5476693 | Lee et al. | Dec 1995 | A |
5478650 | Davanloo et al. | Dec 1995 | A |
5480527 | Welty | Jan 1996 | A |
5529805 | Iacovangelo et al. | Jun 1996 | A |
5529815 | Lemelson | Jun 1996 | A |
5533347 | Ott et al. | Jul 1996 | A |
5541003 | Nakayama et al. | Jul 1996 | A |
5541016 | Schumm | Jul 1996 | A |
5543684 | Kumar et al. | Aug 1996 | A |
5549764 | Biltgen et al. | Aug 1996 | A |
5551903 | Kumar et al. | Sep 1996 | A |
5552675 | Lemelson | Sep 1996 | A |
5554415 | Turchan et al. | Sep 1996 | A |
5571616 | Phillips et al. | Nov 1996 | A |
5589232 | Simpson | Dec 1996 | A |
5593234 | Liston | Jan 1997 | A |
5601966 | Kumar et al. | Feb 1997 | A |
5602679 | Dolgoff et al. | Feb 1997 | A |
5605759 | Prince et al. | Feb 1997 | A |
5609683 | Pike-Biegunski | Mar 1997 | A |
5616372 | Conley et al. | Apr 1997 | A |
5616373 | Karner et al. | Apr 1997 | A |
5620745 | Simpson | Apr 1997 | A |
5626908 | Iio et al. | May 1997 | A |
5626963 | Hirano et al. | May 1997 | A |
5628881 | Lemelson | May 1997 | A |
5629086 | Hirano et al. | May 1997 | A |
5633087 | Simpson | May 1997 | A |
5643423 | Kimock et al. | Jul 1997 | A |
5644130 | Raatz | Jul 1997 | A |
5645601 | Pope et al. | Jul 1997 | A |
5645900 | Ong et al. | Jul 1997 | A |
5648620 | Stenzel et al. | Jul 1997 | A |
5662965 | Deguchi et al. | Sep 1997 | A |
5669144 | Hahn et al. | Sep 1997 | A |
5677051 | Ueda et al. | Oct 1997 | A |
5679404 | Patten et al. | Oct 1997 | A |
5688557 | Lemelson et al. | Nov 1997 | A |
5688677 | Ebert et al. | Nov 1997 | A |
5705271 | Okamura et al. | Jan 1998 | A |
5707409 | Martin et al. | Jan 1998 | A |
5713333 | Cooper et al. | Feb 1998 | A |
5714202 | Lemelson et al. | Feb 1998 | A |
5718948 | Ederyd et al. | Feb 1998 | A |
5718976 | Dorfman et al. | Feb 1998 | A |
5725573 | Dearnaley et al. | Mar 1998 | A |
5728465 | Dorfman et al. | Mar 1998 | A |
5731045 | Dearnaley et al. | Mar 1998 | A |
5740941 | Lemelson | Apr 1998 | A |
5743957 | Kobashi | Apr 1998 | A |
5747118 | Bunshah et al. | May 1998 | A |
5747120 | McLean, II et al. | May 1998 | A |
5750207 | Hammond et al. | May 1998 | A |
5755261 | Fukuzawa et al. | May 1998 | A |
5759623 | Mello et al. | Jun 1998 | A |
5763072 | Kato et al. | Jun 1998 | A |
5763087 | Falabella | Jun 1998 | A |
5780119 | Dearnaley et al. | Jul 1998 | A |
5786038 | Conley et al. | Jul 1998 | A |
5786068 | Dorfman et al. | Jul 1998 | A |
5794801 | Lemelson | Aug 1998 | A |
5799549 | Decker et al. | Sep 1998 | A |
5803967 | Plano et al. | Sep 1998 | A |
5824367 | Park et al. | Oct 1998 | A |
5827613 | Nakayama et al. | Oct 1998 | A |
5829735 | Ikeda | Nov 1998 | A |
5836905 | Lemelson et al. | Nov 1998 | A |
5837322 | Moran et al. | Nov 1998 | A |
5837331 | Menu et al. | Nov 1998 | A |
5837394 | Schumm | Nov 1998 | A |
5840132 | Erdemir et al. | Nov 1998 | A |
5840163 | Welty | Nov 1998 | A |
5849413 | Zhu et al. | Dec 1998 | A |
5853839 | Schmeisser | Dec 1998 | A |
5858471 | Ray et al. | Jan 1999 | A |
