1. Field of the Invention
The present invention relates, in general, to use of nanotechnology, and, more particularly, methods to produce significantly improved material performance through the use of composite nanoparticles.
2. Relevant Background
Powders are used in numerous applications. They are the building blocks of electronic, telecommunication, electrical, magnetic, structural, optical, biomedical, chemical, thermal, and consumer goods. On-going market demands for smaller, faster, superior and more portable products have demanded miniaturization of numerous devices. This, in turn, demands miniaturization of the building blocks, i.e. the powders. Sub-micron and nano-engineered (or nanoscale, nanosize, ultrafine) powders, with a size 10 to 100 times smaller than conventional micron size powders, enable quality improvement and differentiation of product characteristics at scales currently unachievable by commercially available micron-sized powders.
Nanopowders in particular and sub-micron powders in general are a novel family of materials whose distinguishing feature is that their domain size is so small that size confinement effects become a significant determinant of the materials' performance. Such confinement effects can, therefore, lead to a wide range of commercially important properties. Nanopowders, therefore, are an extraordinary opportunity for design, development and commercialization of a wide range of devices and products for various applications. Furthermore, since they represent a whole new family of material precursors where conventional coarse-grain physiochemical mechanisms are not applicable, these materials offer unique combination of properties that can enable novel and multifunctional components of unmatched performance. Yadav et al. in commonly assigned U.S. Pat. No. 6,569,397 which along with the references contained therein are hereby incorporated by reference in full, teach some applications of sub-micron and nanoscale powders.
It has been anticipated by those skilled in the art that size confinement could potentially produce materials with significantly improved strength, toughness, hardness, and other mechanical properties. However, size confinement has been difficult to reduce to commercial practice. The reasons for this failure, in part, include (a) current inability to retain the nanoscale grain size when nanoparticles are post-processed into a final commercial product, and (b) agglomeration and aggregation of nanoparticles that in turn produces defects and poor bonding at interfaces.
Yet another method of improving the mechanical performance of materials that is known to those in the art is to employ particles to dispersion strengthen materials. Dispersion strengthening is a method used to increase the strength and high temperature performance of metal alloys by incorporating a fine distribution of hard particulates within a load-bearing matrix. These materials are formed, for example, by mixing particles with a matrix material comprising the metal, metal alloy, or other material to be strengthened. This method takes advantage of the fact that dislocation motion is hindered by the presence of the fine particulate. It is expected that as nanoparticles replace microparticles in dispersion-strengthened materials, the performance of these materials will increase.
However, it has been difficult to use nanoscale particulates in commercial dispersion strengthening applications because of poor bonding at the matrix and the nanoparticle dispersant interface. The lack of an intimate, uniform bonding between the matrix and dispersant materials results in sub-optimal performance of the composite materials. Further, conventional techniques experience difficulty in achieving and maintaining a homogeneous distribution of the nanoparticles in the matrix.
In general, the commercial promise and social benefits of nanotechnology are currently limited by the difficulty in post-processing nanoparticles into nanotechnology products. There is a need for a technology that can address these post-processing limitations.
Briefly stated, the present invention involves the use of nanotechnology to produce composite nanoparticles, as well as new classes of materials from those composite nanoparticles. The invention addresses known issues with the use of nanoparticles and offers unusual methods for making novel materials useful in a wide range of applications. More specifically, the invention teaches method to create materials from plastics that can compete with metals and alloys in certain applications. The invention further teaches method to create materials from resins, ceramics, metals or alloys that are expected to dramatically improve the performance of the constituent materials they are fabricated from. Further, the invention discloses some illustrative applications and their commercial significance.
This invention is generally directed to size-confined, interface-fused nanocomposite particles and products produced from such particles. Composite nanoparticles produced in accordance with the present invention comprise, for example fine powders in which nanoscale particles are bonded to the surfaces of nanoscale or micron scale particles of a matrix material. An important difference between other methods that merely teach coating of a powder with another substance, is that in present invention the nanoscale particles on the surface and the coated powder chemically bond and form a layer where the two compositions create a state synergistically reducing the free energies from the bonding. Thus, the coated nanocomposite particles taught herein are characterized by the composition of the powder coated, composition of the nanoparticles that form the coating, and the distinct composition of an interface that results from the bonding process and consequent reduction in the chemical potential. Therefore, unlike other techniques in the art that merely teach methods for forming coated powders, this invention teaches a novel composition of matter. Also, unlike prior approaches for forming composites materials, the present invention enables a high degree of control and flexibility in engineering the interface between the nanoparticle dispersant and the matrix material. Further, the resulting powder is uniform at a fine powder scale to that when the composite nanopowders are used to form materials, uniformity and homogeneity of the resulting material is readily controlled.
Definitions
For purposes of clarity the following definitions are provided to aid understanding of description and specific examples provided herein:
“Fine powders”, as the term used herein, are powders that simultaneously satisfy the following:
“Submicron powders”, as the term used herein, are fine powders that simultaneously satisfy the following:
“Nanopowders” (or “nanosize powders” or “nanoscale powders” or “nanoparticles”), as the term used herein, are fine powders that simultaneously satisfy the following:
“Pure powders,” as the term used herein, are powders that have composition purity of at least 99.9%, preferably 99.99% by metal basis.
