• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    This invention relates to methods whereby nanoparticle precursor solutions are used in conventional thermal spray deposition for the fabrication of high-quality nanostructured coatings. The method allows combining nanoparticle synthesis, melting, and quenching into a single operation.
    公开号:US20010004473A1
    申请号:US09/325,822
    申请日:1999-06-04
    公开日:2001-06-21
    发明作者:Peter R. Strutt；Bernard H. Kear；Ross F. Boland
    申请人:Peter R. Strutt；Bernard H. Kear；Ross F. Boland；
    IPC主号:C23C4-06
    专利说明:
    [0001] This application is a divisional of U.S. application Ser. No. 09/019,061, filed Feb. 5, 1998, which is a continuation of U.S. application Ser. No. 08/558,133, filed Nov. 13, 1995, now abandoned, all of which are incorporated herein by reference. [0001] BACKGROUND OF THE INVENTION
    [0002] 1. Field of the Invention [0002]
    [0003] This invention relates generally to the field of nanostructured materials. In particular, this invention relates to nanostructured feeds used in the deposition of high-quality nanostructured coatings via the thermal spraying process. [0003]
    [0004] 2. Brief Description of the Prior Art [0004]
    [0005] Materials with fine-scale microstructures have long been recognized to exhibit technologically attractive properties. In the past few years, a new class of sub-microstructured materials has been identified, composed of ultra fine grains or particles. These materials have been referred to as “nanostructured materials.” Nanostructured materials are characterized by having a high fraction of the material's atoms residing at grain or particle boundaries. For example, with a grain size in the five nanometer range, about one-half of the atoms in a nanocrystalline or a nanophase solid reside at grain or particle interfaces. [0005]
    [0006] Although research in the field of nanostructured materials currently focuses on synthesis and processing of nanostructured bulk materials, there is a growing interest in nanostructured coatings, including thermal barrier, hard and superhard coatings. Nanostructured bulk materials with designed multifunctional coatings present unprecedented opportunities for advances in materials properties and performance for a broad range of structural applications. [0006]
    [0007] Research on nanostructured materials has been a major activity as Rutgers University and the University of Connecticut since the late 1980's. Progress has been made in the synthesis of (1) nanostructured metal powders by the organic solution reaction (OSR) and aqueous solution reaction (ASR) method, (2) nanostructured ceramic-metal (cermet) powders by the spray conversion processing (SCP) method, and (3) nanostructured powders by the gas condensation processing method. Advances have also been made in the consolidation of nanostructured powders by solid and liquid phase sintering methods (for bulk materials) while preserving the desirable nanostructures. [0007]
    [0008] There are three different methods currently in use for the synthesis of nanostructured powders, including (1) the organic solution reaction (OSR) and aqueous solution reaction (ASR) methods for synthesizing nanostructured metal powders, for example, nanostructured Cr[0008] 3C2/Ni powders; (2) the spray conversion processing (SCP) method for synthesizing nanostructured cermet powders, for example, tungsten-carbon/cobalt and Fe3Mo3C/Fe powders; and (3) the gas condensation processing (GCP) method for synthesizing nanostructured ceramic powders, for example, titanium dioxide, zirconium dioxide and silicon/carbon/nitrogen.
    [0009] The OSR and ASR methods for the preparation of nanostructured metals and alloys use three steps: (1) preparation of an organic or aqueous solution of mixed metal chlorides; (2) reductive decomposition of the starting solution with a metal hydride to obtain a colloidal solution of the metallic constituents,; and (3) filtering, washing and drying, followed by gas-phase carburization under controlled carbon and oxygen activity conditions to form the desired nanodispersion of carbide phases in a metallic matrix phase. [0009]
    [0010] This procedure has been used to synthesize a variety of nanostructured metal/carbide powders, including nanostructured Cr[0010] 3C2/NiCr powders for use in thermal spraying of corrosion resistant hard coatings. A small amount of an organic passivation agent, such as a solution of paraffin in hexane added to the final wash provides protection of the high surface area powder against spontaneous combustion when dried and exposed to air. The as-synthesized powders thus produced are loosely agglomerated. As used herein, the term agglomerated also encompasses aggregated particles.
    [0011] The SCP method for synthesizing nanostructured cermet composite powders involves three sequential steps: (1) preparation of an aqueous solution mixture of salts of constituent elements; (2) spray drying of the starting solution to form a homogeneous precursor powder; and (3) fluid bed conversion (reduction and carburization) of the precursor powder to the desired nanostructured cermet powder. The SCP method has been utilized to prepare nanostructured WC/Co, nanostructured Fe[0011] 3Mo3C/Fe and similar cermet materials. The particles may be in the form of hollow spherical shells. The powders are usually passivated after synthesis in order to avoid excessive oxidation when exposed to air.
    [0012] The GCP method is the most versatile process in use today for synthesizing experimental quantities of nanostructured metal and ceramic powders. A feature of the process is its ability to generate loosely agglomerated nanostructured powders, which are sinterable at relatively low temperatures. [0012]
    [0013] In the inert gas condensation (IGC) version of the GCP method, an evaporative source is used to generate the powder particles, which are convectively transported to and collected on a cold substrate. The nanoparticles develop in a thermalizing zone just above the evaporative source, due to interactions between the hot vapor species and the much colder inert gas atoms (typically 1-20 mbar pressure) in the chamber. Ceramic powders are usually produced by a two-stage process: evaporation of a metal source, or preferably a metal suboxide of high vapor pressure, followed by slow oxidation to develop the desired nanostructured ceramic powder particles. [0013]
    [0014] In the chemical vapor condensation (CVC) version of the GCP method, a hot-wall tubular reactor is used to decompose a precursor/carrier gas to form a continuous stream of clusters or nanoparticles exiting the reactor tube. Critical to the success of CVC processing are: (1) a low concentration of precursor in the carrier gas; (2) rapid expansion of the gas stream through the uniformly heated tubular reactor; (3) rapid quenching of the gas phase nucleated clusters or nanoparticles as they exit from the reactor tube; and (4) a low pressure in the reaction chamber. [0014]
    [0015] The resulting nanostructured ceramic powder particles are loosely agglomerated, as in the IGC method, and display low temperature sinterability. This is in contrast to the ultra fine powders produced by conventional ambient pressure combustion flame and arc-plasma powder processing methods, which yield cemented aggregates that can be consolidated only at much higher sintering temperatures. The CVC method has been used to synthesize nanostructured powders of a variety of ceramic materials, which cannot easily be produced by the IGC process, because of their high melting points and/or low vapor pressures. Examples are nanostructured SiC[0015] xNy powders, for which there are many suitable metalorganic precursors, such as hexamethyldisilazane (HMDS). The actual composition of the resulting powder is strongly influenced by the choice of carrier gas. Thus, HMDS/H2O, HMDS/H2 and HMDS/NH3 give nanostructured ceramic powders with compositions close to SiO2, SiC and Si3N4, respectively.