5863606 | Okamura et al. | Jan 1999 | A |
5866195 | Lemelson | Feb 1999 | A |
5871805 | Lemelson | Feb 1999 | A |
5874175 | Li | Feb 1999 | A |
5888638 | Kleinhans et al. | Mar 1999 | A |
5897942 | Karner et al. | Apr 1999 | A |
5900982 | Dolgoff et al. | May 1999 | A |
5902563 | Pinneo | May 1999 | A |
5925413 | Holzer et al. | Jul 1999 | A |
5925422 | Vandenbulcke et al. | Jul 1999 | A |
5927325 | Bensaoula et al. | Jul 1999 | A |
5927727 | Wagner et al. | Jul 1999 | A |
5932302 | Yamazaki et al. | Aug 1999 | A |
5934321 | Miya et al. | Aug 1999 | A |
5935323 | Tanga et al. | Aug 1999 | A |
5940975 | Decker et al. | Aug 1999 | A |
5945656 | Lemelson et al. | Aug 1999 | A |
5952102 | Cutler | Sep 1999 | A |
5955212 | Matsumoto et al. | Sep 1999 | A |
5961719 | Buhaenko et al. | Oct 1999 | A |
5972233 | Becker et al. | Oct 1999 | A |
5985451 | Senda et al. | Nov 1999 | A |
5992268 | Decker et al. | Nov 1999 | A |
6045916 | Shimamura et al. | Apr 2000 | A |
6063455 | Jeong et al. | May 2000 | A |
6066399 | Hirano et al. | May 2000 | A |
6080376 | Iida et al. | Jun 2000 | A |
6080445 | Sugiyama et al. | Jun 2000 | A |
6080470 | Dorfman | Jun 2000 | A |
6083570 | Lemelson et al. | Jul 2000 | A |
6096377 | Karner et al. | Aug 2000 | A |
6099639 | Thomas | Aug 2000 | A |
6099976 | Lemelson et al. | Aug 2000 | A |
6103305 | Friedmann et al. | Aug 2000 | A |
6110240 | Saguchi et al. | Aug 2000 | A |
6131603 | Takano et al. | Oct 2000 | A |
6136386 | Nakahigashi et al. | Oct 2000 | A |
6139964 | Sathrum et al. | Oct 2000 | A |
6165616 | Lemelson et al. | Dec 2000 | A |
6186768 | Schmitt | Feb 2001 | B1 |
6197438 | Faulkner | Mar 2001 | B1 |
6203865 | Badzian et al. | Mar 2001 | B1 |
6204595 | Falabella | Mar 2001 | B1 |
6207281 | Itoh | Mar 2001 | B1 |
6207282 | Deguchi et al. | Mar 2001 | B1 |
6231956 | Brenner et al. | May 2001 | B1 |
6248434 | Westphal et al. | Jun 2001 | B1 |
6250604 | Robert | Jun 2001 | B1 |
6261421 | Meunier et al. | Jul 2001 | B1 |
6287682 | Grab et al. | Sep 2001 | B1 |
6299425 | Hirano et al. | Oct 2001 | B1 |
6302768 | Adachi | Oct 2001 | B1 |
6305416 | Snel et al. | Oct 2001 | B1 |
6314763 | Sakamoto | Nov 2001 | B1 |
6314764 | Sakamoto | Nov 2001 | B1 |
6331332 | Wang | Dec 2001 | B1 |
6342195 | Roy et al. | Jan 2002 | B1 |
6342755 | Russ et al. | Jan 2002 | B1 |
6347905 | Lukschandel | Feb 2002 | B1 |
6368664 | Veerasamy et al. | Apr 2002 | B1 |
6368676 | Gaudreau et al. | Apr 2002 | B1 |
6387443 | Shi et al. | May 2002 | B1 |
6387502 | Okamura et al. | May 2002 | B1 |
6395333 | Veerasamy | May 2002 | B2 |
6406760 | Shepard | Jun 2002 | B1 |
6410125 | Brenner et al. | Jun 2002 | B1 |
6423193 | Miller et al. | Jul 2002 | B1 |
6447843 | Olson | Sep 2002 | B1 |
6453946 | Nichols et al. | Sep 2002 | B2 |
6462467 | Russ | Oct 2002 | B1 |
6471408 | Ikeda et al. | Oct 2002 | B1 |
6478887 | Sue et al. | Nov 2002 | B1 |
6503380 | Buehler | Jan 2003 | B1 |
6508416 | Mastro et al. | Jan 2003 | B1 |
6508453 | Mamyo | Jan 2003 | B2 |