“Powder”, as the term used herein encompasses oxides, carbides, nitrides, chalcogenides, metals, alloys, and combinations thereof. The term includes hollow, dense, porous, semi-porous, coated, uncoated, layered, laminated, simple, complex, dendritic, inorganic, organic, elemental, non-elemental, composite, doped, undoped, spherical, non-spherical, surface functionalized, surface non-functionalized, stoichiometric, and non-stoichiometric form or substance.
The present invention involves size confinement, and in particular involves size confinement through the use of nanoscale particles.
One feature of the present invention involves forming nanocomposite particles (also called nanocomposite powders) that are size-confined in that they retain useful properties associated with size confinement when placed in proximity with other matter as required by most useful applications.
It is known that the mechanical properties of materials can be improved by dispersion strengthening or hard working the materials to introduce interfaces where dislocations get pinned. The emergence of nanotechnology has led those in the art to theoretically suggest that materials having nanoscale dimensions could be used to form unusually superior performing materials, superior in strength, modulus, creep and other commercially useful characteristics. Despite the potential outlined by theory, in practice this has not been reduced to commercial use. In part, this failure is because it is very difficult to retain the nanoscale dimensions as nanoparticles are processed into final useful products. When used as dispersants, it is difficult to disperse the nanoparticles homogeneously in a matrix. Further, it is difficult to process the nanoparticles and a matrix to achieve intimate bonding at the interface; normally, defects or the presence of gases adsorbed onto the interfaces causes the bonding to be poor.
Conventional methods of forming a product from nanoparticles or forming a nano-dispersion strengthened material combines the process of forming the end product and interface engineering. That is, both the product manufacturing step and the interface-engineering step happen together, each affecting and often creating confounding interactions with the other. To be more specific, numerous products prepared from powders require sintering which normally is practiced at elevated temperatures. These elevated temperatures, unfortunately, also cause grain coarsening and the loss of nanoscale confinement. Similarly, dispersion of particulates in alloys is often done at elevated temperatures or in molten form of a metal or alloy. These processing conditions lead to phase segregation or poor distribution and bubbling out of the particles given that they have gases adsorbed at their interface.
It is also common to prepare mixtures of powders in advance of the manufacturing processes used to make a useful article. The prepared mixtures are packaged, stored, and handled in ways that affect the integrity of the powders. For example, separation of the mixture reduces homogeneity leading to variability in performance of the material in the manufacturing processes.
In accordance with the present invention, the product manufacturing operation(s) and the interface-engineering operation(s) are separated. The interface engineering is done first in operations shown in
As shown in
In one embodiment, the nanoscale powders or submicron powders selected in 101 are coated in operation 105 with the powders selected in 103, preferably such that coating is significantly thinner than the composite powder size. On weight basis, it is preferred that the loading of coated nanoparticulate material be less than or equal to 40% by weight of the resultant nanocomposite powder, and more preferred to be less than 5% in some applications. In some applications, this loading can be as small as 0.25% to 2%, or lower than 0.25%, and in others it may be higher than 40% by weight. This coating can be done using techniques such as chemical vapor deposition, physical vapor deposition, monolayer reactive deposition, precipitation, condensation, selective and controlled reaction, infiltration, laser deposition, and those taught by commonly owned co-pending U.S. patent application Ser. No. 10/004,387 filed on Dec. 4, 2001 entitled “NANO-DISPERSED POWDERS AND METHODS FOR THEIR MANUFACTURE”, the specification of which is incorporated herein by reference. The particles so produced can subsequently be processed into useful products. The presence of the coating prevents or limits the coarsening of the nanoparticles and the coated powder, and gives the manufacture greater control over the manner in which size confinement effects of the composite particles affect the properties of the useful article being produced.
In another embodiment, fine powders or submicron powders or nanoscale powders of first composition of material (selected in operation 101) are post-processed in operation 105 with nanoparticles of second composition selected in operation 103. The post-processing produces composite particles where the nanoparticles of second composition coat the powders of first composition. The coating bonds the interface between the first and the second composition. The coating performed in 105 can be complete, partial, dense, porous, monolayer, multi-layer, uniform or non-uniform. The composite particles so produced can then be collected in operation 107, and processed into useful products as suggested in
The presence of the coating and interface bonding (a) prevents or limits the coarsening of the nanoparticles, and (b) helps retain the size confinement of the powders of first composition due the presence of the coating of second composition. For this embodiment, one or more of these methods can be employed to form the composite particles—cyogenic fusion, mechano-chemical fusion caused by various variations of milling, chemical vapor deposition, physical vapor deposition, reactive deposition, precipitation, condensation, selective and controlled reaction of surface, infiltration, laser deposition, and those taught by a commonly-pending U.S. patent application Ser. No. 10/004,387.
Examples of a first composition selected in 103 in a composite particle can be a polymer, metal, ceramic, alloy or a composite. The second composition can also be a polymer, metal, ceramic, alloy or a composite; however, for this invention the substance constituting the first composition is different in one or more way than the second composition.
Some non-limiting illustrations of a polymer useful as a first composition in 103 include polyethylene, polypropylene, polystyrene, polyurethane, polyacrylates, polycarbonates, polyamides, polyamines, polyimines, and any other carbon containing polymeric compound.