    [0016] In current industrial practice, the powders used to deposit metal, ceramic or composite coatings by thermal spray or plasma deposition consist of particles in the range form 5 to 50 microns in diameter. During the short residence time in the flame or plasma, the particles are rapidly heated to form a spray of partially or completely melted droplets. The large impact forces created as these particle arrive at the substrate surface promote strong particle-substrate adhesion and the formation of a dense coating of almost any desired material, with the coatings ranging in thickness from 25 microns to several millimeters, and formed at relatively high deposition rates. [0016]
    [0017] Generally, the conventional powders used in thermal spray coating are produced by a series of steps, involving ball milling, mechanical blending, high temperature reaction, and occasionally spray drying using a binder. Powder delivery systems in thermal spray technology are designed to work with powder agglomerates with particle size in the range from 5 to 25 microns. The minimum size of the constituent grains or particles in conventional powders is in the range of 1 to 0.5 microns. In contrast, in nanostructured materials, the size of the constituent grains or particles is in the range from 1 to 100 nanometers. As-synthesized nanoparticle powders are thus generally unsuitable for conventional thermal spray coating, and need to be reprocessed in order to satisfy the size requirements of conventional spray technology. Accordingly, there remains a need for methods of re-processing as-synthesized powders so that they are suitable for conventional commercial spray deposition. Alternatively, there remains a need for allowing reliable, inexpensive high-throughput direct injection of an as-synthesized powder, or chemical precursor for in-situ particle synthesis into the thermal spray apparatus in order to achieve reproducible, high-quality deposition of nanostructured coatings. [0017] SUMMARY OF THE INVENTION
    [0018] The above-discussed and other problems and deficiencies of the prior art are overcome or alleviated by the methods of the present invention, which for the first time allow the production of nanoparticle feeds suitable for use with conventional thermal spray technology. [0018]
    [0019] Accordingly, in one embodiment of the present invention, there is provided a method for reprocessing as-synthesized nanoparticle powders to an aggregated form suitable for conventional spray deposition of nanostructured coatings, wherein the as-synthesized powders are first dispersed in a liquid medium by means of ultrasound, then spray dried. These spray dried agglomerated nanostructured powders have a spherical shape and narrow particle size distribution in the optimal 10-50 micron range. These powders therefore have superior feed characteristics in thermal spraying and also experience uniform melting behavior in the combustion flame or plasma. As a consequence, the coatings display uniform nanostructures, negligible porosity, good substrate adhesion and excellent wear properties. In contrast to powders mixed by ball milling or mechanical blending, for example, the method of this invention allows mixing of the material's constituent elements at a molecular level. [0019]
    [0020] In an alternative embodiment of the present invention, there is provided a method for direct nanoparticle injection of as-synthesized powders into the combustion flame or plasma of a conventional thermal spray deposition device, wherein the as-synthesized powders are first dispersed in a liquid medium by means of ultrasound. Direct injection by this method allows reproducible deposition of high-quality nanostructured coatings without an intermediate re-processing step. The very short diffusion distance allows fast reactions to occur between nanoparticles and the vapor species in the gas stream, for example, carburization, nitridation, and boridization. This embodiment also allows the constituents of a given material to be mixed at a molecular level. [0020]
    [0021] In yet another embodiment of the present invention, there is provided a method for the manufacture of nanostructured coatings using a metalorganic aerosol feedstock generated ultrasonically, wherein nanoparticle synthesis, melting and quenching are performed in a single operation. [0021]
    [0022] The above-mentioned and other features and advantages of the present invention will be appreciated and understood by those skilled in the art from the following detailed description and drawings [0022] BRIEF DESCRIPTION OF THE DRAWINGS
    [0023] Referring now to the drawings wherein like elements are numbered alike in the several FIGURES: [0023]
    [0024] FIG. 1 is a flow diagram of the examples of the synthesis of agglomerated nanostructured powders for use in thermal spray coating, including the method of the present invention for reprocessing as-synthesized powders; [0024]
    [0025] FIG. 2 is a detailed flow diagram of the method of the present invention for reprocessing as-synthesized nanostructured powders; [0025]
    [0026] FIG. 3 is a scanning electron micrograph of a WC/Co nano structured powder produced by the reprocessing method of the present invention. [0026]
    [0027] FIGS. 4A and 4B are diagrams comparing thermal spraying of conventional cermet powder particles and agglomerated cermet powder particles of the present invention; [0027]
    [0028] FIG. 5 is a depiction of the method of the present invention for the manufacture of nanostructured coatings using a metalorganic aerosol feedstock generated ultrasonically. [0028] DESCRIPTION OF THE PREFERRED EMBODIMENT
    [0029] Referring now to FIGS. 1 and 2, in one embodiment of the present invention, there is provided a method for reprocessing nanoparticle powders to an agglomerated form suitable for thermal spray deposition of nanostructured coatings. According to this method, as-synthesized nanostructured powders [0029] 10, 12 and 14 are ultrasonically disintegrated and dispersed in a liquid medium, and then spray-dried to form spherical nanoparticle agglomerates 16 suitable for thermal spray deposition. The original particles, typically less than 50 microns, can be reduced to submicron dimensions, forming a viscous slurry or a colloidal suspension within minutes. While nanoparticles 10 synthesized via the solution reaction (OSR or ASR) method, nanoparticles 12 synthesized via the SCP method, or nanoparticles 14 synthesized via the CVC method are each suitable for reprocessing by the method of the present invention, it is to be understood that nanoparticles synthesized by any method are suitable for use in the present invention. In addition, while the agglomerated nanoparticle powders are particularly useful for thermal spray deposition, they may also find utility in other applications requiring agglomerated nanoparticles.
    [0030] In the practice of the method of this embodiment, an as-synthesized powder which may comprise the particles [0030] 10, 12, 14 or a mixture thereof is first suspended in a liquid medium to form suspension 18. The liquid medium may be aqueous-based or organic-based, depending on the desired characteristics of the final agglomerated powder. Suitable organic solvents include, but are not limited to, toluene, kerosene, methanol, ethanol, isopropyl alcohol, acetone and the like.
    [0031] The medium is then treated with ultrasound to disperse the nanostructured material, forming dispersion [0031] 20. The ultrasonic dispersal effect is most pronounced in the cavitation zone 22 at the tip of the ultrasonic horn 24. The nanostructured powder may be merely dispersed in solution, or it may form a colloidal suspension, typically within minutes.
    [0032] A binder is also added to the solution, forming mixture [0032] 26. In organic-based liquid mediums, the binder comprises from about 5% to about 15% by weight, and preferably about 10% by weight of paraffin dissolved in a suitable organic solvent. Suitable organic solvents include, but are not limited to, hexane, pentane, toluene and the like. In aqueous-based liquid mediums, the binder comprises an emulsion of commercially available polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), carboxymethyl cellulose (CMC), or some other water soluble polymer, formed in de-ionized water. The binder is present in the range from about 0.5% to about 5% by weight of the total solution, and preferably from about 1% to about 10% by weight of the total solution. The preferred binder is CMC.
    [0033] After mechanical mixing and if required further ultrasound treatment the suspension of nanostructured powder in the liquid medium [0033] 26 is spray-dried in hot air to form agglomerated particles 16. While any suitable non-reactive gas or mixture thereof may be used, hot nitrogen or hot argon is preferred. Because there is no requirement for the treatment of exhaust gases from the spray drier using aqueous-based liquid mediums, these are preferred where possible.