6514565 | Dearnaley et al. | Feb 2003 | B2 |
6517902 | Drake et al. | Feb 2003 | B2 |
6537429 | Daugherty et al. | Mar 2003 | B2 |
6537688 | Silvernail et al. | Mar 2003 | B2 |
6544627 | Vijayen et al. | Apr 2003 | B1 |
6548173 | Erdemir et al. | Apr 2003 | B2 |
6558757 | Scheibe et al. | May 2003 | B1 |
6572936 | Domoto et al. | Jun 2003 | B1 |
6609367 | Nakayasu et al. | Aug 2003 | B2 |
6610360 | Petrmichl et al. | Aug 2003 | B2 |
6634619 | Cusac et al. | Oct 2003 | B2 |
6638570 | Veerasamy | Oct 2003 | B2 |
6641861 | Saito et al. | Nov 2003 | B2 |
6656444 | Pinneo | Dec 2003 | B1 |
6663753 | Veerasamy et al. | Dec 2003 | B2 |
6696157 | David et al. | Feb 2004 | B1 |
6720035 | Andujar et al. | Apr 2004 | B2 |
6793849 | Gruen et al. | Sep 2004 | B1 |
6802457 | Campion et al. | Oct 2004 | B1 |
6895991 | Woessner | May 2005 | B2 |
6902809 | Mittendorf | Jun 2005 | B1 |
6904935 | Welty et al. | Jun 2005 | B2 |
6916004 | Suzuki | Jul 2005 | B2 |
6921469 | Larsen | Jul 2005 | B2 |
6935618 | Welty et al. | Aug 2005 | B2 |
7004197 | Gilbert | Feb 2006 | B2 |
7106939 | LaBrake et al. | Sep 2006 | B2 |
7108012 | Rosko et al. | Sep 2006 | B2 |
7143782 | Bantleon et al. | Dec 2006 | B2 |
7144753 | Swain et al. | Dec 2006 | B2 |
7172142 | Taylor et al. | Feb 2007 | B2 |
7195817 | Lev et al. | Mar 2007 | B2 |
7214600 | Won et al. | May 2007 | B2 |
7216661 | Welty et al. | May 2007 | B2 |
7246586 | Hosenfeldt et al. | Jul 2007 | B2 |
7273536 | Shibata et al. | Sep 2007 | B2 |
7309446 | Kley | Dec 2007 | B1 |
7445026 | Welty et al. | Nov 2008 | B2 |
7866342 | Brondum et al. | Jan 2011 | B2 |
7866343 | Brondum et al. | Jan 2011 | B2 |
20010020693 | Bischofberger et al. | Sep 2001 | A1 |
20010035516 | Nichols et al. | Nov 2001 | A1 |
20020028289 | Veerasamy | Mar 2002 | A1 |
20020071949 | Liu et al. | Jun 2002 | A1 |
20020127404 | Veerasamy | Sep 2002 | A1 |
20020192371 | Veerasamy et al. | Dec 2002 | A1 |
20030099835 | Petrmichl et al. | May 2003 | A1 |
20030170464 | Veerasamy | Sep 2003 | A1 |
20040038033 | Massler et al. | Feb 2004 | A1 |
20040058155 | Windischmann | Mar 2004 | A1 |
20040067362 | Veerasamy et al. | Apr 2004 | A1 |
20040069358 | Knapp et al. | Apr 2004 | A1 |
20040118455 | Welty et al. | Jun 2004 | A1 |
20050241239 | Sung | Nov 2005 | A1 |
20060005900 | Dorfman | Jan 2006 | A1 |
20060038156 | Welty et al. | Feb 2006 | A1 |
20060059688 | Tseng et al. | Mar 2006 | A1 |
20060079863 | Burgmeier et al. | Apr 2006 | A1 |
20060105172 | Yamamoto et al. | May 2006 | A1 |
20060150862 | Zhao et al. | Jul 2006 | A1 |
20060236780 | Hofmann | Oct 2006 | A1 |
20070074664 | Nishimura et al. | Apr 2007 | A1 |
20070181843 | Welty et al. | Aug 2007 | A1 |
20070224242 | Helmuth et al. | Sep 2007 | A1 |
20070278444 | Brondum et al. | Dec 2007 | A1 |
20070284255 | Gorokhovsky et al. | Dec 2007 | A1 |
20080011976 | Scarlin | Jan 2008 | A1 |
20080044451 | Steinmuller-Nethl et al. | Feb 2008 | A1 |
20080070049 | Guo et al. | Mar 2008 | A1 |
20080073505 | Niu et al. | Mar 2008 | A1 |