Some non-limiting illustrations of a ceramic useful as a first composition in 103 include oxides, carbides, nitrides, borides, chalcogenides, halides, silicides, and phosphides. Ceramics for this invention can be single metal compounds or multi-metal compounds. The composition selected in 103 may also comprise complex compositions such as oxycarbides, oxynitrides, carbonitrides, boro-nitrides, and non-stoichiometric compositions.
Some non-limiting illustrations of a metal useful in as a first composition in 103 include transition metals, alkali metals, alkaline earth metals, rare earth metals, and semi-metals. It is preferred that the metal be low cost and otherwise compatible with the processing and intended use for the metal. Some of the preferred metals for dispersion strengthening include those comprising copper, molybdenum, iron, nickel, and cobalt.
Some non-limiting illustrations of an alloy that can be prepared using the nanocomposite powders in accordance with this invention include alloys comprising two metals, alloys comprising three or more metals, alloys comprising metals and semimetal or nomnetal or both. Some of the preferred alloys for dispersion strengthening include those comprising steel, iron alloys, aluminum alloys, brass, bronze, nickel alloys, molybdenum alloys, titanium alloys, superalloys, and alloys comprising of rare earth elements.
Fine powders, submicron powders, and nanoparticles for this invention may be produced and processed by any method including those that have been discussed in commonly owned patents (U.S. Pat. Nos. 6,344,271, 6,228,904, 6,202,471, 5,984,997, 5,952,040, 5,905,000, 5,851,507, and 5,788,738) which along with the references cited therein are incorporated herein by reference.
The manufacturing processes shown in
In
Dispersion strengthening is a method to increase the strength of metal alloys by incorporating a fine distribution of hard particulates. This method takes advantage of the fact that dislocation motion is hindered by the presence of the fine particulate. This can be quantified by the following equation:
where τ=stress to force a dislocation through the particulate, G=shear modulus, b=Burger's vector, λ=spacing between particulate.
One of the primary variables in this equation (for a given chemistry) is the spacing between the particulate. This spacing can be reduced by decreasing the size of the particulate, giving a resultant increase in the shear strength for a given volume fraction of particulate. By decreasing the size of the particulate, the total mass and volume of particulate in the composite need not change. In this manner, valuable properties of the matrix material are expected to remain constant or be improved by decreasing the size of the particulate rather than being altered or compromised as might occur if the particulate loading were increased.
For example, 10 μm powders have a volume of about 5.24×10−10 cc/particle (for spheres), while 100 nm powders have a volume of about 5.24×10−16 cc/particle. Everything else remaining same and assuming uniform distribution, this represents a six order of magnitude difference in the number of reinforcing particles in a given volume of the composite. The increased dispersant concentration by number significantly decreases the inter-particle spacing (λ). By using 100 nm dispersant particles instead of 10 micron dispersant particles, the inter-particle spacing (λ) can be reduced by about 100 fold, which translates to a 100 fold enhancement in failure stress, τ.
In order to improve the performance of the metals like copper and alloys like nickel aluminide, it is preferred that the nanoparticles be fused on the surface of the metal or alloy powder. This can be accomplished using Hosokawa Micron's Mechanochemical Bonding® equipment. For example, 1 wt % of aluminum oxide nanoparticles can be mechanochemically bonded with 5 to 20 micron copper powders. Other weight loadings and different particle sizes can be utilized as appropriate. The resulting nano-engineered composite particles are ready to be used for oxide dispersion strengthened materials. It is anticipated that the uniform distribution and the interface bonding of the powders will significantly enhance the performance of the resulting material.
Alternatively, by using indium tin oxide or conductive nanoparticle dispersant, the electrical properties of the resulting oxide dispersion strengthened alloy can be enhanced. Similarly, by using magnetic compositions, additional functionality can be added to the dispersion strengthened metal or alloy. In yet other applications, the dispersant composition may be chosen to be one that is thermodynamically stable with the matrix at processing and use temperatures and environments. To illustrate, but not limit, the use of yttrium aluminum garnet instead of yttria in aluminum alloys can prevent the degradation of yttria strengthened aluminum alloy over time at high temperatures due to the reaction thermodynamically favored between yttria and aluminum.
Mineral fillers are commonly used in plastics to lower cost or to enhance performance of the plastic. These mineral fillers are often nanoscale powders, submicron powders or fine powders (e.g., calcium carbonates, fumed silicas, carbon black, talc). Everything else remaining same, the shape, the size, and the concentration of mineral filler addition determines the performance the filler-filled plastic. However, an outstanding problem has been the ability to homogeneously distribute nanostructured or submicron mineral fillers as these fillers have tendencies to agglomerate. Another issue is the bonding of the filler interface to the polymer. These reasons, in part, have limited the commercially achieved performance of filled polymers.
To fully appreciate the relevance of nanotechnology to plastics, consider the constitutive equation for tensile strength of a polymer,
σB˜k(Eγ/a)1/2
where,
This equation suggests that the tensile strength of a plastic is, in part, a function of the length of the naturally occurring cracks in a compounded plastic. As a rule of thumb, for compounded plastic powders of about 20 to 50 micron size, this naturally occurring crack length is usually between 1 to 10 microns. When a plastic fails, it is often because of stresses that concentrate around these cracks and grow the crack. The presence of fillers tends to pin these cracks and provide some limited improvement in the performance of the plastic.