    [0034] After spraying, powders [0034] 16 are heat-treated at low temperatures (<250° C.) to expel residual moisture, leaving the organic component (polymer or paraffin) as a binder phase. If necessary, a further heat treatment step at a high temperature effective to remove adsorbed and chemisorbed oxygen and to promote partial sintering may be added. For example, heat treatment at about 600° C. is effective. The resulting powder may then be used in conventional thermal spray deposition processes. The following non-limiting examples illustrate the method of re-processing as-synthesized nanostructured powders using ultrasonic dispersion. EXAMPLE 1
    [0035] Typical processing conditions for preparing nanostructured WC/Co powder agglomerates are as follows. Nanostructured WC/Co, prepared by means well-known in the art, is formed into an approximately 50 wt % solution in de-ionized and deoxygenated water. An ultrasonic horn, operating at a frequency of 20,000 Hertz and power of 300-400 watts, is used to disperse the nanostructured WC/Co to form a low viscosity slurry. With this energy input, original as-synthesized hollow spherical shell particles of 10-50 micron diameter are rapidly disintegrated and dispersed in the fluid medium, forming a dispersed phase of particle size of about 100 nm. Subsequently, 5-10 wt % carbon black and a 2-3% by weight solution of PVP in deionized, deoxygenated water are added to the suspension. Carbon black is optionally added to compensate for the carbon loss of WC particles by high reaction in the flame or plasma. CMC is also suitable for use with WC/Co materials. [0035]
    [0036] After mixing and further ultrasonic treatment, the slurry is spray-dried in a commercial unit to form a powder consisting of solid spherical particles with a mean diameter in the 5-20 micron range as shown in FIG. 3. Finally, it is preferable to clean the powders after agglomeration by a low temperature de-gassing treatment under reduced pressure prior to back filling with dry nitrogen. The powders can then be stored indefinitely in nitrogen without degradation. [0036]
    [0037] Because of the high surface area of the nanostructured WC/Co powder agglomerates, there is the potential for in-situ decarburization within the agglomerates, due to the presence of oxygen or oxygen-rich species. To eliminate this problem it is preferable to introduce a passivation treatment at some stage in the powder processing using a suitable oxygen-free compound, such as paraffin. The paraffin is chemisorbed on the high surface area nanoparticles. Preferably, the paraffin is introduced in a hexane solution (5-10% by weight). [0037]
    [0038] The high velocity oxy-fuel (HVOF) process is ideally suited for depositing nanostructured cermet coatings, because of the relatively low flame temperature and short particle transit time, which minimizes deleterious reactions in the flame. [0038]
    [0039] A feature of using cermet nanostructured powders such as WC/Co reprocessed by the method of the present invention is the homogeneous melting of the matrix (binder) phase upon thermal spray coating, with the formation of semi-solid or “mushy” particles. Referring now to FIGS. 4A and 4B, a conventional powder particle [0039] 40 contains a hard particle phase 42 surrounded by a solid matrix phase 44. In the thermal region of the spray apparatus, the solid matrix phase 44 becomes a molten matrix phase 46. Thus, in a conventional cermet powder particle 40 the large (5-25 micron diameter) carbide grain 42 undergoes little size change in the thermal region, because of the finite time for heat transfer during the 1 millisecond transit time between exiting the gun nozzle and impact with substrate. The coatings 48 formed by these particles may therefore be porous.
    [0040] In contrast, the agglomerated cermet powder particles [0040] 50 of the present invention contain hard particles 52, with a grain size in the range from about 5 to about 50 nanometers, within a matrix phase 54, agglomerated by binder 56. During thermal spraying, the small size of the carbide grains 52 of the agglomerated nanostructured particles 50 allow the particles to rapidly dissolve in the molten matrix 58 to produce a “mushy” cermet particle 60. This mushy particle 60 will readily flow upon impact with the substrate to form a highly adherent dense coating with low porosity 62. The degree of fluidity of the impacting particle can be controlled by selecting the degree of superheat above the eutectic point of the impacting particles. Additionally, a high impact velocity of the mushy nanostructured cermet particles facilitates improved spreading and adhesion to the substrate surface. EXAMPLE 2
    [0041] Nanostructured Cr[0041] 3C2/NiCr powders produced by the ASR and OSR methods are in the form of loose agglomerates of variable size and morphology. Using the above general procedure, these powders can be ultrasonically dispersed in an aqueous or organic liquid medium with a polymer or paraffin binder and spray dried to form uniform-sized spherical agglomerates of 5-25 microns diameter. Moreover, during thermal spraying, the nanocomposite powders experience partial melting and undergo splat quenching when they impact the substrate surface. This behavior is similar to that described for nanostructured WC/Co powders. EXAMPLE 3
    [0042] Nanostructured SiO[0042] 2 powders may be produced by combustion flame synthesis, a commercial process. The as-synthesized powder has a high surface area (>400 m2/gm), and is in the form of hard agglomerates known as “cemented aggregates,” with up to 10-100 nanoparticles per aggregate. Such powders can be readily dispersed in an aqueous solution because they are inherently hydrophilic. The resulting colloidal suspension, containing PVA, PVP or CMC as a binder, can then be converted into spherical agglomerates by spray-drying, as discussed above. The behavior in thermal spraying, however, is different since the SiO2 particles experience softening rather than melting.
    [0043] The spray-dried agglomerated nanostructured powders described in the above examples have a spherical shape and narrow particle size distribution in the optimal 10-50 micron range. As such, they have superior feed characteristics in thermal spraying and also experience uniform melting behavior in the combustion flame or plasma, and the coatings formed therefrom display uniform nanostructures, negligible porosity, good substrate adhesion and excellent wear properties. In particular, coatings formed by this method from cermet materials such as WC/Co, Cr[0043] 3C2/Ni, Fe3Mo3C/Fe have novel nanostructures comprising a nanodispersion of hard carbide phase in an amorphous or nanocrystalline metal-rich matrix phase, thereby displaying superior hardness and wear resistance.
