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US20080078268A1 - Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof - Google Patents

Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof Download PDF

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Publication number
US20080078268A1
US20080078268A1 US11/542,055 US54205506A US2008078268A1 US 20080078268 A1 US20080078268 A1 US 20080078268A1 US 54205506 A US54205506 A US 54205506A US 2008078268 A1 US2008078268 A1 US 2008078268A1
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Prior art keywords
powder
ppm
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metal
bar
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US11/542,055
Inventor
Leonid N. Shekhter
Rong-Chein Richard Wu
Steven A. Miller
Leah F. Haywiser
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Glas Trust Corp Ltd
Materion Newton Inc
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HC Starck Inc
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Priority to US11/542,055 priority Critical patent/US20080078268A1/en
Application filed by HC Starck Inc filed Critical HC Starck Inc
Priority to EP07843733A priority patent/EP2073947A2/en
Priority to CN2007800364699A priority patent/CN101522342B/en
Priority to PCT/US2007/080282 priority patent/WO2008042947A2/en
Priority to CA002664334A priority patent/CA2664334A1/en
Priority to US12/444,263 priority patent/US8226741B2/en
Priority to RU2009116616/02A priority patent/RU2009116616A/en
Publication of US20080078268A1 publication Critical patent/US20080078268A1/en
Assigned to H.C. STARCK INC. reassignment H.C. STARCK INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAYWISER, LEAH F., MILLER, STEVEN A., SHEKHTER, LEONID N., WU, RONG-CHEIN RICHARD
Priority to US13/529,148 priority patent/US8715386B2/en
Assigned to GLAS TRUST CORPORATION LIMITED reassignment GLAS TRUST CORPORATION LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COMMERZBANK AKTIENGESELLSCHAFT, FILIALE LUXEMBOURG, AS SECURITY AGENT FOR THE BENEFIT OF SECOND LIEN SECURED PARTIES
Assigned to GLAS TRUST CORPORATION LIMITED reassignment GLAS TRUST CORPORATION LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COMMERZBANK AKTIENGESELLSCHAFT, FILIALE LUXEMBOURG, AS SECURITY AGENT FOR THE BENEFIT OF SENIOR SECURED PARTIES
Assigned to GLAS TRUST CORPORATION LIMITED reassignment GLAS TRUST CORPORATION LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COMMERZBANK AKTIENGESELLSCHAFT, FILIALE LUXEMBOURG, AS SECURITY AGENT FOR THE BENEFIT OF MEZZANINE SECURED PARTIES
Assigned to H.C. STARCK INC. reassignment H.C. STARCK INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GLAS TRUST CORPORATION LIMITED
Assigned to H.C. STARCK INC. reassignment H.C. STARCK INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GLAS TRUST CORPORATION LIMITED
Assigned to H.C. STARCK INC. reassignment H.C. STARCK INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: GLAS TRUST CORPORATION LIMITED
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/12—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/30—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant
    • B05D2401/32—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant applied as powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • Passive oxide layers are inherent to all metal powders. In general, the presence of such oxides has an adverse effect on one or more of the properties of the products made from such powders.
  • tantalum due to the high melting point of tantalum, its purification method yields a metal powder.
  • tantalum oxidizes and forms an oxide layer, which protects it from further oxidation.
  • this powder In order to make metal parts, this powder must be consolidated to solid form. Due to the inherent stability of this oxide layer, when pressed and sintered into a powder metallurgy form, the oxygen is conserved, yielding a lower quality product. Therefore the oxygen removal becomes a primary objective for tantalum refining.
  • oxygen removal is called deoxidation.
  • deoxidation There is quite a bit of art teaching various ways of removing oxygen.
  • One way to avoid this oxygen is to electron beam melt the powder, vaporizing the oxygen, resulting in an ingot with only the ingot's passive layer of oxygen.
  • a second known method for removal of oxygen from tantalum is using another element to reduce Ta 2 O 5
  • One element that can be used is carbon (see, e.g., U.S. Pat. No. 6,197,082). However, since excess carbon is used for reduction, tantalum, carbides result as a contaminant.
  • U.S. Pat. No. 4,537,641 suggests using magnesium, calcium, or aluminum as the reductant (see also U.S. Pat. Nos. 5,954,856 and 6,136,062). These metals can be then leached out of the tantalum with water and diluted mineral acid.
  • European Patent 1,066,899 suggests purifying tantalum powder in thermal plasma. The process was carried out at atmospheric pressure, at the temperatures exceeding the melting point of tantalum in the presence of hydrogen. The resulting powder had spherical morphology and the oxygen concentration as low as 86 ppm.
  • Cold spray technology is the process by which materials are deposited as a solid onto a substrate without melting.
  • the coating particles are typically heated by carrier gas to only a few hundred degrees Celsius, and are traveling at a supersonic velocity typically in the range of 500 to 1500 meters per second prior to impact with the substrate.
  • the ability to cold spray different materials is determined by their ductility, the measure of a material's ability to undergo appreciable plastic deformation. The more ductile the raw materials, the better the adhesion attained during the cold-spray process due to its ability to deform.
  • refractory metals In the family of refractory metals, currently only tantalum and niobium are used, as they are the softest of the refractory metals. Other refractory metals such as molybdenum, hafnium, zirconium, and particularly tungsten are considered brittle, and therefore cannot plastically deform and adhere upon impact during cold spray.
  • DBTT ductile-to-brittle transition temperature
  • the present invention is directed to the discovery that the oxygen content can be drastically reduced by creating conditions at which the refractory oxide species become thermodynamically unstable, and removed by volatilization.
  • the main challenge was to find the thermodynamic parameters (temperature and total pressure) at which the oxide species became unstable and volatilize while the metal species will continue to stay in the condensed phase.
  • the present invention is broadly directed to a process for the preparation of a metal powder having a purity of at least as high as the starting powder and having an oxygen content of 10 ppm or less comprising heating the metal powder containing oxygen in the form of an oxide, with the total oxygen content being from 50 to 3000 ppm, in an inert atmosphere at a pressure of from 1 bar to 10 ⁇ 7 to a temperature at which the oxide of the metal powder becomes thermodynamically unstable and removing the resulting oxygen via volatilization.
  • the process has the additional advantage of significantly reducing and/or removing any metallic impurities having boiling points lower than that which the oxide of the metal powder becomes thermodynamically unstable.
  • the metal powder is preferably selected from the group consisting of tantalum, niobium, molybdenum, hafnium, zirconium, titanium, vanadium, rhenium and tungsten.
  • the inert atmosphere can be substantially any “inert” gas, such as argon, helium, neon, krypton or xenon.
  • the metal powder is tantalum
  • such powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10 ⁇ 7 bar and a temperature of from about 1700° C. to about 3800° C.
  • the resultant unpassivated powder has a purity of at least as high as the starting powder, and preferably at least 99.9%, a surface area of from about 100 cm 2 /g to about 10,000 cm 2 /g, an oxygen content of 10 ppm or less, a hydrogen content of 1 ppm or less, a magnesium content of 1 ppm or less, an alkali metal content of 1 ppm or less, and a combined iron plus nickel plus chromium content of 1 ppm or less.
  • the process has the advantage of significantly reducing any metallic impurities (such as alkali metals, magnesium, iron, nickel and chromium) having boiling points lower than the temperature at which the tantalum oxide becomes thermodynamically unstable.
  • the metal powder is niobium
  • such powder is heated in an inert gas atmosphere at a pressure of from 10 ⁇ 3 bar to 10 ⁇ 7 bar and a temperature of from about 1750° C. to about 3850° C.
  • the resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm 2 /g to about 10,000 cm 2 /g, an oxygen content of 10 ppm or less, a hydrogen content of 1 ppm or less, a magnesium content of 1 ppm or less, an alkali metal content of 1 ppm or less, and a combined iron plus nickel plus chromium content of 1 ppm or less.
  • the metal powder is tungsten
  • such powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10 ⁇ 7 bar and a temperature of from about 1200° C. to about 1800° C.
  • the resultant unpassivated powder has a purity of at least of as high as the starting powder, a surface area of from about 100 cm 2 /g to about 10,000 cm 2 /g, an oxygen content of 5 ppm or less, a carbon content of 5 ppm or less and a hydrogen content of 1 ppm or less.
  • the metal powder is molybdenum
  • such powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10 ⁇ 7 bar and a temperature of from about 1450° C. to about 2300° C.
  • the resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm 2 /g to about 10,000 cm 2 /g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • the metal powder is titanium
  • such powder is heated in an inert gas atmosphere at a pressure of from 10 ⁇ 3 bar to 10 ⁇ 7 bar and a temperature of from about 1800° C. to about 2500° C.
  • the resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm 2 /g to about 10,000 cm 2 /g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • the metal powder is zirconium
  • such powder is heated in an inert gas atmosphere at a pressure of from 10 ⁇ 3 bar to 10 ⁇ 7 bar and a temperature of from about 2300° C. to about 2900° C.
  • the resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm 2 /g to about 10,000 cm 2 /g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • the metal powder is hafnium
  • such powder is heated in an inert gas atmosphere at a pressure of from 10 ⁇ 3 bar to 10 ⁇ 7 bar and a temperature of from about 2400° C. to about 3200° C.