Everything else remaining same, if plastic powders can be size-confined by a well-bonded mineral filler, the crack length can be confined to a domain size less than the plastic powder size. This can significantly enhance the tensile strength of the compounded plastic. Other mechanical properties can similarly be enhanced.
The superior performing plastic can be achieved as follows. Produce plastic powders of less than 5 microns, preferably less than 1 micron, more preferably 0.5 micron, and most preferably 100 nm in size. Coat (with good interface bonding) or mechano-chemically bond a nanoscale filler on the surface of this plastic powder by any technique thereby forming coated size-confined plastic powders. Ultimately, the present invention is used to produce a product from the coated size-confined plastic powder.
In another embodiment, a further step can comprise processing the coated size-confined plastic powders with additional plastic material to form a compounded plastic powder of a size suitable for injection molding. Such process can include agglomeration with uncoated plastic powders or ball milling or any other technique, and performed, for example, in post-processing operation 203 shown in
Table 1 presents specific data on the benefits of nanoparticle enabled size-confined plastic powders in contrast with conventional polymers, metals and alloys.
Table 1 suggests that nanoparticle enabled size confinement can enhance the tensile strength of a plastic to a level where they may be able to compete with certain metals and alloys. Size-confined nanocomposite plastics become particularly attractive when the tensile strength exceeds 75 MPa. Given that plastics can be injection molded and formed by other techniques into net shape parts, this approach can significantly reduce the cost of making complex parts while delivering competitive structural performance. Plastics are lighter than metals and the consequent weight related savings could significantly enhance the system wide performance. Such enhanced plastics can be useful in automobiles, mobile consumer products such as laptops, phones and hand-held computers, architecture, and aircraft).
Additionally, size-confined plastic powders with enhanced mechanical properties can also reduce capital, operating, and labor costs associated with such tasks as post-machining, finishing, and others that are necessary when complex metal parts are being formed. The consequent reduction in environmental waste and the possibility of recycling or reuse further make such nanotechnology attractive. At the end of their useful life, such materials can also be used as precursors to make metal carbides and other inorganics through pyrolysis and related methods.
As in example 2, nanoscale fillers can also be used with ceramics, metals and alloys to form superior performing materials. The constitutive equation presented in example 2 applies to other compositions of matter with the modification that many compositions do not experience plastic flow and therefore fracture energy has to be replaced with surface energy per unit area or other suitable quantity.
The superior performing ceramic or metal or alloy can be achieved as follows. Produce powders of desired composition of average size less than 50 microns, preferably less than 5 micron, more preferably 0.5 micron, and most preferably 100 nm in size. Coat (with good interface bonding) or fuse a nanoscale filler on the surface of this powder by any technique thereby forming coated size-confined powders with an average domain size of the confinement of less than 5 microns, preferably less than 1 micron, more preferably 0.5 micron, and most preferably 100 nm in size. Produce a product from the coated size-confined powder.
In another embodiment, a further step can comprise processing the coated size-confined powders with additional material to form a compounded powder of a size suitable for injection molding or other processing technique. Such process can include agglomeration with uncoated powders or ball milling or any other technique.
Compared with parts produced using 20+ micron powders of conventional metals, alloys, and ceramics, parts produced using size-confined materials prepared by the method outlined above can improve tensile strengths by greater than 25%. Other mechanical, magnetic, electrical, thermal, optical, and other properties of commonly available materials can similarly be improved by 25% or more.
Uses
This invention can be utilized to further improve the performance of known oxide dispersion strengthened alloys. These alloys are particularly desirable for engines, lighting parts, medical devices, x-ray imaging systems, cryogenic equipment, automotive parts, medical implants, nuclear industry, offshore piping, dental alloys, sporting goods, parts subject to high temperatures or corrosion, and environmental cleaning equipment.
Size-confined materials that can offer significantly improved performance are useful in wide range of new applications. Of particular interest are fuel cell system parts and micro-turbines given the importance of weight and costs for their wide spread commercial acceptance.
This invention can also be used where dissimilar materials need to be bonded. The filler, in such cases can be prepared with a composition of the dissimilar material thereby aiding the bonding process between matrix and the dissimilar material.
Further, this invention can be used to engineer other properties of materials, e.g., magnetic, electrical, electrochemical, optical, chemical, catalytic, and thermal. This can be achieved because of the fact that the bonding of another material on the surface of a submicron or nanoscale powder isolates the core particle. To illustrate but not limit, by coating magnetically soft nanoscale powders (less than 250 nm average size) on magnetically hard micron-scale powders (greater than 1 micron but less than 1000 microns), the nanocomposite produced is anticipated to exhibit unusual magnetic performance such as the hard magnetic domains that are functionally isolated from the other similar domains. Such materials are expected to be particularly useful in data storage, signal transmission, signal interception, intelligence gathering devices, and power conversion devices.
Similarly, by bonding electrically insulating nanoscale powder compositions on magnetic micron-scale powders, energy storage capacity can be increased while reducing losses due to eddy currents. In contrast, current technology using oxidized coatings to provide such insulation are limited to magnetic materials that oxidize readily, and can not independently control the insulator composition or thickness. In this manner, the present invention enables production of novel materials for electronic components and electrical and energy devices. It is expected that these devices and components can significantly reduce losses and/or improve energy efficiency and/or improve size to performance ratio and/or weight to performance ratios by at least by 5% when compared with equivalent devices and components prepared from uncoated micron-scale powders.