    [0044] In an alternative embodiment of this invention, nanostructured powder feeds are introduced into a thermal spray system directly after ultrasound dispersion. Suitable assynthesized nanostructured powders for the practice of this invention are those produced by any physical method, such as GCP, or by chemical processing methods, such as the IGC and CVC methods. Such powders are monodispersed and loosely agglomerated. Particle size is easily controlled over the range 3-30 nanometer range by careful adjustments of certain critical processing parameters known in the art. These loosely agglomerated powders can be readily dispersed in de-ionized water, various alcohols or liquid hydrocarbons by ultrasonic agitation to form a colloidal suspension or slurry. This nanoparticle suspension or slurry can then be introduced, along with liquid kerosene fuel, directly into the combustion zone of an HVOF gun via the liquid feed. Alternatively, the suspension or slurry may be introduced in the form of an aerosol into the gas feed of a plasma or HVOF gun. [0044]
    [0045] Characteristics of this embodiment are that the particles rapidly heat up in a short distance from the gun nozzle and almost instantaneously achieve the velocity of the gas stream, which is in the supersonic range. In some cases, the nanoparticles vaporize, prior to condensation on the cold substrate. In this case, the method becomes in effect a very high rate CVD process. [0045]
    [0046] Where applicable for an individual composition, direct nanoparticle injection by this method offers a number of advantages. First, it eliminates the need for powder reprocessing. Secondly, two or more nanoparticle feed systems, operating continuously or sequentially, can produce nanomultilayers or compositionally modulated structures, even down to nanoscale dimensions. Thirdly, the dispersion may be done in the same liquid used as the fuel for the thermal spray apparatus, e.g., kerosene. And finally, because of the short diffusion distances, very fast reactions occur between nanoparticles and the vapor species in the gas stream (e.g., carburization, nitridation and boridization). [0046]
    [0047] The direct injection method may also be used to incorporate ceramic nanostructured whiskers, hollow shells and other particulate forms into the nanocomposite coating. Hollow ceramic microspheres (1-5 microns diameter) are available commercially. More generally, mixtures of different phases and particle morphologies may be used to generate almost any desired coating structure, including whisker-reinforced and laminated nanocomposites. [0047]
    [0048] The simplicity, versatility, and scaleability of the direct nanoparticles injection method thus presents opportunities to develop new classes of thermal sprayed nanostructured coatings. Moreover, because direct injection in thermal spray apparatuses can be adapted to existing thermal spray systems, it is inherently cost effective. The following non-limiting examples illustrate the method of this embodiment for injection of as-synthesized nanostructured powders directly after ultrasonic dispersion. [0048] EXAMPLE 4
    [0049] Nanostructured ZrO[0049] 2, Al2O3, SiO2 and SiCxNy powders produced by the CVC method, or nanostructured Cr3C2/NiCr produced by the OSR process, are readily dispersed in organic liquid media to form colloidal suspensions, because of their ultra-fine particle size. Thus, these materials are ideal for direct injection of nanoparticles into the fluid stream of a typical thermal spray gun. High density coatings with amorphous and partially amorphous structures were produced from nanostructured SiO2 and nanostructured Cr3C2/NiCr powders respectively. EXAMPLE 5
    [0050] Submicron nanostructured WC/Co particles can be maintained in a highly dispersed state in a liquid phase after ultrasonic treatment provided that mechanical agitation is continuously applied. Thus, it is not necessary to form completely stable colloidal suspensions with nanostructured WC/Co powders. The coatings produced by subsequent direct injection into the combustion zone of a thermal spray gun are similar to those generated using powder agglomerates as feed materials. [0050] EXAMPLE 6
    [0051] The direct injection method was used to spray-deposit nanostructured yttria-stabilized zirconia (YSZ) coatings on pre-oxidized metal-CrAlY substrates. The coatings are preferentially compositionally graded to minimize thermal expansion mismatch stresses, which is a prerequisite to enhancing their resistance to spallation under thermal cycling conditions. [0051] EXAMPLE 7
    [0052] A novel type of thermal barrier coating (TBC) may be produced by introducing hollow ceramic microspheres into a nanostructured YSZ overlay coating, which is supported on a metal-CrAlY bond coat. Alternatively, the ceramic microspheres may be incorporated into the metal-CrAlY bond coat. In this case, a high volume fraction of microspheres is required to ensure a high thermal impedance for the coating layer. [0052] EXAMPLE 8
    [0053] When a slurry mixture of ceramic nanoparticles and hollow microspheres is introduced into a combustion flame or plasma, it is possible to selectively melt the nanoparticles while leaving the microspheres unmelted. Thus, a composite coating is developed in which the hollow ceramic spheres are bonded to the substrate by a dense nanograined ceramic coating. [0053]
    [0054] Thermal barrier coatings of nanostructured YSZ may be prepared by either the reprocessing method or by the direct injection method. In either case, the final coating may consist of either equiaxed or columnar grains, depending primarily on the particle deposition rate and temperature gradient in the deposited coating. [0054]
    [0055] In yet another embodiment of this invention, metalorganic precursor aerosols generated by an ultrasonic nozzle serve as feedstock materials for thermal spraying processing. This offers the advantage of combining of nanoparticle synthesis, melting and quenching in a single operation. Referring now to FIG. 5, liquid precursor [0055] 80 is introduced into ultrasonic nozzle 82. The nozzle sprays the resulting aerosol 84 into a plasma flame 86, generated by the passage of plasma gas over electrode 88, yielding nanoparticles 90, which may then be quenched on a substrate. For example, the metalorganic precursor hexamethyldisilazane (HMDS) was ultrasonically atomized in air and delivered to the exit nozzle of a DC plasma gun. Rapid pyrolysis of the precursor compound led to the formation of clusters or nanoparticles of nanostructured SiCxNy, which emerged as a high velocity beam from the gun. The coating formed when these hot particles impinged and coalesced on the substrate surface.
    [0056] The nanostructured coatings formed by the methods of this invention find utility in a broad range of applications. In particular, nanostructured coatings formed from hydroxyapatite or vitellium are useful in medical devices. The coatings display uniform nanostructures, negligible porosity, good substrate adhesion and excellent wear properties. In contrast to powders mixed by ball milling or mechanical blending, for example, the method of this invention allows mixing of the material's constituent elements at a molecular level. The very short diffusion distance in the direct injection embodiment allows fast reactions to occur between nanoparticles and the vapor species in the gas stream, for example, carburization, nitridation, and boridization. [0056]
    [0057] While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustrations and not limitation. [0057]
    权利要求:
    Claims (12)
    [1" id="US-20010004473-A1-CLM-00001] 1. A method of forming a nanostructured coating comprising
    (a) delivering a solution of a liquid precursor to a thermal spray device;
    (b) forming nanaostructured particles from the liquid precursor solution within the thermal spray device; and
    (c) delivering the formed nanostructured particles from the thermal spray device to a substrate, thereby forming a nanostructured coating on the substrate.
    [2" id="US-20010004473-A1-CLM-00002] 2. The method of
    claim 2 , wherein the solution of liquid precursor is a metalorganic feedstock solution.
    [3" id="US-20010004473-A1-CLM-00003] 3. The method of
    claim 2 , wherein the metalorganic feedstock is hexamethyldisilazane.
    [4" id="US-20010004473-A1-CLM-00004] 4. The method of
    claim 2 , wherein the coating is SiCxNy.
    [5" id="US-20010004473-A1-CLM-00005] 5. A method of forming a nanostructured coating comprising
    (a) atomizing a precurosr solution;
    (b) delivering the atomized solution to a plasma flame of a thermal spray device, thereby forming nanostructured particles; and
    (c) delivering the formed nanostructured particles from the thermal spray device to a substrate, thereby forming a nanostructured coating on the substrate.
    [6" id="US-20010004473-A1-CLM-00006] 6. The method of
    claim 5 , wherein the solution of liquid precursor is a metalorganic feedstock solution.
    [7" id="US-20010004473-A1-CLM-00007] 7. The method of
    claim 6 , wherein the metalorganic feedstock is hexamethyldisilazane.