  • the resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm 2 /g to about 10,000 cm 2 /g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • the range of temperatures described above can usually be reached using the gas plasma process.
  • the temperature in the plasma flame is not constant; due to the particle size distribution, it may not be possible to heat all particles to the set temperature. Since the residence time in the plasma flame is extremely short, the particles inherently will be at different temperatures. Therefore, there is a potential to underheat the coarse particles (not enough volatilization) and overheat the fine particles (excessive volatilization, not only of the metal oxide but also the metal itself). It is, however, not the only means of reaching the desired temperature range. For example, the induction melting can be also used.
  • the requirements of temperature and pressure can be met by using vacuum plasma technique, or other equipment such as electric-resistant furnace, rotary kiln, induction furnace, e-beam furnace in high vacuum and the like.
  • the equipment that is preferable is one that is capable of vacuum and allows flexible residence time.
  • the process of the invention allows for the production of a metal powder with very low oxygen content typical of the consolidated solid metal. This was made possible due to the application of the process requiring no reducing agent.
  • the prior art used either magnesium or hydrogen for the reduction of oxygen and therefore, the product (powder) had to be passivated (exposed to air) prior to its further usage.
  • Processing metal powders under the conditions described has the additional advantage of significantly reducing and/or removing any metallic impurities having boiling points lower than that which the oxide of the metal powder becomes thermodynamically unstable (e.g., depending upon the starting metal powder, such impurities as iron, nickel, chromium, sodium, boron, phosphorous, nitrogen and hydrogen may be significantly reduced).
  • impurities as iron, nickel, chromium, sodium, boron, phosphorous, nitrogen and hydrogen may be significantly reduced.
  • the nitrogen content will be reduced to 20 ppm or less and the phosphorous content will be reduced to 10 ppm or less.
  • Another reaction that will occur under these conditions would be the removal of carbon due to the reaction of the carbide with the oxide. This is particularly important in the case of tungsten, even small amounts of oxygen and carbon can make the tungsten brittle. It is critical to reduce carbon (to a level of 5 ppm or less) and oxygen (to a level of 5 ppm or less) from tungsten to a level at
  • the powder particles produced via the process of the invention have virtually the same low oxygen content regardless of their size. Furthermore, the obtained powder has this low oxygen content regardless of its surface area. Depending on the total pressure, the powder may or may not have to be melted.
  • the powder may be used as a raw material for the ensuing operations without removal of either fine or coarse fraction. Powder can be produced in different types of furnaces including but not limited to plasma, induction, or any resistance furnace capable of working under vacuum.
  • the process of the invention is a relatively low cost process since it does not require any reducing agent, is a one step process, does not call for the product passivation, does not require screening out powder fractions, and could be run continuously. Moreover, due to the low oxygen and other impurities content, the obtained powder will be of superior grade quality.
  • the result of the present invention is the drastic reduction of the oxygen and carbon contents, for example, that would increase the ductility of the previously unusable refractory metals, and make them potentially usable. This would potentially expand the usage of previously high DBTT metals.
  • the products of the present invention and blends thereof can be used as raw material for the cold spray process for sealing gaps in refractory metal cladding, for producing sputtering targets, for the rejuvenation of used sputtering targets, for the coating of different geometries in electronics, chemical industrial processes, and other market segments and for X-ray anode substrates.
  • the low content of oxygen and other impurities will dramatically improve the consolidation process.
  • the products can be used for pressing and sintering of different components, tools and parts.
  • the powders and their blends can be used in both CIP and HIP processes.
  • Low content of oxygen and other impurities will lead to an extremely high sintering activity of the powders. This will allow for the production of sputtering targets with the content of oxygen and other impurities comparable to that of the standard rolling process.
  • the products of the invention could also be used in a cold spray process to produce near net-shape parts.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention is directed to a process for the preparation of a metal powder having a purity at least as high as the starting powder and having an oxygen content of 10 ppm or less comprising heating said metal powder containing oxygen in the form of an oxide, with the total oxygen content being from 50 to 3000 ppm, in an inert atmosphere at a pressure of from 1 bar to 10−7 to a temperature at which the oxide of the metal powder becomes thermodynamically unstable and removing the resulting oxygen via volatilization. The metal powder is preferably selected from the group consisting of tantalum, niobium, molybdenum, hafnium, zirconium, titanium, vanadium, rhenium and tungsten. The invention also relates to the powders produced by the process and the use of such powders in a cold spray process.

Description

    BACKGROUND OF THE INVENTION
  • Passive oxide layers are inherent to all metal powders. In general, the presence of such oxides has an adverse effect on one or more of the properties of the products made from such powders.
  • For example, due to the high melting point of tantalum, its purification method yields a metal powder. When exposed to air, tantalum oxidizes and forms an oxide layer, which protects it from further oxidation. In order to make metal parts, this powder must be consolidated to solid form. Due to the inherent stability of this oxide layer, when pressed and sintered into a powder metallurgy form, the oxygen is conserved, yielding a lower quality product. Therefore the oxygen removal becomes a primary objective for tantalum refining.
  • The operation of oxygen removal is called deoxidation. There is quite a bit of art teaching various ways of removing oxygen. One way to avoid this oxygen is to electron beam melt the powder, vaporizing the oxygen, resulting in an ingot with only the ingot's passive layer of oxygen.
  • A second known method for removal of oxygen from tantalum is using another element to reduce Ta2O5 One element that can be used is carbon (see, e.g., U.S. Pat. No. 6,197,082). However, since excess carbon is used for reduction, tantalum, carbides result as a contaminant. U.S. Pat. No. 4,537,641 suggests using magnesium, calcium, or aluminum as the reductant (see also U.S. Pat. Nos. 5,954,856 and 6,136,062). These metals can be then leached out of the tantalum with water and diluted mineral acid. U.S. Pat. Nos. 6,261,337, 5,580,516 and 5,242,481 suggest this method for use on low surface area powders, which are used in the manufacture of solid tantalum parts. The byproduct of this process is a layer of MgO on the surface of the tantalum powder. As such it is necessary to expose this powder to air and water during the leaching and drying processes, creating the passive oxide layer. Another potential contaminant, which may result during this process, is magnesium. Magnesium tantalates are stable enough to survive the pressing and sintering processes that yield solid tantalum parts.
  • European Patent 1,066,899 suggests purifying tantalum powder in thermal plasma. The process was carried out at atmospheric pressure, at the temperatures exceeding the melting point of tantalum in the presence of hydrogen. The resulting powder had spherical morphology and the oxygen concentration as low as 86 ppm.
  • A more recent development for the removal of oxygen from tantalum is the use of atomic hydrogen as described in U.S. patent application Ser. No. 11/085,876, filed on Mar. 22, 2005. This process requires significant hydrogen excess and is thermodynamically favorable in a relatively narrow temperature range. Theoretically this process is capable of producing very low oxygen powder.
  • Other techniques for reducing the oxygen content of tantalum are described in U.S. Pat. No. 4,508,563 (contacting tantalum with an alkali metal halide), U.S. Pat. No. 4,722,756 (heating the tantalum under a hydrogen atmosphere in the presence of an oxygen-active metal), U.S. Pat. No. 4,964,906 (heating the tantalum under a hydrogen atmosphere in the presence of a tantalum getter metal having an initial oxygen content lower than the tantalum), U.S. Pat. No. 5,972,065 (plasma arc melting using a gas mixture of helium and hydrogen), and U.S. Pat. No. 5,993,513 (leaching a deoxidized valve metal in an acid leach solution).
  • Other techniques for reducing the oxygen content in other metals are also known. See, e.g., U.S. Pat. Nos. 6,171,363, 6,328,927, 6,521,173, 6,558,447 and 7,067,197.
  • Cold spray technology is the process by which materials are deposited as a solid onto a substrate without melting. During the cold spray process, the coating particles are typically heated by carrier gas to only a few hundred degrees Celsius, and are traveling at a supersonic velocity typically in the range of 500 to 1500 meters per second prior to impact with the substrate.
  • The ability to cold spray different materials is determined by their ductility, the measure of a material's ability to undergo appreciable plastic deformation. The more ductile the raw materials, the better the adhesion attained during the cold-spray process due to its ability to deform.
  • Different metals have different plastic properties, soft metals, with excellent ductility characteristics, therefore have been used in the cold spray technology, such as copper, iron, nickel, and cobalt as well as some composites and ceramics.
  • In the family of refractory metals, currently only tantalum and niobium are used, as they are the softest of the refractory metals. Other refractory metals such as molybdenum, hafnium, zirconium, and particularly tungsten are considered brittle, and therefore cannot plastically deform and adhere upon impact during cold spray.
  • Metals with body centered cubic (BCC) and hexagonal close-packed (HCP) structures exhibit what is called a ductile-to-brittle transition temperature (DBTT). This is defined as the transition from ductile to brittle behavior with a decrease in temperature. The refractory metals, which perform poorly when cold-sprayed, exhibit a higher DBTT. The DBTT, in metals, can be impacted by its purity. Oxygen and carbon are notoriously deleterious to the ductility. Due to their surface area and affinity for oxygen and carbon, these elements tend to be particularly prevalent impurities in metal powders. Since the cold-spray process requires metals powders as a raw material, it makes the use of high DBTT refractory metals prohibitive, with the exception of tantalum and niobium, which have lower DBTT.