The use of appropriate composition on the surface can help engineer the surface contributed electrical properties of the composite particles. The disclosed materials can also be used for enabling electrical conductivity in materials used commercially at cryogenic or high temperatures or unusual environments or in materials processed at high temperatures to produce a product where the electrical conductivity is normally poor. Electrical conductivity can be achieved as follows: (a) provide a powder that meets the thermal, structural, and other performance requirements of the product, (b) coat the powder with nanoparticles of an electrically conducting substance such as metal or alloy or defect oxides or nitride or carbide or boride to achieve a nanocomposite form disclosed herein, (c) process the nanocomposite powders into a product. This method can enable multifunctional materials, i.e. products that provide structural function and provide one or more additional function. For example, aerospace parts can be produced with such multifunctional materials in order to provide structural support during routine use and provide a method for non-destructive testing of the parts' integrity during routine maintenance tests. If the part integrity is good, it is anticipated that the electrical conductivity of the part will not change. However, cracks and other incipient failures would change the electrical properties and therefore would be an easy way to detect incipient failure before the failure occurs.
Similarly, the use of appropriate composition on the surface can help engineer the surface contributed properties of the composite particles. The disclosed materials can also be used for targeted drug delivery and programmable drug delivery vehicles. Targeted drug delivery can be achieved as follows: (a) provide a magnetic powder that is physiologically acceptable, (b) coat the magnetic powder with the drug or a polymer containing the drug or a slow-release formulation of the drug in a composite particle form disclosed herein, (c) administer the drug orally, by injection, as skin cream, as fluid drops, using surgical procedures, or through inhalation, (d) apply electromagnetic field to concentrate the drug in the area of interest to deliver the drug in the area of interest.
Programmable drug delivery can be achieved as follows: (a) provide a fine powder, submicron powder or nanoscale powder with electromagnetic characteristics that is physiologically acceptable, (b) coat the powder with the drug or a polymer containing the drug or a slow-release formulation of the drug into a composite particle form disclosed herein, (c) if the drug diffuses rapidly, add a diffusion barrier coating that controls the diffusion rate to the preferred rate (d) administer the drug orally, by injection, as skin cream, as fluid drops, using surgical procedures, or through inhalation, (e) apply magnetic or electrical field to concentrate the drug in the area of interest to deliver the drug in the area of interest, (f) develop a program for preferred administration of the drug, (g) in accordance with this program, apply an electromagnetic field of sufficient intensity causing the electromagnetic powders to warm up and thereby thermally inducing increased drug diffusion and delivery rates. Such drug delivery procedures can be combined with blood or other body fluid monitors that monitor the administered drug or a resultant marker or a byproduct of the drug or a waste product of the drug to provide real time information to make the drug delivery administration program safer, cost effective, and more physiologically optimal.
Fine powders have numerous applications in industries such as, but not limiting to biomedical, pharmaceuticals, sensor, electronic, telecom, optics, electrical, photonic, thermal, piezo, magnetic, catalytic and electrochemical products.
Other embodiments of the invention will be apparent to those skilled in the art from a consideration of the specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.
This application is a divisional of U.S. application Ser. No. 10/143,995. filed May 10, 2002, now U.S. Pat. No. 6.855,426, which claims the benefit of U.S. Application No. 60/357,946, filed Feb. 19, 2002, the specification of which is incorporated herein by reference in its entirety, and is a continuation-in-part of U.S. application Ser. No. 10/004,387, filed Dec. 4, 2001, now U.S. Pat. No. 6,652,967, which is incorporated herein by reference in its entirety, which claims the benefit of U.S. Application No. 60/310,967, filed Aug. 8, 2001.