    [8" id="US-20010004473-A1-CLM-00008] 8. The method of
    claim 6 , wherein the coating is SiCxNy.
    [9" id="US-20010004473-A1-CLM-00009] 9. A method of forming a nanostructured coating comprising
    (a) atomizing a solution of a liquid precursor;
    (b) delivering the atomized solution to a plasma flame in a thermal spray device;
    (c) forming nanostructured particles from the liquid precursor solution within the plasma flame; and
    (d) delivering the formed nanostructured particles from the thermal spray device to a substrate, thereby forming a nanostructured coating on the substrate.
    [10" id="US-20010004473-A1-CLM-00010] 10. The method of
    claim 9 , wherein the solution of liquid precursor is a metalorganic feedstock solution.
    [11" id="US-20010004473-A1-CLM-00011] 11. The method of
    claim 10 , wherein the metalorganic feedstock is hexamethyldisilazane.
    [12" id="US-20010004473-A1-CLM-00012] 12. The method of
    claim 9 , wherein the formed coating is SiCxNy.
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    Pelleg2021|Basic Concepts for Producing Nanomaterials
    Zou et al.2008|TEM characterization of the TiN coatings fabricated by reactive plasma spraying
    Vaishnavi et al.0|Cermet Based Nanocomposites for Automotive Body Frame
    McCandlish1993|Chemical processing of nanostructured materials
    Ground et al.0|Novel Cold Spray Nanostructured Aluminum
    同族专利:
    公开号 | 公开日
    CN1195884C|2005-04-06|
    WO1997018341A1|1997-05-22|
    EP0866885A1|1998-09-30|
    EP0866885A4|2000-09-20|
    CN1175984A|1998-03-11|
    US20030077398A1|2003-04-24|
    RU2196846C2|2003-01-20|
    US6025034A|2000-02-15|
    US6579573B2|2003-06-17|
    CA2237588A1|1997-05-22|
    US6277448B2|2001-08-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20030180796A1|1997-08-26|2003-09-25|Genentech, Inc.|Secreted and transmembrane polypeptides and nucleic acids encoding the same|
    US20050235493A1|2004-04-22|2005-10-27|Siemens Westinghouse Power Corporation|In-frame repair of gas turbine components|
    EP1741826A1|2005-07-08|2007-01-10|Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO|Method for depositing a polymer layer containing nanomaterial on a substrate material and apparatus|
    US7416108B2|2002-01-24|2008-08-26|Siemens Power Generation, Inc.|High strength diffusion brazing utilizing nano-powders|
    US20080220373A1|2007-03-07|2008-09-11|Samsung Electro-Mechanics Co., Ltd.|Method for forming a photoresist-laminated substrate, method for plating an insulating substrate, method for surface treating of a metal layer of a circuit board, and method for manufacturing a multi layer ceramic condenser using metal nanoparticles aerosol|
    US20080241570A1|2007-03-26|2008-10-02|Howmedica Osteonics Corp.|Method for fabricating a medical component from a material having a high carbide phase and such medical component|
    US20090173467A1|2006-05-19|2009-07-09|Metso Paper, Inc.|Static Dewatering Element for a Web Forming Machine and a Method for Covering a Static Dewatering Element Designed for a Web Forming Machine|
    US20090324442A1|2007-03-26|2009-12-31|Howmedica Osteonics Corp.|Method for fabricating a biocompatible material having a high carbide phase and such material|
    US20110207333A1|2004-11-24|2011-08-25|Felix Mayer|Method for applying a layer to a substrate|
    US20130332362A1|2012-06-11|2013-12-12|Visa International Service Association|Systems and methods to customize privacy preferences|
    US20160082404A1|2014-09-19|2016-03-24|NanoSynthesis Plus, Ltd.|Methods and apparatuses for producing dispersed nanostructures|
    US9999721B2|2015-05-26|2018-06-19|Medtronic Minimed, Inc.|Error handling in infusion devices with distributed motor control and related operating methods|
    CN110129711A|2019-06-28|2019-08-16|沈阳富创精密设备有限公司|A kind of heat spraying method of novel prepares coating|
    CN112063959A|2020-08-06|2020-12-11|西安交通大学|Column-layer/tree composite structure thermal barrier coating and preparation method thereof|US3419415A|1964-09-29|1968-12-31|Metco Inc|Composite carbide flame spray material|
    US3617358A|1967-09-29|1971-11-02|Metco Inc|Flame spray powder and process|
    JPH0324255B2|1985-05-17|1991-04-02|Mitsubishi Materiaru Kk||
    JPS63121647A|1986-11-12|1988-05-25|Mitsubishi Heavy Ind Ltd|Method for coating yttria-stabilized zirconia film|
    SU1463799A1|1987-06-12|1989-03-07|Московский институт тонкой химической технологии|Method of producing charge for gas-flame coatings|
    US4982067A|1988-11-04|1991-01-01|Marantz Daniel Richard|Plasma generating apparatus and method|
    US5688565A|1988-12-27|1997-11-18|Symetrix Corporation|Misted deposition method of fabricating layered superlattice materials|
    US5213851A|1990-04-17|1993-05-25|Alfred University|Process for preparing ferrite films by radio-frequency generated aerosol plasma deposition in atmosphere|
    US5155071A|1991-08-16|1992-10-13|E. I. Du Pont De Nemours And Company|Flame-produced partially stabilized zirconia powder|
    AT233327T|1993-03-24|2003-03-15|Georgia Tech Res Inst|METHOD AND DEVICE FOR COMBUSTION CVD OF FILMS AND COATINGS|
    DE4334639A1|1993-10-11|1995-04-13|Inst Neue Mat Gemein Gmbh|Process for the production of TiN sintered bodies and layers|
    DE4402890A1|1994-02-01|1995-08-03|Basf Ag|Process for the production of compositions containing metal particles in the nanometer size range|
    US5609921A|1994-08-26|1997-03-11|Universite De Sherbrooke|Suspension plasma spray|
    US5874134A|1996-01-29|1999-02-23|Regents Of The University Of Minnesota|Production of nanostructured materials by hypersonic plasma particle deposition|
    US5932293A|1996-03-29|1999-08-03|Metalspray U.S.A., Inc.|Thermal spray systems|
    US5986277A|1997-10-29|1999-11-16|National Research Council Of Canada|Method and apparatus for on-line monitoring the temperature and velocity of thermally sprayed particles|
    US6071324A|1998-05-28|2000-06-06|Sulzer Metco Inc.|Powder of chromium carbide and nickel chromium|US6447848B1|1995-11-13|2002-09-10|The United States Of America As Represented By The Secretary Of The Navy|Nanosize particle coatings made by thermally spraying solution precursor feedstocks|
    US6933331B2|1998-05-22|2005-08-23|Nanoproducts Corporation|Nanotechnology for drug delivery, contrast agents and biomedical implants|
    US6433154B1|1997-06-12|2002-08-13|Bristol-Myers Squibb Company|Functional receptor/kinase chimera in yeast cells|