    • DESCRIPTION OF THE INVENTION
  • The present invention is directed to the discovery that the oxygen content can be drastically reduced by creating conditions at which the refractory oxide species become thermodynamically unstable, and removed by volatilization. The main challenge was to find the thermodynamic parameters (temperature and total pressure) at which the oxide species became unstable and volatilize while the metal species will continue to stay in the condensed phase.
  • More particularly, the present invention is broadly directed to a process for the preparation of a metal powder having a purity of at least as high as the starting powder and having an oxygen content of 10 ppm or less comprising heating the metal powder containing oxygen in the form of an oxide, with the total oxygen content being from 50 to 3000 ppm, in an inert atmosphere at a pressure of from 1 bar to 10−7 to a temperature at which the oxide of the metal powder becomes thermodynamically unstable and removing the resulting oxygen via volatilization. The process has the additional advantage of significantly reducing and/or removing any metallic impurities having boiling points lower than that which the oxide of the metal powder becomes thermodynamically unstable.
  • The metal powder is preferably selected from the group consisting of tantalum, niobium, molybdenum, hafnium, zirconium, titanium, vanadium, rhenium and tungsten.
  • The inert atmosphere can be substantially any “inert” gas, such as argon, helium, neon, krypton or xenon.
  • When the metal powder is tantalum, such powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10−7 bar and a temperature of from about 1700° C. to about 3800° C. The resultant unpassivated powder has a purity of at least as high as the starting powder, and preferably at least 99.9%, a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less, a hydrogen content of 1 ppm or less, a magnesium content of 1 ppm or less, an alkali metal content of 1 ppm or less, and a combined iron plus nickel plus chromium content of 1 ppm or less. As noted above, the process has the advantage of significantly reducing any metallic impurities (such as alkali metals, magnesium, iron, nickel and chromium) having boiling points lower than the temperature at which the tantalum oxide becomes thermodynamically unstable.
  • When the metal powder is niobium, such powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 1750° C. to about 3850° C. The resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less, a hydrogen content of 1 ppm or less, a magnesium content of 1 ppm or less, an alkali metal content of 1 ppm or less, and a combined iron plus nickel plus chromium content of 1 ppm or less.
  • When the metal powder is tungsten, such powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10−7 bar and a temperature of from about 1200° C. to about 1800° C. The resultant unpassivated powder has a purity of at least of as high as the starting powder, a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 5 ppm or less, a carbon content of 5 ppm or less and a hydrogen content of 1 ppm or less.
  • When the metal powder is molybdenum, such powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10−7 bar and a temperature of from about 1450° C. to about 2300° C. The resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • When the metal powder is titanium, such powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 1800° C. to about 2500° C. The resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • When the metal powder is zirconium, such powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 2300° C. to about 2900° C. The resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • When the metal powder is hafnium, such powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 2400° C. to about 3200° C. The resultant unpassivated powder has a purity of at least as high as the starting powder, a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
  • From the kinetic standpoint, it is generally preferable to run the process at the temperatures above the melting point of the particular metal as both chemical and diffusion processes proceed at a higher rate in the molten state. The temperature of the system should not be too high in order to minimize the evaporation of the particular metal.
  • The range of temperatures described above can usually be reached using the gas plasma process. The temperature in the plasma flame is not constant; due to the particle size distribution, it may not be possible to heat all particles to the set temperature. Since the residence time in the plasma flame is extremely short, the particles inherently will be at different temperatures. Therefore, there is a potential to underheat the coarse particles (not enough volatilization) and overheat the fine particles (excessive volatilization, not only of the metal oxide but also the metal itself). It is, however, not the only means of reaching the desired temperature range. For example, the induction melting can be also used.
  • The requirements of temperature and pressure can be met by using vacuum plasma technique, or other equipment such as electric-resistant furnace, rotary kiln, induction furnace, e-beam furnace in high vacuum and the like. The equipment that is preferable is one that is capable of vacuum and allows flexible residence time.
  • The process of the invention allows for the production of a metal powder with very low oxygen content typical of the consolidated solid metal. This was made possible due to the application of the process requiring no reducing agent. The prior art used either magnesium or hydrogen for the reduction of oxygen and therefore, the product (powder) had to be passivated (exposed to air) prior to its further usage.
  • Processing metal powders under the conditions described has the additional advantage of significantly reducing and/or removing any metallic impurities having boiling points lower than that which the oxide of the metal powder becomes thermodynamically unstable (e.g., depending upon the starting metal powder, such impurities as iron, nickel, chromium, sodium, boron, phosphorous, nitrogen and hydrogen may be significantly reduced). In the case of tantalum, the nitrogen content will be reduced to 20 ppm or less and the phosphorous content will be reduced to 10 ppm or less. Another reaction that will occur under these conditions would be the removal of carbon due to the reaction of the carbide with the oxide. This is particularly important in the case of tungsten, even small amounts of oxygen and carbon can make the tungsten brittle. It is critical to reduce carbon (to a level of 5 ppm or less) and oxygen (to a level of 5 ppm or less) from tungsten to a level at which the tungsten becomes ductile and therefore useable in the cold spray process.
  • The powder particles produced via the process of the invention have virtually the same low oxygen content regardless of their size. Furthermore, the obtained powder has this low oxygen content regardless of its surface area. Depending on the total pressure, the powder may or may not have to be melted. The powder may be used as a raw material for the ensuing operations without removal of either fine or coarse fraction. Powder can be produced in different types of furnaces including but not limited to plasma, induction, or any resistance furnace capable of working under vacuum.
  • The process of the invention is a relatively low cost process since it does not require any reducing agent, is a one step process, does not call for the product passivation, does not require screening out powder fractions, and could be run continuously. Moreover, due to the low oxygen and other impurities content, the obtained powder will be of superior grade quality.
  • Due to the extremely high reactivity of the powder in air, its transfer and further treatment or usage has to be done in the inert atmosphere until the powder is fully consolidated. If the final product is to be used in a cold spray process, it is important that the material not be exposed to any oxygen containing atmosphere before it is sprayed. This can be achieved by either storage under vacuum or other inert gas. For the same reason, the use of inert gas during the cold spray process is necessary.
  • The result of the present invention is the drastic reduction of the oxygen and carbon contents, for example, that would increase the ductility of the previously unusable refractory metals, and make them potentially usable. This would potentially expand the usage of previously high DBTT metals.
  • The products of the present invention and blends thereof can be used as raw material for the cold spray process for sealing gaps in refractory metal cladding, for producing sputtering targets, for the rejuvenation of used sputtering targets, for the coating of different geometries in electronics, chemical industrial processes, and other market segments and for X-ray anode substrates. The low content of oxygen and other impurities will dramatically improve the consolidation process.
  • In addition, the products can be used for pressing and sintering of different components, tools and parts. For example, the powders and their blends can be used in both CIP and HIP processes. Low content of oxygen and other impurities will lead to an extremely high sintering activity of the powders. This will allow for the production of sputtering targets with the content of oxygen and other impurities comparable to that of the standard rolling process.
  • The products of the invention could also be used in a cold spray process to produce near net-shape parts.
  • The drastic decrease of oxygen and other impurities could potentially allow for the production of parts via powder metallurgy processes which will be comparable to those produced via standard melting/rolling techniques.
  • Although illustrated and described herein with reference to certain specific embodiments, the present invention is not intended to be limited to the details described. Various modifications may be made within the scope and range of equivalents of the claims that follow without departing from the spirit of the invention.

Claims (24)

1. A process for the preparation of a metal powder having a purity of at least as high as the starting powder and having an oxygen content of 10 ppm or less comprising heating said metal powder containing oxygen in the form of an oxide, with the total oxygen content being from 50 to 3000 ppm, in an inert atmosphere at a pressure of from 1 bar to 10−7 to a temperature at which the oxide of the metal powder becomes thermodynamically unstable and removing the resulting oxygen via volatilization.
2. The process of claim 1, wherein said metal powder is selected from the group consisting of tantalum, niobium, molybdenum, hafnium, zirconium, titanium, vanadium, rhenium and tungsten.
3. The process of claim 1, wherein the metal powder has a purity of at least 99.9%.
4. The process of claim 2, wherein said metal is tantalum and wherein said powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10−7 bar and a temperature of from about 1700° C. to about 3800° C.
5. The process of claim 2, wherein said metal is niobium and said powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 1750° C. to about 3850° C.
6. The process of claim 2, wherein said metal is tungsten and wherein said powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10−7 bar and a temperature of from about 1200° C. to about 1800° C.
7. The process of claim 2, wherein said metal is molybdenum and wherein said powder is heated in an inert gas atmosphere at a pressure of from 1 bar to 10−7 bar and a temperature of from about 1450° C. to about 2300° C.
8. The process of claim 2, wherein said metal is titanium and said powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 1800° C. to about 2500° C.
9. The process of claim 2, wherein said metal is zirconium and said powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 2300° C. to about 2900° C.