20080315146 | Brondum et al. | Dec 2008 | A1 |
20090186206 | Ito et al. | Jul 2009 | A1 |
20100252130 | Brondum et al. | Oct 2010 | A1 |
20110011476 | Brondum | Jan 2011 | A1 |
Number | Date | Country |
---|---|---|
683844 | May 1994 | CH |
1729368 | Feb 2006 | CN |
101432462 | May 2009 | CN |
3728946 | Mar 1989 | DE |
0265533 | May 1988 | EP |
0361206 | Apr 1990 | EP |
0207467 | Dec 1990 | EP |
0509630 | Oct 1992 | EP |
0509875 | Oct 1992 | EP |
0520567 | Dec 1992 | EP |
0462734 | Sep 1993 | EP |
0318998 | Oct 1993 | EP |
0388861 | Sep 1994 | EP |
0440326 | Dec 1994 | EP |
0378378 | Jan 1995 | EP |
0676902 | Oct 1995 | EP |
0520566 | Mar 1996 | EP |
0520832 | Mar 1996 | EP |
0605814 | Sep 1996 | EP |
0611331 | Jun 1997 | EP |
0826798 | Mar 1998 | EP |
0632344 | Jul 1998 | EP |
0884509 | Dec 1998 | EP |
0603422 | May 2000 | EP |
0519472 | Mar 2002 | EP |
0730129 | Mar 2003 | EP |
0892092 | Oct 2003 | EP |
2083095 | Jul 2009 | EP |
2083095 | Jul 2009 | EP |
57106513 | Jul 1982 | JP |
60195094 | Oct 1985 | JP |
61106494 | May 1986 | JP |
61124573 | Jun 1986 | JP |
6272921 | Apr 1987 | JP |
62196371 | Aug 1987 | JP |
223190 | Oct 1991 | JP |
04165170 | Jun 1992 | JP |
2295084 | Mar 2007 | RU |
8606758 | Nov 1986 | WO |
8704471 | Jul 1987 | WO |
9005701 | May 1990 | WO |
9201314 | Jan 1992 | WO |
9215082 | Sep 1992 | WO |
9309921 | May 1993 | WO |
9407613 | Apr 1994 | WO |
9601913 | Jan 1996 | WO |
2005015065 | Aug 2005 | WO |
2007020139 | Feb 2007 | WO |
Entry |
---|
Aksenov et al., High-efficiency Source of pure carbon plasma, Sov. Phys. Tech. Phys., Sep. 1980, pp. 1164-1166, vol. 25(9). |
Angus et al., Low-Pressure, Metastable Growth of Diamond and “Diamondlike” Phases, Structure and Properties of Diamond, Aug. 19, 1988, pp. 913-921. |
Bakai et al., Structure of carbon films formed by the deposition of fast ions, Sov. Phys. Tech. Phys, Nov. 1981, pp. 1425-1426, vol. 26(11). |
Berger et al., EELS analysis of vacuum arc-deposited diamond-like films, CSIRO, Division of Applied Physics, Philosophical Magazine Letters, 1988, pp. 285-290, vol. 57, No. 6, Lindfield, New South Wales, 2070 Australia. |
Cheung et al., Growth of Thin Films by Laser-Induced Evaporation, 1988, pp. 63-109 plus back page (47 total pages), vol. 15, Issue 1. |
Chinese Patent Office, Chinese Office Action for Chinese Patent Application No. 201110237454.7, dated May 9, 2013, 12 pages. |
Coll et al., Diamond-like carbon films synthesized by cathodic arc evaporation, Thin Solid Films, 1992, pp. 165-173, vol. 209. |
Collins et al., “Laser plasma source of amorphic diamond,” Applied Physics Letters, Jan. 16, 1989, 4 pages, vol. 54, No. 3. |
Collins et al., Microstructural and Mechanical Properties of Amorphic Diamond, Diamond Files and Technology, 1992, pp. 25-50, vol. 2, No. 1, MY Tokyo. |
Cuomo et al., Energetic Carbon Deposition at Oblique Angles, J. Vac. Sci. Technol, A., Nov./Dec.1992, 7 pages, vol. 10, No. 6, ISSN 0734-2101, Coden JVTAD6, Society by the American Institute of Physics. |