    WO1999010120A1|1997-08-22|1999-03-04|Inframat Corporation|Grain growth inhibitor for nanostructured materials|
    US20080311306A1|1997-08-22|2008-12-18|Inframat Corporation|Superfine ceramic thermal spray feedstock comprising ceramic oxide grain growth inhibitor and methods of making|
    US6630257B2|1998-06-10|2003-10-07|U.S. Nanocorp.|Thermal sprayed electrodes|
    US6653519B2|1998-09-15|2003-11-25|Nanoscale Materials, Inc.|Reactive nanoparticles as destructive adsorbents for biological and chemical contamination|
    US6926997B2|1998-11-02|2005-08-09|Sandia Corporation|Energy storage and conversion devices using thermal sprayed electrodes|
    US6689453B2|1998-11-24|2004-02-10|Research Foundation Of State University Of New York|Articles with nanocomposite coatings|
    US6258417B1|1998-11-24|2001-07-10|Research Foundation Of State University Of New York|Method of producing nanocomposite coatings|
    US6524744B1|1998-12-07|2003-02-25|T/J Technologies, Inc.|Multi-phase material and electrodes made therefrom|
    US6235351B1|1999-01-22|2001-05-22|Northrop Grumman Corporation|Method for producing a self decontaminating surface|
    US6881604B2|1999-05-25|2005-04-19|Forskarpatent I Uppsala Ab|Method for manufacturing nanostructured thin film electrodes|
    US6689424B1|1999-05-28|2004-02-10|Inframat Corporation|Solid lubricant coatings produced by thermal spray methods|
    US6723387B1|1999-08-16|2004-04-20|Rutgers University|Multimodal structured hardcoatings made from micro-nanocomposite materials|
    WO2001012431A1|1999-08-16|2001-02-22|Rutgers, The State University|Multimodal structured hardcoatings made from micro-nanocomposite materials|
    US20070044513A1|1999-08-18|2007-03-01|Kear Bernard H|Shrouded-plasma process and apparatus for the production of metastable nanostructured materials|
    US6517995B1|1999-09-14|2003-02-11|Massachusetts Institute Of Technology|Fabrication of finely featured devices by liquid embossing|
    DE19958474A1|1999-12-04|2001-06-21|Bosch Gmbh Robert|Process for producing functional layers with a plasma beam source|
    DE19958473A1|1999-12-04|2001-06-07|Bosch Gmbh Robert|Process for the production of composite layers with a plasma beam source|
    US6794086B2|2000-02-28|2004-09-21|Sandia Corporation|Thermally protective salt material for thermal spraying of electrode materials|
    US6359325B1|2000-03-14|2002-03-19|International Business Machines Corporation|Method of forming nano-scale structures from polycrystalline materials and nano-scale structures formed thereby|
    EP1134302A1|2000-03-17|2001-09-19|Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grande Interfase, C.S.G.I|New process for the production of nanostructured solid powders and nano-particles films by compartimentalised solution thermal spraying |
    US7247338B2|2001-05-16|2007-07-24|Regents Of The University Of Minnesota|Coating medical devices|
    CN1830536A|2000-05-16|2006-09-13|明尼苏达大学评议会|High mass throughput particle generation using multiple nozzle spraying|
    US6494932B1|2000-06-06|2002-12-17|Birch Mountain Resources, Ltd.|Recovery of natural nanoclusters and the nanoclusters isolated thereby|
    EP1301341B1|2000-06-30|2006-08-23|nGimat Co.|Method for applying polymer coatings|
    US6638575B1|2000-07-24|2003-10-28|Praxair Technology, Inc.|Plasma sprayed oxygen transport membrane coatings|
    US6428596B1|2000-11-13|2002-08-06|Concept Alloys, L.L.C.|Multiplex composite powder used in a core for thermal spraying and welding, its method of manufacture and use|
    US6513728B1|2000-11-13|2003-02-04|Concept Alloys, L.L.C.|Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use|
    US6674047B1|2000-11-13|2004-01-06|Concept Alloys, L.L.C.|Wire electrode with core of multiplex composite powder, its method of manufacture and use|
    DE10057953A1|2000-11-22|2002-06-20|Eduard Kern|Thermally sprayed ceramic composite layers consist of nanocrystalline crystals and a coating of aluminum oxide and silicon carbide, in which the silicon carbide grains are homogeneously distributed in the aluminum oxide matrix|
    EP1339533B1|2000-12-08|2012-05-09|Sulzer MetcoInc.|Pre-alloyed stabilized zirconia powder and improved thermal barrier coating|
    DE10061749C2|2000-12-12|2003-08-07|Federal Mogul Burscheid Gmbh|Piston ring for internal combustion engines|
    US7066977B2|2001-05-02|2006-06-27|Fu-Kuo Huang|Flame synthesis and non-vacuum physical evaporation|
    JP3812368B2|2001-06-06|2006-08-23|豊田合成株式会社|Group III nitride compound semiconductor device and method for manufacturing the same|
    US7201940B1|2001-06-12|2007-04-10|Advanced Cardiovascular Systems, Inc.|Method and apparatus for thermal spray processing of medical devices|
    US6974640B2|2001-07-09|2005-12-13|The University Of Connecticut|Duplex coatings and bulk materials, and methods of manufacture thereof|
    US20070134432A1|2002-07-09|2007-06-14|Maurice Gell|Methods of making duplex coating and bulk materials|
    US6630207B1|2001-07-17|2003-10-07|Science Applications International Corporation|Method and apparatus for low-pressure pulsed coating|
    WO2003022741A2|2001-09-12|2003-03-20|F.W. Gartner Thermal Spraying Company|Nanostructured titania coated titanium|
    US6730616B2|2001-09-24|2004-05-04|Texas Instruments Incorporated|Versatile plasma processing system for producing oxidation resistant barriers|
    US6936181B2|2001-10-11|2005-08-30|Kovio, Inc.|Methods for patterning using liquid embossing|
    US20090004296A1|2006-01-04|2009-01-01|Do-Coop Technologies Ltd.|Antiseptic Compositions and Methods of Using Same|
    EP1468143A1|2002-01-15|2004-10-20|Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grande Interfase, C.S.G.I|Basic suspension, its preparation and process for paper deacidification|
    US20040018409A1|2002-02-28|2004-01-29|Shiqiang Hui|Solid oxide fuel cell components and method of manufacture thereof|
    US6787194B2|2002-04-17|2004-09-07|Science Applications International Corporation|Method and apparatus for pulsed detonation coating of internal surfaces of small diameter tubes and the like|
    US6755886B2|2002-04-18|2004-06-29|The Regents Of The University Of California|Method for producing metallic microparticles|
    WO2003090937A1|2002-04-24|2003-11-06|Wisconsin Alumni Research Foundation|Apparatus and method of fabricating small-scale devices|
    US7316748B2|2002-04-24|2008-01-08|Wisconsin Alumni Research Foundation|Apparatus and method of dispensing small-scale powders|