10. The process of claim 2, wherein said metal is hafnium and said powder is heated in an inert gas atmosphere at a pressure of from 10−3 bar to 10−7 bar and a temperature of from about 2400° C. to about 3200° C.
11. An unpassivated tantalum powder having a surface area of from about 100 cm2/g to about 10,000 cm2/g, having an oxygen content of 10 ppm or less, having a hydrogen content of 1 ppm or less, a magnesium content of 1 ppm or less, an alkali metal content of 1 ppm or less, and a combined iron plus nickel plus chromium content of 1 ppm or less.
12. A unpassivated niobium powder having a surface area of from about 100 cm2/g to about 10,000 cm2/g, having an oxygen content of 10 ppm or less, having a hydrogen content of 1 ppm or less, a magnesium content of 1 ppm or less, an alkali metal content of 1 ppm or less, and a combined iron plus nickel plus chromium content of 1 ppm or less.
13. A unpassivated tungsten having a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 5 ppm or less, a carbon content of 5 ppm or less and a hydrogen content of 1 ppm or less.
14. A unpassivated molybdenum powder having a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
15. A unpassivated titanium powder having a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
16. A unpassivated zirconium powder having a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
17. A unpassivated hafnium powder having a surface area of from about 100 cm2/g to about 10,000 cm2/g, an oxygen content of 10 ppm or less and a hydrogen content of 1 ppm or less.
18. In a cold spray process comprising spraying a metal powder onto a substrate at a supersonic velocity, the improvement wherein the powder is the tantalum powder of claim 11.
19. In a cold spray process comprising spraying a metal powder onto a substrate at a supersonic velocity, the improvement wherein the powder is the niobium powder of claim 12.
20. In a cold spray process comprising spraying a metal powder onto a substrate at a supersonic velocity, the improvement wherein the powder is the tungsten powder of claim 13.
21. In a cold spray process comprising spraying a metal powder onto a substrate at a supersonic velocity, the improvement wherein the powder is the molybdenum powder of claim 14.
22. In a cold spray process comprising spraying a metal powder onto a substrate at a supersonic velocity, the improvement wherein the powder is the titanium powder of claim 15.
23. In a cold spray process comprising spraying a metal powder onto a substrate at a supersonic velocity, the improvement wherein the powder is the zirconium powder of claim 16.
24. In a cold spray process comprising spraying a metal powder onto a substrate at a supersonic velocity, the improvement wherein the powder is the hafnium powder of claim 17.
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CN2007800364699A CN101522342B (en) 2006-10-03 2007-10-03 Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
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US12/444,263 US8226741B2 (en) 2006-10-03 2007-10-03 Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
RU2009116616/02A RU2009116616A (en) 2006-10-03 2007-10-03 METHOD FOR PRODUCING METAL POWDERS WITH LOW OXYGEN CONTENT OBTAINED BY THIS METHOD OF POWDER AND USE THEREOF
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080145688A1 (en) * 2006-12-13 2008-06-19 H.C. Starck Inc. Method of joining tantalum clade steel structures
US20080216602A1 (en) * 2005-05-05 2008-09-11 H. C. Starck Gmbh Coating process for manufacture or reprocessing of sputter targets and x-ray anodes
US20080271779A1 (en) * 2007-05-04 2008-11-06 H.C. Starck Inc. Fine Grained, Non Banded, Refractory Metal Sputtering Targets with a Uniformly Random Crystallographic Orientation, Method for Making Such Film, and Thin Film Based Devices and Products Made Therefrom
US20090082229A1 (en) * 2007-09-24 2009-03-26 Texas United Chemical Company, Llc Process for Drying Boron-Containing Minerals and Products Thereof
US20100015467A1 (en) * 2006-11-07 2010-01-21 H.C. Starck Gmbh & Co., Kg Method for coating a substrate and coated product
US20100055487A1 (en) * 2005-05-05 2010-03-04 H.C. Starck Gmbh Method for coating a substrate surface and coated product
US20100086800A1 (en) * 2008-10-06 2010-04-08 H.C. Starck Inc. Method of manufacturing bulk metallic structures with submicron grain sizes and structures made with such method
US20100272889A1 (en) * 2006-10-03 2010-10-28 H.C. Starch Inc. Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
US20110094879A1 (en) * 2008-06-02 2011-04-28 Jx Nippon Mining & Metals Corporation Tungsten Sintered Sputtering Target
US20120063947A1 (en) * 2009-04-10 2012-03-15 Saint-Gobain Coating Solutions Molybdenum-based target and process for producing a target by thermal spraying
CN102615288A (en) * 2012-03-26 2012-08-01 宁波福沃德新材料科技有限公司 Method for preparing spherical metal molybdenum particles for cold spraying
US8246903B2 (en) 2008-09-09 2012-08-21 H.C. Starck Inc. Dynamic dehydriding of refractory metal powders
CN103658670A (en) * 2014-01-16 2014-03-26 山东昊轩电子陶瓷材料有限公司 Ultrafine titanium powder and preparation method thereof
US8703233B2 (en) 2011-09-29 2014-04-22 H.C. Starck Inc. Methods of manufacturing large-area sputtering targets by cold spray
US10023953B2 (en) 2014-04-11 2018-07-17 H.C. Starck Inc. High purity refractory metal powders and their use in sputtering targets which may have random texture
CN109518141A (en) * 2019-01-16 2019-03-26 广州市尤特新材料有限公司 A kind of niobium rotary target material and preparation method thereof
WO2020091854A1 (en) * 2018-10-31 2020-05-07 Arconic Inc. Method and system for processing metal powders, and articles produced therefrom
CN111118460A (en) * 2020-01-10 2020-05-08 广州市尤特新材料有限公司 Rotary titanium target and preparation method thereof
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US11458519B2 (en) * 2016-03-03 2022-10-04 H.C. Stark Solutions Coldwater, LLC High-density, crack-free metallic parts
US12091730B2 (en) 2019-07-19 2024-09-17 Global Advanced Metals Usa, Inc. Spherical tantalum-titanium alloy powder, products containing the same, and methods of making the same

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* Cited by examiner, † Cited by third party
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CN117086318B (en) * 2022-05-12 2025-08-19 中国科学院过程工程研究所 Preparation method of low-oxygen metal titanium powder

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508563A (en) * 1984-03-19 1985-04-02 Sprague Electric Company Reducing the oxygen content of tantalum
US4537641A (en) * 1983-03-18 1985-08-27 Hermann C. Starck Berlin Process for producing valve-metal anodes for electrolytic capacitors
US4722756A (en) * 1987-02-27 1988-02-02 Cabot Corp Method for deoxidizing tantalum material
US4964906A (en) * 1989-09-26 1990-10-23 Fife James A Method for controlling the oxygen content of tantalum material
US5242481A (en) * 1989-06-26 1993-09-07 Cabot Corporation Method of making powders and products of tantalum and niobium
US5954856A (en) * 1996-04-25 1999-09-21 Cabot Corporation Method of making tantalum metal powder with controlled size distribution and products made therefrom
US5972065A (en) * 1997-07-10 1999-10-26 The Regents Of The University Of California Purification of tantalum by plasma arc melting
US5993513A (en) * 1996-04-05 1999-11-30 Cabot Corporation Method for controlling the oxygen content in valve metal materials
US6136062A (en) * 1998-10-13 2000-10-24 H. C. Starck Gmbh & Co. Kg Niobium powder and a process for the production of niobium and/or tantalum powders
US6171363B1 (en) * 1998-05-06 2001-01-09 H. C. Starck, Inc. Method for producing tantallum/niobium metal powders by the reduction of their oxides with gaseous magnesium
US6197082B1 (en) * 1999-02-17 2001-03-06 H.C. Starck, Inc. Refining of tantalum and tantalum scrap with carbon
US6261337B1 (en) * 1999-08-19 2001-07-17 Prabhat Kumar Low oxygen refractory metal powder for powder metallurgy
US6328927B1 (en) * 1998-12-24 2001-12-11 Praxair Technology, Inc. Method of making high-density, high-purity tungsten sputter targets
US20030019326A1 (en) * 1999-07-07 2003-01-30 Hitachi Metals, Ltd. Sputtering target, method of making same, and high-melting metal powder material
US6521173B2 (en) * 1999-08-19 2003-02-18 H.C. Starck, Inc. Low oxygen refractory metal powder for powder metallurgy
US6558447B1 (en) * 1999-05-05 2003-05-06 H.C. Starck, Inc. Metal powders produced by the reduction of the oxides with gaseous magnesium
US6589377B2 (en) * 1998-08-11 2003-07-08 Arova Schaffhausen Ag Manufacture of sections of fiber-plastic compound materials
US20050084701A1 (en) * 2003-10-20 2005-04-21 The Boeing Company Sprayed preforms for forming structural members
US7067197B2 (en) * 2003-01-07 2006-06-27 Cabot Corporation Powder metallurgy sputtering targets and methods of producing same

Family Cites Families (216)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3436299A (en) 1965-12-17 1969-04-01 Celanese Corp Polymer bonding
US3990784A (en) 1974-06-05 1976-11-09 Optical Coating Laboratory, Inc. Coated architectural glass system and method
US4011981A (en) 1975-03-27 1977-03-15 Olin Corporation Process for bonding titanium, tantalum, and alloys thereof
US4059442A (en) * 1976-08-09 1977-11-22 Sprague Electric Company Method for making a porous tantalum pellet
US4073427A (en) 1976-10-07 1978-02-14 Fansteel Inc. Lined equipment with triclad wall construction
US4140172A (en) 1976-12-23 1979-02-20 Fansteel Inc. Liners and tube supports for industrial and chemical process equipment
US4135286A (en) 1977-12-22 1979-01-23 United Technologies Corporation Sputtering target fabrication method
US4291104A (en) 1978-04-17 1981-09-22 Fansteel Inc. Brazed corrosion resistant lined equipment
US4202932A (en) 1978-07-21 1980-05-13 Xerox Corporation Magnetic recording medium
US4349954A (en) 1980-11-26 1982-09-21 The United States Of America As Represented By The United States National Aeronautics And Space Administration Mechanical bonding of metal method
DE3130392C2 (en) 1981-07-31 1985-10-17 Hermann C. Starck Berlin, 1000 Berlin Process for the production of pure agglomerated valve metal powder for electrolytic capacitors, their use and process for the production of sintered anodes
US4510171A (en) 1981-09-11 1985-04-09 Monsanto Company Clad metal joint closure
US4459062A (en) 1981-09-11 1984-07-10 Monsanto Company Clad metal joint closure
CA1173128A (en) 1981-10-13 1984-08-21 Pok F. Lee Echo cancellation using transversal filters
CA1202599A (en) 1982-06-10 1986-04-01 Michael G. Down Upgrading titanium, zirconium and hafnium powders by plasma processing
US4818629A (en) 1985-08-26 1989-04-04 Fansteel Inc. Joint construction for lined equipment
BR8702042A (en) 1986-12-22 1988-07-12 Kawasaki Steel Co APPLIANCE AND PROCESS FOR RECOVERY BY SPRAYING REFRACTORY MATERIAL ON REFRACTORY CONSTRUCTION
US4731111A (en) 1987-03-16 1988-03-15 Gte Products Corporation Hydrometallurical process for producing finely divided spherical refractory metal based powders
JPH0275887A (en) 1988-09-12 1990-03-15 Toshiba Corp Metal melting crucible
US4915745A (en) 1988-09-22 1990-04-10 Atlantic Richfield Company Thin film solar cell and method of making
US5147125A (en) 1989-08-24 1992-09-15 Viratec Thin Films, Inc. Multilayer anti-reflection coating using zinc oxide to provide ultraviolet blocking
DE69016433T2 (en) 1990-05-19 1995-07-20 Papyrin Anatolij Nikiforovic COATING METHOD AND DEVICE.