Number | Name | Date | Kind |
---|---|---|---|
3531413 | Rosensweig | Sep 1970 | A |
3565676 | Holzl | Feb 1971 | A |
3635819 | Kaiser | Jan 1972 | A |
3700575 | Paine | Oct 1972 | A |
3734790 | Kirshenbaum | May 1973 | A |
3764540 | Khalafalla et al. | Oct 1973 | A |
3806449 | Kaiser | Apr 1974 | A |
3905109 | Cohen et al. | Sep 1975 | A |
3917538 | Rosensweig | Nov 1975 | A |
3981844 | Romankiw | Sep 1976 | A |
4017820 | Ross | Apr 1977 | A |
4019994 | Kelley | Apr 1977 | A |
4094804 | Shimoiizaka | Jun 1978 | A |
4208294 | Khalafalla et al. | Jun 1980 | A |
4234437 | Friberg et al. | Nov 1980 | A |
4252678 | Smith | Feb 1981 | A |
4280918 | Homola et al. | Jul 1981 | A |
4315827 | Bottenberg et al. | Feb 1982 | A |
4329241 | Massart | May 1982 | A |
4356098 | Chagnon | Oct 1982 | A |
4381244 | Berkowitz et al. | Apr 1983 | A |
4381922 | Frey et al. | May 1983 | A |
4416721 | Deregibus | Nov 1983 | A |
4426356 | Nair | Jan 1984 | A |
4430239 | Wyman | Feb 1984 | A |
4453199 | Ritchie et al. | Jun 1984 | A |
4484943 | Miura et al. | Nov 1984 | A |
4485085 | David et al. | Nov 1984 | A |
4534917 | Walz | Aug 1985 | A |
4584244 | Fenton | Apr 1986 | A |
4588575 | David | May 1986 | A |
4609608 | Solc | Sep 1986 | A |
4610857 | Ogawa et al. | Sep 1986 | A |
4619845 | Ayers et al. | Oct 1986 | A |
4631952 | Donaghey | Dec 1986 | A |
4642207 | Uda et al. | Feb 1987 | A |
4701218 | Barker et al. | Oct 1987 | A |
4721610 | Yoshida et al. | Jan 1988 | A |
4760296 | Johnston et al. | Jul 1988 | A |
4842832 | Inoue et al. | Jun 1989 | A |
4851262 | McFeaters | Jul 1989 | A |
4857492 | Bradley et al. | Aug 1989 | A |
4944985 | Alexander et al. | Jul 1990 | A |
4984446 | Yagawara et al. | Jan 1991 | A |
4988539 | Breuil et al. | Jan 1991 | A |
5011627 | Lutz et al. | Apr 1991 | A |
5030669 | Hendrickson et al. | Jul 1991 | A |
5093286 | Nogami et al. | Mar 1992 | A |
5127951 | Imasato et al. | Jul 1992 | A |
5128081 | Siegel et al. | Jul 1992 | A |
5130210 | Iwasaki et al. | Jul 1992 | A |
5130277 | Ueda et al. | Jul 1992 | A |
5134039 | Alexander et al. | Jul 1992 | A |
5147448 | Roberts et al. | Sep 1992 | A |
5149381 | Grewe et al. | Sep 1992 | A |
5149596 | Smith et al. | Sep 1992 | A |
5180394 | Davidson | Jan 1993 | A |
5180650 | Sacripante et al. | Jan 1993 | A |
5187209 | Hirai et al. | Feb 1993 | A |
5190583 | Menzel et al. | Mar 1993 | A |
5194128 | Beaty et al. | Mar 1993 | A |
5215580 | Elfenthal et al. | Jun 1993 | A |
5252949 | Kirby et al. | Oct 1993 | A |
5258338 | Maher | Nov 1993 | A |
5264157 | Bidan et al. | Nov 1993 | A |
5308804 | Lee | May 1994 | A |
5334292 | Rajeshwar et al. | Aug 1994 | A |
5338430 | Parsonage et al. | Aug 1994 | A |
5350641 | Mogensen et al. | Sep 1994 | A |
5355764 | Marinos et al. | Oct 1994 | A |
5356120 | König et al. | Oct 1994 | A |
5356842 | Yamakawa et al. | Oct 1994 | A |
5368951 | Shiratori et al. | Nov 1994 | A |
5381664 | Bennett et al. | Jan 1995 | A |
5385776 | Maxfield et al. | Jan 1995 | A |
5387462 | Debe | Feb 1995 | A |
5403375 | König et al. | Apr 1995 | A |
5407458 | König et al. | Apr 1995 | A |
5414588 | Barbee, Jr. et al. | May 1995 | A |
5417956 | Moser | May 1995 | A |
5420083 | Brandt | May 1995 | A |
5427672 | Böcker et al. | Jun 1995 | A |
5433906 | Dasch et al. | Jul 1995 | A |
5447708 | Helble et al. | Sep 1995 | A |
5460830 | Kossovsky et al. | Oct 1995 | A |
5462751 | Kossovsky et al. | Oct 1995 | A |
5462903 | Rousset et al. | Oct 1995 | A |
5466575 | Cozzette et al. | Nov 1995 | A |
5466587 | Fitzpatrick-McElligott et al. | Nov 1995 | A |
5466652 | Paparizos et al. | Nov 1995 | A |
5468358 | Ohkawa et al. | Nov 1995 | A |
5472477 | König | Dec 1995 | A |
5476003 | Neumann | Dec 1995 | A |
5482656 | Hiraoka et al. | Jan 1996 | A |
5486277 | Barbee, Jr. et al. | Jan 1996 | A |
5486435 | Brochu et al. | Jan 1996 | A |
5486675 | Taylor et al. | Jan 1996 | A |
5489449 | Umeya et al. | Feb 1996 | A |