    US7160577B2|2002-05-02|2007-01-09|Micron Technology, Inc.|Methods for atomic-layer deposition of aluminum oxides in integrated circuits|
    US7279129B2|2002-05-14|2007-10-09|Nanoscale Corporation|Method and apparatus for control of chemical or biological warfare agents|
    US20030219544A1|2002-05-22|2003-11-27|Smith William C.|Thermal spray coating process with nano-sized materials|
    US20040012124A1|2002-07-10|2004-01-22|Xiaochun Li|Apparatus and method of fabricating small-scale devices|
    FR2842750B1|2002-07-26|2004-10-08|Toulouse Inst Nat Polytech|PROCESS FOR COVERING SURFACES AT LOW TEMPERATURES WITH NANOCRYSTALLINE APATITIC PHOSPHATES FROM AN AQUEOUS AMORPHOUS PHOSPHATE SUSPENSION|
    US6957608B1|2002-08-02|2005-10-25|Kovio, Inc.|Contact print methods|
    US6878184B1|2002-08-09|2005-04-12|Kovio, Inc.|Nanoparticle synthesis and the formation of inks therefrom|
    GB2393452B|2002-08-28|2005-12-28|C A Technology Ltd|Improvements to powder production and spraying|
    US7258934B2|2002-09-25|2007-08-21|Volvo Aero Corporation|Thermal barrier coating and a method of applying such a coating|
    US6924249B2|2002-10-02|2005-08-02|Delphi Technologies, Inc.|Direct application of catalysts to substrates via a thermal spray process for treatment of the atmosphere|
    EP1422308B1|2002-11-22|2008-03-26|Sulzer MetcoInc.|Spray powder for manufacturing by thermal spraying of a thermal barrier coating being stable at high temperatures|
    DE50309456D1|2002-11-22|2008-05-08|Sulzer Metco Us Inc|Spray powder for the production of a high temperature resistant thermal barrier coating by means of a thermal spray process|
    US7078276B1|2003-01-08|2006-07-18|Kovio, Inc.|Nanoparticles and method for making the same|
    WO2004063416A2|2003-01-10|2004-07-29|Inframat Corporation|Apparatus and method for solution plasma spraying|
    US7563503B2|2003-01-10|2009-07-21|The University Of Connecticut|Coatings, materials, articles, and methods of making thereof|
    BRPI0407007A|2003-01-28|2006-01-10|Enviroscrub Technologies Corp|Method and system for fast and adaptable processing of manganese oxides and integrated sorbent processing and pollution control system|
    US6942897B2|2003-02-19|2005-09-13|The Board Of Trustees Of Western Michigan University|Nanoparticle barrier-coated substrate and method for making the same|
    US20040202789A1|2003-03-31|2004-10-14|Council Of Scientific And Industrila Research|Process for preparing thin film solids|
    US7488464B2|2003-07-31|2009-02-10|Enviroscrub Technologies Corporation|Metal oxide processing methods and systems|
    US8083907B1|2003-09-26|2011-12-27|University Of South Florida|Hydrogen storage nano-foil and method of manufacture|
    JP2007507604A|2003-09-29|2007-03-29|ゼネラル・エレクトリック・カンパニイ|Nanostructured coating systems, components and related manufacturing methods|
    DE10357535A1|2003-12-10|2005-07-07|Mtu Aero Engines Gmbh|Ceramic material and method for repairing thermal barrier coatings with local damage|
    KR100743188B1|2003-12-26|2007-07-27|재단법인 포항산업과학연구원|Manufacturing Method Nano-Structured Super-High Hardness WC-Co Coating|
    US20080260952A1|2004-01-22|2008-10-23|The University Of Manchester|Ceramic Coating|
    WO2005071141A1|2004-01-22|2005-08-04|The University Of Manchester|Ceramic coating|
    US7635515B1|2004-04-08|2009-12-22|Powdermet, Inc|Heterogeneous composite bodies with isolated lenticular shaped cermet regions|
    US8334079B2|2004-04-30|2012-12-18|NanoCell Systems, Inc.|Metastable ceramic fuel cell and method of making the same|
    US20050282032A1|2004-06-18|2005-12-22|General Electric Company|Smooth outer coating for combustor components and coating method therefor|
    DE102004030523A1|2004-06-18|2006-01-12|Siemens Ag|Transport system for nanoparticles and method for its operation|
    EP1809793A2|2004-09-27|2007-07-25|Auburn University|Selection and deposition of nanoparticles using co2-expanded liquids|
    FR2877015B1|2004-10-21|2007-10-26|Commissariat Energie Atomique|NANOSTRUCTURE COATING AND COATING PROCESS.|
    US20060251821A1|2004-10-22|2006-11-09|Science Applications International Corporation|Multi-sectioned pulsed detonation coating apparatus and method of using same|
    DE102004053221B3|2004-11-04|2006-02-02|Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken|Liquid and its use for the treatment of hard metals|
    KR100601096B1|2004-11-08|2006-07-19|재단법인 포항산업과학연구원|METHOD FOR MANUFACTURING NANO-STRUCTURED WC-Co POWDERS FOR THERMAL SPRAY COATING|
    US7402347B2|2004-12-02|2008-07-22|Siemens Power Generation, Inc.|In-situ formed thermal barrier coating for a ceramic component|
    US20060184251A1|2005-01-07|2006-08-17|Zongtao Zhang|Coated medical devices and methods of making and using|
    US20060172141A1|2005-01-27|2006-08-03|Xinyu Huang|Joints and methods of making and using|
    CA2499202A1|2005-03-01|2006-09-01|National Research Council Of Canada|Biocompatible titania thermal spray coating made from a nanostructured feedstock|
    JP4518410B2|2005-03-09|2010-08-04|エボニックデグサゲーエムベーハー|Plasma sprayed aluminum oxide layer|
    EP1700926A1|2005-03-09|2006-09-13|Degussa AG|Plasma-sprayed alumina layers|
    EP1707651A1|2005-03-31|2006-10-04|Siemens Aktiengesellschaft|Coating system and process of manufacturing a coating system|
    US20060222777A1|2005-04-05|2006-10-05|General Electric Company|Method for applying a plasma sprayed coating using liquid injection|
    US8058188B2|2005-04-13|2011-11-15|Albany International Corp|Thermally sprayed protective coating for industrial and engineered fabrics|
    US8629371B2|2005-05-02|2014-01-14|National Research Council Of Canada|Method and apparatus for fine particle liquid suspension feed for thermal spray system and coatings formed therefrom|
    KR100684275B1|2005-05-11|2007-02-20|한국과학기술원|Thin or Thick Film deposition Unit Using Electrospray-assisted Combustion CVD|
    DE102006019137A1|2005-05-17|2007-10-31|Wolfgang Dr.-Ing. Beck|Coating material for in-mold coatingbased on an amino-functional reaction partner for isocyanates and process for the preparation|
    DE102005025054A1|2005-05-30|2006-12-07|Forschungszentrum Jülich GmbH|Process for producing gas-tight layers and layer systems by means of thermal spraying|
    US20060275542A1|2005-06-02|2006-12-07|Eastman Kodak Company|Deposition of uniform layer of desired material|
    GB0512666D0|2005-06-22|2005-07-27|Univ Loughborough|Method for concentrating nanosuspensions|
    US7927948B2|2005-07-20|2011-04-19|Micron Technology, Inc.|Devices with nanocrystals and methods of formation|