European Search Report for European Application No. 08005755, date of completion, Jun. 21, 2010, 6 pages. |
European Search Report for European Application No. 09160427.2, mail date Aug. 24, 2009, 5 pages. |
European Search Report for European Application No. 11177721.5, date of completion Nov. 28, 2011, 9 pages. |
Extended European Search Report for European Application No. 10184285.4, completed Aug. 30, 2011, 5 pages. |
Falabella et al., Fabrication of Amorphous Diamond Films, Thin Solid Films, 1993, pp. 82-86 (5 pages), vol. 236. |
Feldman et al., Diamond Optics II, Proceedings—SPIE—The International Society for Optical Engineering, Spie P Proceeding Series, Aug. 7-8, 1989, pp. 37-47 plus cover pages (13 total pages), vol. 1146, San Diego, California. |
Grill A: “Diamond-Like Carbon: State of the Art”, Diamond and Related Materials, Elsevier Science Publishers, Amsterdam, Netherlands, vol. 8, No. 2-5, Mar. 1, 1999, pp. 428-434. |
Hirvonen et al., Preparation and Properties of High Density, Hydrogen Free Hard Carbon Films with Direct ION Beam or ARC Discharge Deposition, Materials Science Forum, 1989, pp. 197-216,, vols. 52 & 53, University of Helsinki, Department of Physics, SF-00170 Helsinki, Finland. |
International Preliminary Report on Patentability for International Application No. PCT/US03/46081, date of completion of report Aug. 6, 2006, 3 pages. |
International Search Report for PCT/US03/040681, date of mailing Feb. 22, 2005, 1 page. |
Kitabatake et al., Growth of diamond at room temperature by an ion-beam sputter deposition under hydrogen-ion bombardment, J. Appl. Phys., Aug. 15, 1985, pp. 1693-1695, vol. 58(4). |
Kitahama et al., Synthesis of diamond by laser-induced chemical vapor desposition, Appl. Phys. Lett., Sep. 15, 1986, pp. 634-635, vol. 49(11). |
Marquardt et al., Deposition of Amorphous Carbon Films from Laser-Produced Plasmas, Mat. Res. Symp. Proc., Materials Research Society, 1985, pp. 326-335 plus cover page (11 total pages), vol. 38. |
Martin et al., ION-Beam-Deposited Films Produced by Filtered ARC Evaporation, Thin Solid Films, 1990, pp. 77-83, vol. 193/194. |
Martin et al., Structure and hardness of diamond-like carbon films prepared by arc evaporation, Journal of Materials Science Letters 7, 1988, pp. 410-412. |
Maslov et al., Pulsed Carbon-Plasma Source for Production Processes, UDC 533.9.07, 1985, pp. 662-665, Plenum Publishing Corporation. |
Messier et al., From Diamond-Like Carbon to Diamond Coatings, Thin Solid Films, 1987, pp. 1-9. |
Milne, Tetrahedrally Bonded Amorphous Carbon, Journal of Non-Crystalline Solids, 1996, 8 pages. |
Mirtich et al., “Diamondlike Carbon Protective Coatings for IR Materials,” 1985, 14 pages. |
Mirtich et al., Diamond-like Carbon Protective Coatings for IR Materials, 14 pages. |
Notice of Allowance for U.S. Appl. No. 11/784,765, mail date Oct. 12, 2010, 7 pages. |
Notice of Allowance for U.S. Appl. No. 12/141,848, mail date Sep. 28, 2010, 7 pages. |