5503081 | Lindblom et al. | Apr 1996 | A |
5507965 | Padoy et al. | Apr 1996 | A |
5514734 | Maxfield et al. | May 1996 | A |
5518810 | Nishihara et al. | May 1996 | A |
5527849 | Roman et al. | Jun 1996 | A |
5539965 | Safari et al. | Jul 1996 | A |
5548000 | Nagel et al. | Aug 1996 | A |
5548474 | Chen et al. | Aug 1996 | A |
5549700 | Graham et al. | Aug 1996 | A |
5552086 | Siiman et al. | Sep 1996 | A |
5554670 | Giannelis et al. | Sep 1996 | A |
5560960 | Singh et al. | Oct 1996 | A |
5569561 | Exnar et al. | Oct 1996 | A |
5571401 | Lewis et al. | Nov 1996 | A |
5571612 | Motohiro et al. | Nov 1996 | A |
5590387 | Schmidt et al. | Dec 1996 | A |
5593939 | Saito et al. | Jan 1997 | A |
5614011 | Binder et al. | Mar 1997 | A |
5618475 | Johnson et al. | Apr 1997 | A |
5624718 | Dearnaley | Apr 1997 | A |
5629075 | Ishikawa et al. | May 1997 | A |
5629474 | Williams | May 1997 | A |
5635654 | Hebsur et al. | Jun 1997 | A |
5650156 | Grinstaff et al. | Jul 1997 | A |
5665277 | Johnson et al. | Sep 1997 | A |
5665807 | Roman et al. | Sep 1997 | A |
5679471 | Cheng et al. | Oct 1997 | A |
5681575 | Burrell et al. | Oct 1997 | A |
5688417 | Cadre et al. | Nov 1997 | A |
5690706 | Sigalas et al. | Nov 1997 | A |
5709786 | Friese et al. | Jan 1998 | A |
5714536 | Ziolo et al. | Feb 1998 | A |
5718047 | Nakayama et al. | Feb 1998 | A |
5720805 | Wellinghoff et al. | Feb 1998 | A |
5726247 | Michalczyk et al. | Mar 1998 | A |
5739193 | Walpita et al. | Apr 1998 | A |
5764004 | Rabinowitz | Jun 1998 | A |
5770022 | Chang et al. | Jun 1998 | A |
5770126 | Singh et al. | Jun 1998 | A |
5788738 | Pirzada et al. | Aug 1998 | A |
5840387 | Berlowitz-Tarrant et al. | Nov 1998 | A |
5851507 | Pirzada et al. | Dec 1998 | A |
5858080 | Bugnon | Jan 1999 | A |
5874134 | Rao et al. | Feb 1999 | A |
5876683 | Glumac et al. | Mar 1999 | A |
5880197 | Beall et al. | Mar 1999 | A |
5891986 | Yamaguchi et al. | Apr 1999 | A |
5897945 | Lieber et al. | Apr 1999 | A |
5905000 | Yadav et al. | May 1999 | A |
5922537 | Ewart et al. | Jul 1999 | A |
5935461 | Witherspoon et al. | Aug 1999 | A |
5939146 | Lavernia | Aug 1999 | A |
5952040 | Yadav et al. | Sep 1999 | A |
5981415 | Waku et al. | Nov 1999 | A |
5984997 | Bickmore et al. | Nov 1999 | A |
5989648 | Phillips | Nov 1999 | A |
6020419 | Bock et al. | Feb 2000 | A |
6027742 | Lee et al. | Feb 2000 | A |
6036774 | Lieber et al. | Mar 2000 | A |
6042900 | Rakhimov et al. | Mar 2000 | A |
6045925 | Klabunde et al. | Apr 2000 | A |
6057637 | Zettl et al. | May 2000 | A |
6065476 | Agrawal et al. | May 2000 | A |
6080232 | Sperlich et al. | Jun 2000 | A |
6109095 | Addiego | Aug 2000 | A |
6110266 | Gonzalez-Blanco et al. | Aug 2000 | A |
6110399 | McArdle et al. | Aug 2000 | A |
6110557 | Weir et al. | Aug 2000 | A |
6114038 | Castro et al. | Sep 2000 | A |
6117541 | Frisk | Sep 2000 | A |
6127450 | Angeletakis | Oct 2000 | A |
6132563 | Frach et al. | Oct 2000 | A |
6132905 | Kumar et al. | Oct 2000 | A |
6139618 | Hayashi et al. | Oct 2000 | A |
6143356 | Jablonski | Nov 2000 | A |
6162532 | Black et al. | Dec 2000 | A |
6165247 | Kodas et al. | Dec 2000 | A |
6170292 | Boulos et al. | Jan 2001 | B1 |
6180389 | Douglas et al. | Jan 2001 | B1 |
6194481 | Furman et al. | Feb 2001 | B1 |
6214368 | Lee et al. | Apr 2001 | B1 |
6228904 | Yadav et al. | May 2001 | B1 |
6232372 | Brothers et al. | May 2001 | B1 |
6258417 | Goswami et al. | Jul 2001 | B1 |
6258974 | Wellinghoff et al. | Jul 2001 | B1 |
6261484 | Phillips et al. | Jul 2001 | B1 |
6268054 | Costantino et al. | Jul 2001 | B1 |
6268222 | Chandler et al. | Jul 2001 | B1 |
6270347 | Webster et al. | Aug 2001 | B1 |
6291070 | Arpac et al. | Sep 2001 | B1 |
6294009 | Letschert et al. | Sep 2001 | B1 |
6299937 | Richart | Oct 2001 | B1 |
6300640 | Bhargava et al. | Oct 2001 | B1 |
6306610 | Bawendi et al. | Oct 2001 | B1 |
6312831 | Crawley et al. | Nov 2001 | B1 |
6326144 | Bawendi et al. | Dec 2001 | B1 |