    DE102005036309A1|2005-08-02|2007-02-08|Linde Ag|Introduction of nanoparticles|
    DE102005038453B4|2005-08-03|2011-06-09|TTI-Technologie-Transfer-Initiative GmbH an der Universität Stuttgart|Method and device for thermal spraying of suspensions|
    US7575978B2|2005-08-04|2009-08-18|Micron Technology, Inc.|Method for making conductive nanoparticle charge storage element|
    US7989290B2|2005-08-04|2011-08-02|Micron Technology, Inc.|Methods for forming rhodium-based charge traps and apparatus including rhodium-based charge traps|
    US8518123B2|2005-09-09|2013-08-27|Board Of Trustees Of The University Of Arkansas|System and method for tissue generation and bone regeneration|
    US9763788B2|2005-09-09|2017-09-19|Board Of Trustees Of The University Of Arkansas|Bone regeneration using biodegradable polymeric nanocomposite materials and applications of the same|
    US8936805B2|2005-09-09|2015-01-20|Board Of Trustees Of The University Of Arkansas|Bone regeneration using biodegradable polymeric nanocomposite materials and applications of the same|
    US9399234B2|2005-10-17|2016-07-26|National Research Council Of Canada|Reactive spray formation of coatings and powders|
    US20070099014A1|2005-11-03|2007-05-03|Sulzer Metco , Inc.|Method for applying a low coefficient of friction coating|
    CN1962155A|2005-11-10|2007-05-16|鸿富锦精密工业（深圳）有限公司|CO2 laser welding apparatus|
    US7579087B2|2006-01-10|2009-08-25|United Technologies Corporation|Thermal barrier coating compositions, processes for applying same and articles coated with same|
    CA2637883C|2006-01-31|2015-07-07|Regents Of The University Of Minnesota|Electrospray coating of objects|
    US9108217B2|2006-01-31|2015-08-18|Nanocopoeia, Inc.|Nanoparticle coating of surfaces|
    CA2641117C|2006-01-31|2018-01-02|Nanocopoeia, Inc.|Nanoparticle coating of surfaces|
    DE102006005775A1|2006-02-07|2007-08-09|Forschungszentrum Jülich GmbH|Thermal spraying with colloidal suspension|
    IL175045D0|2006-04-20|2006-09-05|Joma Int As|A coating formed by thermal spraying and methods for the formation thereof|
    FR2900351B1|2006-04-26|2008-06-13|Commissariat Energie Atomique|PROCESS FOR PREPARING A NANOPOROUS LAYER OF NANOPARTICLES AND THE LAYER THUS OBTAINED|
    CN101588826A|2006-08-02|2009-11-25|英孚拉玛特公司|Lumen-supporting devices and methods of making and using|
    WO2008016712A2|2006-08-02|2008-02-07|Inframat Corporation|Medical devices and methods of making and using|
    ES2534215T3|2006-08-30|2015-04-20|Oerlikon Metco Ag, Wohlen|Plasma spray device and a method for introducing a liquid precursor into a plasma gas system|
    EP1895818B1|2006-08-30|2015-03-11|Sulzer Metco AG|Plasma spraying device and a method for introducing a liquid precursor into a plasma gas system|
    US20080072790A1|2006-09-22|2008-03-27|Inframat Corporation|Methods of making finely structured thermally sprayed coatings|
    DE102006047101B4|2006-09-28|2010-04-01|Siemens Ag|Method for feeding particles of a layer material into a cold gas spraying process|
    US9149750B2|2006-09-29|2015-10-06|Mott Corporation|Sinter bonded porous metallic coatings|
    US20080081007A1|2006-09-29|2008-04-03|Mott Corporation, A Corporation Of The State Of Connecticut|Sinter bonded porous metallic coatings|
    EP1911858B1|2006-10-02|2012-07-11|Sulzer Metco AG|Process of manufacturing of a coating with columnar structure|
    WO2008049080A1|2006-10-18|2008-04-24|Inframat Corporation|Superfine/nanostructured cored wires for thermal spray applications and methods of making|
    US20080138538A1|2006-12-06|2008-06-12|General Electric Company|Barrier layer, composite article comprising the same, electroactive device, and method|
    US7781031B2|2006-12-06|2010-08-24|General Electric Company|Barrier layer, composite article comprising the same, electroactive device, and method|
    US20080138624A1|2006-12-06|2008-06-12|General Electric Company|Barrier layer, composite article comprising the same, electroactive device, and method|
    US9040816B2|2006-12-08|2015-05-26|Nanocopoeia, Inc.|Methods and apparatus for forming photovoltaic cells using electrospray|
    US8465602B2|2006-12-15|2013-06-18|Praxair S. T. Technology, Inc.|Amorphous-nanocrystalline-microcrystalline coatings and methods of production thereof|
    US20080166493A1|2007-01-09|2008-07-10|Inframat Corporation|Coating compositions for marine applications and methods of making and using the same|
    CA2619331A1|2007-01-31|2008-07-31|Scientific Valve And Seal, Lp|Coatings, their production and use|
    US8367506B2|2007-06-04|2013-02-05|Micron Technology, Inc.|High-k dielectrics with gold nano-particles|
    KR100981368B1|2007-06-25|2010-09-10|한국과학기술연구원|Tungsten composite powders, coated materials formed from the same and method for manufacturing the tungsten composite powders|
    US8530000B2|2007-09-19|2013-09-10|Micron Technology, Inc.|Methods of forming charge-trapping regions|
    US7763325B1|2007-09-28|2010-07-27|The United States Of America As Represented By The National Aeronautics And Space Administration|Method and apparatus for thermal spraying of metal coatings using pulsejet resonant pulsed combustion|
    US20110003084A1|2008-02-25|2011-01-06|National Research Council Of Canada|Process of Making Ceria-Based Electrolyte Coating|
    DE102008001721B4|2008-05-13|2021-01-14|Voith Patent Gmbh|Method of coating a blade|
    DE102008026101B4|2008-05-30|2010-02-18|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Thermally sprayed Al 2 O 3 layers with a high content of corundum without property-reducing additives and process for their preparation|
    US20100068405A1|2008-09-15|2010-03-18|Shinde Sachin R|Method of forming metallic carbide based wear resistant coating on a combustion turbine component|
    KR101110588B1|2009-04-22|2012-02-15|한국세라믹기술원|Method and Apparatus depositing trans-phase aerosol|
    FR2947568B1|2009-07-02|2011-07-22|Snecma|THERMAL PROTECTION COATING FOR A TURBOMACHINE PART AND METHOD FOR PRODUCING THE SAME|
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    优先权:
    申请号 | 申请日 | 专利标题
    US55813395A| true| 1995-11-13|1995-11-13||
    US09/019,061|US6025034A|1995-11-13|1998-02-05|Method of manufacture of nanostructured feeds|
    US09/325,822|US6277448B2|1995-11-13|1999-06-04|Thermal spray method for the formation of nanostructured coatings|US09/325,822| US6277448B2|1995-11-13|1999-06-04|Thermal spray method for the formation of nanostructured coatings|
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