US5091244A (en) 1990-08-10 1992-02-25 Viratec Thin Films, Inc. Electrically-conductive, light-attenuating antireflection coating
US5270858A (en) 1990-10-11 1993-12-14 Viratec Thin Films Inc D.C. reactively sputtered antireflection coatings
US5271965A (en) 1991-01-16 1993-12-21 Browning James A Thermal spray method utilizing in-transit powder particle temperatures below their melting point
US5269899A (en) 1992-04-29 1993-12-14 Tosoh Smd, Inc. Cathode assembly for cathodic sputtering apparatus
US5612254A (en) 1992-06-29 1997-03-18 Intel Corporation Methods of forming an interconnect on a semiconductor substrate
US5693203A (en) 1992-09-29 1997-12-02 Japan Energy Corporation Sputtering target assembly having solid-phase bonded interface
US5305946A (en) 1992-11-05 1994-04-26 Nooter Corporation Welding process for clad metals
JP3197640B2 (en) 1992-11-30 2001-08-13 朝日興業株式会社 Bubble generator
US5330798A (en) 1992-12-09 1994-07-19 Browning Thermal Systems, Inc. Thermal spray method and apparatus for optimizing flame jet temperature
US5679473A (en) 1993-04-01 1997-10-21 Asahi Komag Co., Ltd. Magnetic recording medium and method for its production
US5853866A (en) 1993-12-10 1998-12-29 Toto Ltd. Multi-functional material with photocalytic functions and method of manufacturing same
US5433835B1 (en) 1993-11-24 1997-05-20 Applied Materials Inc Sputtering device and target with cover to hold cooling fluid
US5487822A (en) 1993-11-24 1996-01-30 Applied Materials, Inc. Integrated sputtering target assembly
US5392981A (en) 1993-12-06 1995-02-28 Regents Of The University Of California Fabrication of boron sputter targets
US5687600A (en) 1994-10-26 1997-11-18 Johnson Matthey Electronics, Inc. Metal sputtering target assembly
US6103392A (en) 1994-12-22 2000-08-15 Osram Sylvania Inc. Tungsten-copper composite powder
CA2188592C (en) 1995-02-22 1999-08-31 Toshihiro Fukushima Seam welding method and seam welding apparatus
US5836506A (en) 1995-04-21 1998-11-17 Sony Corporation Sputter target/backing plate assembly and method of making same
US5795626A (en) 1995-04-28 1998-08-18 Innovative Technology Inc. Coating or ablation applicator with a debris recovery attachment
EP0852266B1 (en) 1995-08-23 2004-10-13 Asahi Glass Ceramics Co., Ltd. Target, process for production thereof, and method of forming highly refractive film
DE19532244C2 (en) 1995-09-01 1998-07-02 Peak Werkstoff Gmbh Process for the production of thin-walled tubes (I)
US5738770A (en) 1996-06-21 1998-04-14 Sony Corporation Mechanically joined sputtering target and adapter therefor
KR100237316B1 (en) 1996-08-01 2000-01-15 박호군 Sputtering target for forming magnetic thin film and the manufacturing method thereof
US5863398A (en) 1996-10-11 1999-01-26 Johnson Matthey Electonics, Inc. Hot pressed and sintered sputtering target assemblies and method for making same
US5859654A (en) 1996-10-31 1999-01-12 Hewlett-Packard Company Print head for ink-jet printing a method for making print heads
JP3794713B2 (en) 1997-02-19 2006-07-12 エイチ・シー・スタルク・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング Tantalum powder, its production method and sintered anode obtained therefrom
US20030052000A1 (en) 1997-07-11 2003-03-20 Vladimir Segal Fine grain size material, sputtering target, methods of forming, and micro-arc reduction method
US6010583A (en) 1997-09-09 2000-01-04 Sony Corporation Method of making unreacted metal/aluminum sputter target
EP1034566A1 (en) 1997-11-26 2000-09-13 Applied Materials, Inc. Damage-free sculptured coating deposition
US6911124B2 (en) 1998-09-24 2005-06-28 Applied Materials, Inc. Method of depositing a TaN seed layer
US6189663B1 (en) 1998-06-08 2001-02-20 General Motors Corporation Spray coatings for suspension damper rods
US6875324B2 (en) 1998-06-17 2005-04-05 Tanaka Kikinzoku Kogyo K.K. Sputtering target material
US6071389A (en) 1998-08-21 2000-06-06 Tosoh Smd, Inc. Diffusion bonded sputter target assembly and method of making
US6749103B1 (en) 1998-09-11 2004-06-15 Tosoh Smd, Inc. Low temperature sputter target bonding method and target assemblies produced thereby
FR2785897B1 (en) 1998-11-16 2000-12-08 Commissariat Energie Atomique THIN FILM OF HAFNIUM OXIDE AND DEPOSITION METHOD
US6176947B1 (en) 1998-12-31 2001-01-23 H-Technologies Group, Incorporated Lead-free solders
US6139913A (en) 1999-06-29 2000-10-31 National Center For Manufacturing Sciences Kinetic spray coating method and apparatus
US6478902B2 (en) 1999-07-08 2002-11-12 Praxair S.T. Technology, Inc. Fabrication and bonding of copper sputter targets
US6165413A (en) 1999-07-08 2000-12-26 Praxair S.T. Technology, Inc. Method of making high density sputtering targets
US6283357B1 (en) 1999-08-03 2001-09-04 Praxair S.T. Technology, Inc. Fabrication of clad hollow cathode magnetron sputter targets
DE19942916A1 (en) 1999-09-08 2001-03-15 Linde Gas Ag Manufacture of foamable metal bodies and metal foams
US6245390B1 (en) 1999-09-10 2001-06-12 Viatcheslav Baranovski High-velocity thermal spray apparatus and method of forming materials
JP2001085378A (en) 1999-09-13 2001-03-30 Sony Corp Semiconductor device and manufacturing method thereof
JP4240679B2 (en) 1999-09-21 2009-03-18 ソニー株式会社 Method for producing sputtering target
US6258402B1 (en) 1999-10-12 2001-07-10 Nakhleh Hussary Method for repairing spray-formed steel tooling
US6267851B1 (en) 1999-10-28 2001-07-31 Applied Komatsu Technology, Inc. Tilted sputtering target with shield to block contaminants
RU2166421C1 (en) 1999-12-06 2001-05-10 Государственный космический научно-производственный центр им. М.В. Хруничева Method of machine parts reconditioning
US6878250B1 (en) 1999-12-16 2005-04-12 Honeywell International Inc. Sputtering targets formed from cast materials
KR100418331B1 (en) 1999-12-28 2004-02-14 가부시끼가이샤 도시바 Parts for vacuum film-forming device
US6331233B1 (en) 2000-02-02 2001-12-18 Honeywell International Inc. Tantalum sputtering target with fine grains and uniform texture and method of manufacture
US7122069B2 (en) 2000-03-29 2006-10-17 Osram Sylvania Inc. Mo-Cu composite powder
US6502767B2 (en) 2000-05-03 2003-01-07 Asb Industries Advanced cold spray system
US6432804B1 (en) 2000-05-22 2002-08-13 Sharp Laboratories Of America, Inc. Sputtered silicon target for fabrication of polysilicon thin film transistors
US20030023132A1 (en) 2000-05-31 2003-01-30 Melvin David B. Cyclic device for restructuring heart chamber geometry
US6582572B2 (en) 2000-06-01 2003-06-24 Seagate Technology Llc Target fabrication method for cylindrical cathodes
JP2001347672A (en) 2000-06-07 2001-12-18 Fuji Photo Film Co Ltd Ink jet recording head and its manufacturing method and ink jet printer
US6725522B1 (en) 2000-07-12 2004-04-27 Tosoh Smd, Inc. Method of assembling target and backing plates
US6497797B1 (en) 2000-08-21 2002-12-24 Honeywell International Inc. Methods of forming sputtering targets, and sputtering targets formed thereby
US6409897B1 (en) 2000-09-20 2002-06-25 Poco Graphite, Inc. Rotatable sputter target
EP1320872A2 (en) 2000-09-27 2003-06-25 NUP2 Incorporated Fabrication of semiconductor devices
US7041204B1 (en) 2000-10-27 2006-05-09 Honeywell International Inc. Physical vapor deposition components and methods of formation
US6498091B1 (en) 2000-11-01 2002-12-24 Applied Materials, Inc. Method of using a barrier sputter reactor to remove an underlying barrier layer
US6946039B1 (en) 2000-11-02 2005-09-20 Honeywell International Inc. Physical vapor deposition targets, and methods of fabricating metallic materials