Notice of Allowance for U.S. Appl. No. 10/741,848, mail date Apr. 26, 2005, 8 pages. |
Notice of Allowance for U.S. Appl. No. 11/201,395, mail date Jan. 12, 2007, 4 pages. |
Notice of Allowance for U.S. Appl. No. 11/322,871 mail date Sep. 24, 2009, 11 pages. |
Notice of Allowance for U.S. Appl. No. 11/732,948, mail date Jun. 30, 2008, 7 pages. |
Office Action for Canadian Application No. 2510168, mail date Jan. 2, 2007, 12 pages. |
Office Action for Canadian Application No. 2510168, mail date Oct. 11, 2007, 12 pages. |
Office Action for Chinese Application No. 2003800106691.3 with English translation, mail date Oct. 27, 2006, 12 pages. |
Office Action for Chinese Application No. 200710153717 with English translation, mail date Jul. 31, 2009, 11 pages. |
Office Action for Chinese Application No. 200710153719.9 (English translations), mail date Jun. 5, 2009, 2007, 4 pages. |
Office Action for Chinese Application No. 200710153719.9, mail date Apr. 6, 2010, 3 pages. |
Office Action for Chinese Application No. 200810090600.6 and translation, mail date Aug. 4, 2010, 13 pages. |
Office Action for Chinese Application No. 200810090600.6 and translation, mail date Jan. 29, 2010, 12 pages. |
Office Action for European Application No. 03816756.5, mail date Nov. 12, 2007, 4 pages. |
Office Action for Indian Application No. 1391/KOLNP/05, date received Aug. 14, 2009, 20 pages. |
Office Action for Mexican Application No. MX/a/2007/015120, mail date May 7, 2010, 2 pages. |
Office Action for Mexican Application No. PA/a/2005/006402, mail date Aug. 14, 2007, 2 pages. |
Office Action for Russian Application No. 2009122558, mail date Jun. 15, 2009, 2 pages. |
Office Action for U.S. Appl. No. 10/741,848, mail date Feb. 15, 2005, 6 pages. |
Office Action for U.S. Appl. No. 10/741,848, mail date May 14, 2004, 5 pages. |
Office Action for U.S. Appl. No. 10/741,848, mail date Oct. 1, 2004, 5 pages. |
Office Action for U.S. Appl. No. 11/201,395, mail date Jan. 26, 2006, 6 pages. |
Office Action for U.S. Appl. No. 11/201,395, mail date Sep. 26, 2006, 10 pages. |
Office Action for U.S. Appl. No. 11/322,871, mail date Mar. 12, 2004, 5 pages. |
Office Action of Mexican Application No. MX/a/2007/015120, mail date May 7, 2010, 2 pages. |
Office Action of Mexican Application No. MX/a/2007/015121, mail date May 7, 2010, 2 pages. |
Perlow et al., Applied Physics Letters, CODEN: APPLAB, pp. 215-218, ISSN: 0003-6951. |
Response to Office Action for Canadian Application No. 2510168, mail date Apr. 2, 2008, 6 pages. |
Response to Office Action for Canadian Application No. 2510168, mail date Jul. 3, 2007, 17 pages. |
Response to Office Action for Canadian Application No. 2510168, mail date Mar. 31, 2008. |
Response to Office Action for Chinese Application No. 2007/10153719.9, mail date Jun. 4, 2010, 6 pages. |
Response to Office Action for Chinese Application No. 200710153719.9 with English translation, mail date Oct. 20, 2009, 18 pages. |