6328798 | Bostrom et al. | Dec 2001 | B1 |
6331312 | Lee et al. | Dec 2001 | B1 |
6344271 | Yadav et al. | Feb 2002 | B1 |
6361161 | Anstadt et al. | Mar 2002 | B1 |
6375864 | Phillips et al. | Apr 2002 | B1 |
6387519 | Anderson et al. | May 2002 | B1 |
6387981 | Zhang et al. | May 2002 | B1 |
6399037 | Pflug et al. | Jun 2002 | B1 |
6410765 | Wellinghoff et al. | Jun 2002 | B1 |
6413638 | Mager et al. | Jul 2002 | B1 |
6416818 | Aikens et al. | Jul 2002 | B1 |
6416868 | Sullivan et al. | Jul 2002 | B1 |
6417127 | Yamamoto et al. | Jul 2002 | B1 |
6419989 | Betz et al. | Jul 2002 | B1 |
6432526 | Arney et al. | Aug 2002 | B1 |
6432866 | Tennent et al. | Aug 2002 | B1 |
6440243 | Tan et al. | Aug 2002 | B1 |
6440561 | Hayashi et al. | Aug 2002 | B2 |
6447806 | Gassmann et al. | Sep 2002 | B1 |
6447848 | Chow et al. | Sep 2002 | B1 |
6467897 | Wu et al. | Oct 2002 | B1 |
6468497 | Khan et al. | Oct 2002 | B1 |
6468808 | Nie et al. | Oct 2002 | B1 |
6479156 | Schmidt et al. | Nov 2002 | B1 |
6485557 | Swiler | Nov 2002 | B1 |
6497729 | Moussy et al. | Dec 2002 | B1 |
6498208 | Border et al. | Dec 2002 | B2 |
6503316 | Sakoske et al. | Jan 2003 | B1 |
6503475 | McCormick et al. | Jan 2003 | B1 |
6528029 | Dettling et al. | Mar 2003 | B1 |
6541112 | Swiler et al. | Apr 2003 | B1 |
6541114 | Katou et al. | Apr 2003 | B2 |
6548171 | Barbera-Guillem et al. | Apr 2003 | B1 |
6569397 | Yadav et al. | May 2003 | B1 |
6572672 | Yadav et al. | Jun 2003 | B2 |
6572693 | Wu et al. | Jun 2003 | B1 |
6589312 | Snow et al. | Jul 2003 | B1 |
6600127 | Peterson et al. | Jul 2003 | B1 |
6602595 | Yadav et al. | Aug 2003 | B2 |
6616968 | Bostrom et al. | Sep 2003 | B2 |
6623557 | Hayashi et al. | Sep 2003 | B2 |
6652967 | Yadav et al. | Nov 2003 | B2 |
6653356 | Sherman | Nov 2003 | B2 |
6663948 | Takiyama et al. | Dec 2003 | B1 |
6667360 | Ng et al. | Dec 2003 | B1 |
6680279 | Cai et al. | Jan 2004 | B2 |
6682872 | Sachdev et al. | Jan 2004 | B2 |
6689192 | Phillips et al. | Feb 2004 | B1 |
6689823 | Bellare et al. | Feb 2004 | B1 |
6693143 | Pflug | Feb 2004 | B2 |
6716525 | Yadav et al. | Apr 2004 | B1 |
6726992 | Yadav et al. | Apr 2004 | B1 |
6746791 | Yadav et al. | Jun 2004 | B2 |
6800127 | Babler | Oct 2004 | B2 |
6830710 | Bonnet et al. | Dec 2004 | B2 |
6830822 | Yadav | Dec 2004 | B2 |
6849109 | Yadav et al. | Feb 2005 | B2 |
6855426 | Yadav | Feb 2005 | B2 |
6855749 | Yadav et al. | Feb 2005 | B1 |
6916872 | Yadav et al. | Jul 2005 | B2 |
6933331 | Yadav et al. | Aug 2005 | B2 |
6989195 | Anderson | Jan 2006 | B2 |
20010038803 | Morales et al. | Nov 2001 | A1 |
20020033131 | Bostrom et al. | Mar 2002 | A1 |
20020100164 | Tanaka et al. | Aug 2002 | A1 |
20020149656 | Nohr et al. | Oct 2002 | A1 |
20030035955 | Yadav | Feb 2003 | A1 |
20030102099 | Yadav et al. | Jun 2003 | A1 |
20030122114 | Dobler et al. | Jul 2003 | A1 |
20030124050 | Yadav et al. | Jul 2003 | A1 |
20030199624 | Yadav et at. | Oct 2003 | A1 |
20030207112 | Yadav | Nov 2003 | A1 |
20030207977 | Yadav et al. | Nov 2003 | A1 |
20030207978 | Yadav et at. | Nov 2003 | A1 |
20030209057 | Yadav et at. | Nov 2003 | A1 |
20030224214 | Garito et al. | Dec 2003 | A1 |
20040021133 | Nagpal et al. | Feb 2004 | A1 |
20040127987 | Evans et al. | Jul 2004 | A1 |
20040178530 | Yadav et al. | Sep 2004 | A1 |
20040180203 | Yadav et al. | Sep 2004 | A1 |
20040233526 | Kaminsky et al. | Nov 2004 | A1 |
Number | Date | Country | |
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20050147747 A1 | Jul 2005 | US |
Number | Date | Country | |
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60357946 | Feb 2002 | US | |
60310967 | Aug 2001 | US |
Number | Date | Country | |
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Parent | 10143995 | May 2002 | US |
Child | 11054786 | US |
Number | Date | Country | |
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Parent | 10004387 | Dec 2001 | US |
Child | 10143995 | US |