US6669782B1 (en) 2000-11-15 2003-12-30 Randhir P. S. Thakur Method and apparatus to control the formation of layers useful in integrated circuits
US6491208B2 (en) 2000-12-05 2002-12-10 Siemens Westinghouse Power Corporation Cold spray repair process
KR100817742B1 (en) 2000-12-18 2008-03-31 토소우 에스엠디, 인크 Method for manufacturing sputter target assembly and target assembly
US6444259B1 (en) 2001-01-30 2002-09-03 Siemens Westinghouse Power Corporation Thermal barrier coating applied with cold spray technique
EP1362132B1 (en) 2001-02-14 2006-05-10 H. C. Starck, Inc. Rejuvenation of a tantalum sputtering target.
US7794554B2 (en) 2001-02-14 2010-09-14 H.C. Starck Inc. Rejuvenation of refractory metal products
CA2438819A1 (en) 2001-02-20 2002-09-12 Peter R. Jepson Refractory metal plates with uniform texture and methods of making the same
TW558471B (en) * 2001-03-28 2003-10-21 Phild Co Ltd Method and device for manufacturing metallic particulates and manufactured metallic particulates
US6915964B2 (en) 2001-04-24 2005-07-12 Innovative Technology, Inc. System and process for solid-state deposition and consolidation of high velocity powder particles using thermal plastic deformation
US6722584B2 (en) 2001-05-02 2004-04-20 Asb Industries, Inc. Cold spray system nozzle
DE10126100A1 (en) 2001-05-29 2002-12-05 Linde Ag Production of a coating or a molded part comprises injecting powdered particles in a gas stream only in the divergent section of a Laval nozzle, and applying the particles at a specified speed
US7201940B1 (en) 2001-06-12 2007-04-10 Advanced Cardiovascular Systems, Inc. Method and apparatus for thermal spray processing of medical devices
JP4332832B2 (en) 2001-07-06 2009-09-16 富士電機デバイステクノロジー株式会社 Perpendicular magnetic recording medium and manufacturing method thereof
US7053294B2 (en) 2001-07-13 2006-05-30 Midwest Research Institute Thin-film solar cell fabricated on a flexible metallic substrate
US6780458B2 (en) 2001-08-01 2004-08-24 Siemens Westinghouse Power Corporation Wear and erosion resistant alloys applied by cold spray technique
KR100617402B1 (en) 2001-09-17 2006-09-01 헤래우스 인코포레이티드 How to Repair Used Sputtering Targets and Repaired Sputter Targets
US6770154B2 (en) 2001-09-18 2004-08-03 Praxair S.T. Technology, Inc. Textured-grain-powder metallurgy tantalum sputter target
US7081148B2 (en) 2001-09-18 2006-07-25 Praxair S.T. Technology, Inc. Textured-grain-powder metallurgy tantalum sputter target
US20030178301A1 (en) 2001-12-21 2003-09-25 Lynn David Mark Planar magnetron targets having target material affixed to non-planar backing plates
US6861101B1 (en) 2002-01-08 2005-03-01 Flame Spray Industries, Inc. Plasma spray method for applying a coating utilizing particle kinetics
US6986471B1 (en) 2002-01-08 2006-01-17 Flame Spray Industries, Inc. Rotary plasma spray method and apparatus for applying a coating utilizing particle kinetics
MXPA04007103A (en) 2002-01-24 2004-10-29 Starck H C Inc Refractrory metal and alloy refining by laser forming and melting.
US20030175142A1 (en) 2002-03-16 2003-09-18 Vassiliki Milonopoulou Rare-earth pre-alloyed PVD targets for dielectric planar applications
US6627814B1 (en) 2002-03-22 2003-09-30 David H. Stark Hermetically sealed micro-device package with window
BE1014736A5 (en) 2002-03-29 2004-03-02 Alloys For Technical Applic S Manufacturing method and charging for target sputtering.
US6623796B1 (en) 2002-04-05 2003-09-23 Delphi Technologies, Inc. Method of producing a coating using a kinetic spray process with large particles and nozzles for the same
US6896933B2 (en) 2002-04-05 2005-05-24 Delphi Technologies, Inc. Method of maintaining a non-obstructed interior opening in kinetic spray nozzles
JP3624898B2 (en) * 2002-04-26 2005-03-02 昭和電工株式会社 Niobium powder, sintered body using the same, and capacitor using the same
US20030219542A1 (en) 2002-05-25 2003-11-27 Ewasyshyn Frank J. Method of forming dense coatings by powder spraying
DE10224780A1 (en) 2002-06-04 2003-12-18 Linde Ag High-velocity cold gas particle-spraying process for forming coating on workpiece, is carried out below atmospheric pressure
DE10224777A1 (en) 2002-06-04 2003-12-18 Linde Ag High-velocity cold gas particle-spraying process for forming coating on workpiece, intercepts, purifies and collects carrier gas after use
US6759085B2 (en) 2002-06-17 2004-07-06 Sulzer Metco (Us) Inc. Method and apparatus for low pressure cold spraying
DE10231203B4 (en) 2002-07-10 2009-09-10 Interpane Entwicklungs-Und Beratungsgesellschaft Mbh Target support assembly
CA2433613A1 (en) 2002-08-13 2004-02-13 Russel J. Ruprecht, Jr. Spray method for mcralx coating
US7128988B2 (en) 2002-08-29 2006-10-31 Lambeth Systems Magnetic material structures, devices and methods
JP4883546B2 (en) 2002-09-20 2012-02-22 Ｊｘ日鉱日石金属株式会社 Method for manufacturing tantalum sputtering target
US7108893B2 (en) 2002-09-23 2006-09-19 Delphi Technologies, Inc. Spray system with combined kinetic spray and thermal spray ability
US6743468B2 (en) 2002-09-23 2004-06-01 Delphi Technologies, Inc. Method of coating with combined kinetic spray and thermal spray
JP2006509617A (en) 2002-09-25 2006-03-23 アルコア インコーポレイテッド Coated automotive wheel and coating method
US20040065546A1 (en) 2002-10-04 2004-04-08 Michaluk Christopher A. Method to recover spent components of a sputter target
CA2444917A1 (en) 2002-10-18 2004-04-18 United Technologies Corporation Cold sprayed copper for rocket engine applications
US6749002B2 (en) 2002-10-21 2004-06-15 Ford Motor Company Method of spray joining articles
DE10253794B4 (en) 2002-11-19 2005-03-17 Hühne, Erwin Dieter Low temperature high speed flame spraying system
TW571342B (en) 2002-12-18 2004-01-11 Au Optronics Corp Method of forming a thin film transistor
US6872427B2 (en) 2003-02-07 2005-03-29 Delphi Technologies, Inc. Method for producing electrical contacts using selective melting and a low pressure kinetic spray process
ATE359384T1 (en) 2003-02-20 2007-05-15 Bekaert Sa Nv METHOD FOR PRODUCING AN ATOMIZATION TARGET
CA2556786C (en) 2003-02-24 2012-07-24 Tekna Plasma Systems Inc. Process and apparatus for the manufacture of sputtering targets
US20040262157A1 (en) 2003-02-25 2004-12-30 Ford Robert B. Method of forming sputtering target assembly and assemblies made therefrom
JP4422975B2 (en) 2003-04-03 2010-03-03 株式会社コベルコ科研 Sputtering target and manufacturing method thereof
US7278353B2 (en) 2003-05-27 2007-10-09 Surface Treatment Technologies, Inc. Reactive shaped charges and thermal spray methods of making same
JP4008388B2 (en) 2003-06-30 2007-11-14 シャープ株式会社 Film for semiconductor carrier, semiconductor device using the same, and liquid crystal module
US6992261B2 (en) 2003-07-15 2006-01-31 Cabot Corporation Sputtering target assemblies using resistance welding
US7425093B2 (en) 2003-07-16 2008-09-16 Cabot Corporation Thermography test method and apparatus for bonding evaluation in sputtering targets
US7170915B2 (en) 2003-07-23 2007-01-30 Intel Corporation Anti-reflective (AR) coating for high index gain media
US7314650B1 (en) 2003-08-05 2008-01-01 Leonard Nanis Method for fabricating sputter targets
US7208230B2 (en) 2003-08-29 2007-04-24 General Electric Company Optical reflector for reducing radiation heat transfer to hot engine parts
US7951275B2 (en) 2003-09-12 2011-05-31 Jx Nippon Mining & Metals Corporation Sputtering target and method for finishing surface of such target