Response to Office Action for European Application No. 03816756.5, mail date Mar. 19, 2008, 17 pages. |
Response to Office Action for European Application No. 03816756.5, mail date Mar. 25, 2008, 16 pages. |
Response to Office Action for Indian Application No. 1391/KOLNP/05, mail date Apr. 28, 2008, 29 pages. |
Response to Office Action for U.S. Appl. No. 10/741,848, mail date Jan. 3, 2005, 14 pages. |
Response to Office Action for U.S. Appl. No. 10/741,848, mail date Mar. 8, 2005, 8 pages. |
Response to Office Action for U.S. Appl. No. 11/201,395, mail date May 23, 2006, 20 pages. |
Response to Office Action for U.S. Appl. No. 11/201,395, mail date Oct. 20, 2006, 14 pages. |
Response to Office Action for U.S. Appl. No. 11/322,871, mail date Jul. 8, 2004, 15 pages. |
Response to Restriction Requirement for U.S. Appl. No. 11/784,765, mail date Apr. 14, 2010, 8 pages. |
Response to Restriction Requirement for U.S. Appl. No. 11/784,765, mail date Jul. 26, 2010, 7 pages. |
Restriction Requirement for U.S. Appl. No. 11/784,765, mail date Mar. 25, 2010, 7 pages. |
Richter et al., About the Structure and Bonding of Laser Generated Carbon Films by Raman and Electron Energy Loss Spectroscopy, Journal of Non-Crystalline Solide, 1986, pp. 131-144, vol. 88, North-Holland, Amsterdam. |
Robertson, Amorphouse Carbon, Current Opinion in Solid State & Materials Science, 1996, 6 pages, ISSN 1359-0286. |
Sato et al., Deposition of Diamond-Like Carbon Films by Pulsed-Laser Evaporation, Department of Electrical and Electronic Engineering, Aug. 17, 1987, pp. L1487-L1488. |
Sato et al., Diamond-Like Carbon Films Prepared by Pulsed-Laser Evaporation, Applied Physics A © Springer-Verlag, 1988, pp. 355-360. |
Strel'nitskii et al., Properties of diamond-like carbon coating produced by plasma condensation, Sov. Tech. Phys. Lett., Nov. 1978, pp. 546-547, vol. 4(11). |
Strel'nitskii et al., Properties of the diamond-like carbon film produced by the condensation of a plasma stream with an rf potential, Sov. Phys. Tech. Phys., Feb. 1978, pp. 222-224, vol. 23(2). |
Supplemental Notice of Allowance for U.S. Appl. No. 11/201,395, mail date Feb. 6, 2007, 3 pages. |
Supplementary European Search Report for European Application No. 03816756, date of completion Aug. 2, 2007, 2 pages. |
Written Opinion for International Application No. PCT/US03/46081, mail date May 15, 2006, 4 pages. |
Number | Date | Country | |
---|---|---|---|
20140076437 A1 | Mar 2014 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 12641008 | Dec 2009 | US |
Child | 14021277 | US | |
Parent | 11201395 | Aug 2005 | US |
Child | 11732948 | US | |
Parent | 10741848 | Dec 2003 | US |
Child | 11201395 | US | |
Parent | 10322871 | Dec 2002 | US |
Child | 10741848 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 12141848 | Jun 2008 | US |
Child | 12641008 | US | |
Parent | 11732948 | Apr 2007 | US |
Child | 12141848 | US | |
Parent | 11784765 | Apr 2007 | US |
Child | 12641008 | US | |
Parent | 11201395 | Aug 2005 | US |
Child | 11784765 | US |