US7335341B2 (en) 2003-10-30 2008-02-26 Delphi Technologies, Inc. Method for securing ceramic structures and forming electrical connections on the same
US20050147742A1 (en) 2004-01-07 2005-07-07 Tokyo Electron Limited Processing chamber components, particularly chamber shields, and method of controlling temperature thereof
WO2005073418A1 (en) 2004-01-30 2005-08-11 Nippon Tungsten Co., Ltd. Tungsten based sintered compact and method for production thereof
US6905728B1 (en) 2004-03-22 2005-06-14 Honeywell International, Inc. Cold gas-dynamic spray repair on gas turbine engine components
US7244466B2 (en) 2004-03-24 2007-07-17 Delphi Technologies, Inc. Kinetic spray nozzle design for small spot coatings and narrow width structures
US20050220995A1 (en) 2004-04-06 2005-10-06 Yiping Hu Cold gas-dynamic spraying of wear resistant alloys on turbine blades
JP4826066B2 (en) 2004-04-27 2011-11-30 住友金属鉱山株式会社 Amorphous transparent conductive thin film and method for producing the same, and sputtering target for obtaining the amorphous transparent conductive thin film and method for producing the same
DE102004029354A1 (en) 2004-05-04 2005-12-01 Linde Ag Method and apparatus for cold gas spraying
WO2006001976A2 (en) 2004-06-15 2006-01-05 Tosoh Smd, Inc. High purity target manufacturing methods
US20060006064A1 (en) 2004-07-09 2006-01-12 Avi Tepman Target tiles in a staggered array
US20060011470A1 (en) 2004-07-16 2006-01-19 Hatch Gareth P Sputtering magnetron control devices
US20060021870A1 (en) 2004-07-27 2006-02-02 Applied Materials, Inc. Profile detection and refurbishment of deposition targets
US20060045785A1 (en) 2004-08-30 2006-03-02 Yiping Hu Method for repairing titanium alloy components
US20060042728A1 (en) 2004-08-31 2006-03-02 Brad Lemon Molybdenum sputtering targets
EP1797212A4 (en) 2004-09-16 2012-04-04 Vladimir Belashchenko Deposition system, method and materials for composite coatings
CN101052746B (en) 2004-09-25 2010-04-14 Abb技术股份公司 For the manufacture of ablation-resistant coatings and corresponding shielding for vacuum switchgears
US20060090593A1 (en) 2004-11-03 2006-05-04 Junhai Liu Cold spray formation of thin metal coatings
US20060121187A1 (en) 2004-12-03 2006-06-08 Haynes Jeffrey D Vacuum cold spray process
DE102004059716B3 (en) 2004-12-08 2006-04-06 Siemens Ag Cold gas spraying method uses particles which are chemical components of high temperature superconductors and are sprayed on to substrate with crystal structure corresponding to that of superconductors
US20060137969A1 (en) 2004-12-29 2006-06-29 Feldewerth Gerald B Method of manufacturing alloy sputtering targets
US7479299B2 (en) 2005-01-26 2009-01-20 Honeywell International Inc. Methods of forming high strength coatings
US7399335B2 (en) 2005-03-22 2008-07-15 H.C. Starck Inc. Method of preparing primary refractory metal
US7354659B2 (en) 2005-03-30 2008-04-08 Reactive Nanotechnologies, Inc. Method for fabricating large dimension bonds using reactive multilayer joining
DE102005018618A1 (en) 2005-04-21 2006-10-26 Rheinmetall Waffe Munition Gmbh Gun barrel and method of coating the inner surface of the barrel
BRPI0611539B1 (en) 2005-05-05 2017-04-04 Starck H C Gmbh method of applying a coating to a surface, cold spray coat and coated object
US20060251872A1 (en) 2005-05-05 2006-11-09 Wang Jenn Y Conductive barrier layer, especially an alloy of ruthenium and tantalum and sputter deposition thereof
CN101368262B (en) 2005-05-05 2012-06-06 H.C.施塔克有限公司 Method for coating surface
US20060266639A1 (en) 2005-05-24 2006-11-30 Applied Materials, Inc. Sputtering target tiles having structured edges separated by a gap
US7316763B2 (en) 2005-05-24 2008-01-08 Applied Materials, Inc. Multiple target tiles with complementary beveled edges forming a slanted gap therebetween
US7550055B2 (en) 2005-05-31 2009-06-23 Applied Materials, Inc. Elastomer bonding of large area sputtering target
US7644745B2 (en) 2005-06-06 2010-01-12 Applied Materials, Inc. Bonding of target tiles to backing plate with patterned bonding agent
US7652223B2 (en) 2005-06-13 2010-01-26 Applied Materials, Inc. Electron beam welding of sputtering target tiles
US20060289305A1 (en) 2005-06-27 2006-12-28 Applied Materials, Inc. Centering mechanism for aligning sputtering target tiles
US20070012557A1 (en) 2005-07-13 2007-01-18 Applied Materials, Inc Low voltage sputtering for large area substrates
US7837929B2 (en) 2005-10-20 2010-11-23 H.C. Starck Inc. Methods of making molybdenum titanium sputtering plates and targets
US7624910B2 (en) 2006-04-17 2009-12-01 Lockheed Martin Corporation Perforated composites for joining of metallic and composite materials
US7618500B2 (en) 2005-11-14 2009-11-17 Lawrence Livermore National Security, Llc Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals
US8480864B2 (en) 2005-11-14 2013-07-09 Joseph C. Farmer Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings
US20070116890A1 (en) 2005-11-21 2007-05-24 Honeywell International, Inc. Method for coating turbine engine components with rhenium alloys using high velocity-low temperature spray process
CA2560030C (en) 2005-11-24 2013-11-12 Sulzer Metco Ag A thermal spraying material, a thermally sprayed coating, a thermal spraying method an also a thermally coated workpiece
KR101380793B1 (en) 2005-12-21 2014-04-04 슐저메트코(유에스)아이엔씨 Hybrid plasma-cold spray method and apparatus
EP1806429B1 (en) 2006-01-10 2008-07-09 Siemens Aktiengesellschaft Cold spray apparatus and method with modulated gasstream
US7402277B2 (en) 2006-02-07 2008-07-22 Exxonmobil Research And Engineering Company Method of forming metal foams by cold spray technique
TW200738896A (en) 2006-04-12 2007-10-16 Wintek Corp Sputtering target
EP1849887A1 (en) 2006-04-26 2007-10-31 Sulzer Metco AG Mounting device for a sputter source
JP5210498B2 (en) 2006-04-28 2013-06-12 株式会社アルバック Joining type sputtering target and method for producing the same
US20070289869A1 (en) 2006-06-15 2007-12-20 Zhifei Ye Large Area Sputtering Target
US20070289864A1 (en) 2006-06-15 2007-12-20 Zhifei Ye Large Area Sputtering Target
US7815782B2 (en) 2006-06-23 2010-10-19 Applied Materials, Inc. PVD target
KR101377574B1 (en) 2006-07-28 2014-03-26 삼성전자주식회사 Security management method in a mobile communication system using proxy mobile internet protocol and system thereof
US20080041720A1 (en) 2006-08-14 2008-02-21 Jaeyeon Kim Novel manufacturing design and processing methods and apparatus for PVD targets
WO2008079461A2 (en) 2006-09-08 2008-07-03 Reactive Nanotechnologies, Inc. Reactive multilayer joining with improved metallization techniques
US20080078268A1 (en) 2006-10-03 2008-04-03 H.C. Starck Inc. Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
NZ576664A (en) 2006-11-07 2012-03-30 Starck H C Gmbh Method for coating a substrate surface and coated product
US8197781B2 (en) 2006-11-07 2012-06-12 Infinite Power Solutions, Inc. Sputtering target of Li3PO4 and method for producing same
US20080145688A1 (en) 2006-12-13 2008-06-19 H.C. Starck Inc. Method of joining tantalum clade steel structures
US8784729B2 (en) 2007-01-16 2014-07-22 H.C. Starck Inc. High density refractory metals and alloys sputtering targets
US8197894B2 (en) 2007-05-04 2012-06-12 H.C. Starck Gmbh Methods of forming sputtering targets
US7914856B2 (en) 2007-06-29 2011-03-29 General Electric Company Method of preparing wetting-resistant surfaces and articles incorporating the same
US20090010792A1 (en) 2007-07-02 2009-01-08 Heraeus Inc. Brittle metal alloy sputtering targets and method of fabricating same
US7901552B2 (en) 2007-10-05 2011-03-08 Applied Materials, Inc. Sputtering target with grooves and intersecting channels
US9334557B2 (en) 2007-12-21 2016-05-10 Sapurast Research Llc Method for sputter targets for electrolyte films
GB2459917B (en) 2008-05-12 2013-02-27 Sinito Shenzhen Optoelectrical Advanced Materials Company Ltd A process for the manufacture of a high density ITO sputtering target
DE102008024504A1 (en) 2008-05-21 2009-11-26 Linde Ag Method and apparatus for cold gas spraying
EP2135973A1 (en) 2008-06-18 2009-12-23 Centre National de la Recherche Scientifique Method for the manufacturing of sputtering targets using an inorganic polymer
JP5092939B2 (en) 2008-07-01 2012-12-05 日立電線株式会社 Flat plate copper sputtering target material for TFT and sputtering method
US20100012488A1 (en) 2008-07-15 2010-01-21 Koenigsmann Holger J Sputter target assembly having a low-temperature high-strength bond
US8246903B2 (en) 2008-09-09 2012-08-21 H.C. Starck Inc. Dynamic dehydriding of refractory metal powders
US8043655B2 (en) 2008-10-06 2011-10-25 H.C. Starck, Inc. Low-energy method of manufacturing bulk metallic structures with submicron grain sizes
US8192799B2 (en) 2008-12-03 2012-06-05 Asb Industries, Inc. Spray nozzle assembly for gas dynamic cold spray and method of coating a substrate with a high temperature coating
US8268237B2 (en) 2009-01-08 2012-09-18 General Electric Company Method of coating with cryo-milled nano-grained particles
US8363787B2 (en) 2009-03-25 2013-01-29 General Electric Company Interface for liquid metal bearing and method of making same
US8673122B2 (en) 2009-04-07 2014-03-18 Magna Mirrors Of America, Inc. Hot tile sputtering system
US8821701B2 (en) 2010-06-02 2014-09-02 Clifton Higdon Ion beam sputter target and method of manufacture

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4537641A (en) * 1983-03-18 1985-08-27 Hermann C. Starck Berlin Process for producing valve-metal anodes for electrolytic capacitors
US4508563A (en) * 1984-03-19 1985-04-02 Sprague Electric Company Reducing the oxygen content of tantalum
US4722756A (en) * 1987-02-27 1988-02-02 Cabot Corp Method for deoxidizing tantalum material
US5242481A (en) * 1989-06-26 1993-09-07 Cabot Corporation Method of making powders and products of tantalum and niobium
US5580516A (en) * 1989-06-26 1996-12-03 Cabot Corporation Powders and products of tantalum, niobium and their alloys
US4964906A (en) * 1989-09-26 1990-10-23 Fife James A Method for controlling the oxygen content of tantalum material
US5993513A (en) * 1996-04-05 1999-11-30 Cabot Corporation Method for controlling the oxygen content in valve metal materials
US5954856A (en) * 1996-04-25 1999-09-21 Cabot Corporation Method of making tantalum metal powder with controlled size distribution and products made therefrom
US5972065A (en) * 1997-07-10 1999-10-26 The Regents Of The University Of California Purification of tantalum by plasma arc melting
US6171363B1 (en) * 1998-05-06 2001-01-09 H. C. Starck, Inc. Method for producing tantallum/niobium metal powders by the reduction of their oxides with gaseous magnesium
US6589377B2 (en) * 1998-08-11 2003-07-08 Arova Schaffhausen Ag Manufacture of sections of fiber-plastic compound materials
US6136062A (en) * 1998-10-13 2000-10-24 H. C. Starck Gmbh & Co. Kg Niobium powder and a process for the production of niobium and/or tantalum powders
US6328927B1 (en) * 1998-12-24 2001-12-11 Praxair Technology, Inc. Method of making high-density, high-purity tungsten sputter targets
US6197082B1 (en) * 1999-02-17 2001-03-06 H.C. Starck, Inc. Refining of tantalum and tantalum scrap with carbon
US6558447B1 (en) * 1999-05-05 2003-05-06 H.C. Starck, Inc. Metal powders produced by the reduction of the oxides with gaseous magnesium
US20030019326A1 (en) * 1999-07-07 2003-01-30 Hitachi Metals, Ltd. Sputtering target, method of making same, and high-melting metal powder material
US6261337B1 (en) * 1999-08-19 2001-07-17 Prabhat Kumar Low oxygen refractory metal powder for powder metallurgy
US6521173B2 (en) * 1999-08-19 2003-02-18 H.C. Starck, Inc. Low oxygen refractory metal powder for powder metallurgy
US7067197B2 (en) * 2003-01-07 2006-06-27 Cabot Corporation Powder metallurgy sputtering targets and methods of producing same
US20050084701A1 (en) * 2003-10-20 2005-04-21 The Boeing Company Sprayed preforms for forming structural members

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7910051B2 (en) 2005-05-05 2011-03-22 H.C. Starck Gmbh Low-energy method for fabrication of large-area sputtering targets
US20080216602A1 (en) * 2005-05-05 2008-09-11 H. C. Starck Gmbh Coating process for manufacture or reprocessing of sputter targets and x-ray anodes
US8802191B2 (en) 2005-05-05 2014-08-12 H. C. Starck Gmbh Method for coating a substrate surface and coated product
US20100055487A1 (en) * 2005-05-05 2010-03-04 H.C. Starck Gmbh Method for coating a substrate surface and coated product
US8226741B2 (en) 2006-10-03 2012-07-24 H.C. Starck, Inc. Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
US8715386B2 (en) 2006-10-03 2014-05-06 H.C. Starck Inc. Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
US20100272889A1 (en) * 2006-10-03 2010-10-28 H.C. Starch Inc. Process for preparing metal powders having low oxygen content, powders so-produced and uses thereof
US20100015467A1 (en) * 2006-11-07 2010-01-21 H.C. Starck Gmbh & Co., Kg Method for coating a substrate and coated product
US8777090B2 (en) 2006-12-13 2014-07-15 H.C. Starck Inc. Methods of joining metallic protective layers
US9095932B2 (en) 2006-12-13 2015-08-04 H.C. Starck Inc. Methods of joining metallic protective layers
US8002169B2 (en) 2006-12-13 2011-08-23 H.C. Starck, Inc. Methods of joining protective metal-clad structures
US20080145688A1 (en) * 2006-12-13 2008-06-19 H.C. Starck Inc. Method of joining tantalum clade steel structures
US8113413B2 (en) 2006-12-13 2012-02-14 H.C. Starck, Inc. Protective metal-clad structures
US8448840B2 (en) 2006-12-13 2013-05-28 H.C. Starck Inc. Methods of joining metallic protective layers
US8197894B2 (en) 2007-05-04 2012-06-12 H.C. Starck Gmbh Methods of forming sputtering targets
US8883250B2 (en) 2007-05-04 2014-11-11 H.C. Starck Inc. Methods of rejuvenating sputtering targets
US20080271779A1 (en) * 2007-05-04 2008-11-06 H.C. Starck Inc. Fine Grained, Non Banded, Refractory Metal Sputtering Targets with a Uniformly Random Crystallographic Orientation, Method for Making Such Film, and Thin Film Based Devices and Products Made Therefrom
US8491959B2 (en) 2007-05-04 2013-07-23 H.C. Starck Inc. Methods of rejuvenating sputtering targets
US9783882B2 (en) 2007-05-04 2017-10-10 H.C. Starck Inc. Fine grained, non banded, refractory metal sputtering targets with a uniformly random crystallographic orientation, method for making such film, and thin film based devices and products made therefrom
US20090082229A1 (en) * 2007-09-24 2009-03-26 Texas United Chemical Company, Llc Process for Drying Boron-Containing Minerals and Products Thereof
US20110094879A1 (en) * 2008-06-02 2011-04-28 Jx Nippon Mining & Metals Corporation Tungsten Sintered Sputtering Target
US8961867B2 (en) 2008-09-09 2015-02-24 H.C. Starck Inc. Dynamic dehydriding of refractory metal powders
US8246903B2 (en) 2008-09-09 2012-08-21 H.C. Starck Inc. Dynamic dehydriding of refractory metal powders
US8470396B2 (en) 2008-09-09 2013-06-25 H.C. Starck Inc. Dynamic dehydriding of refractory metal powders
US20100086800A1 (en) * 2008-10-06 2010-04-08 H.C. Starck Inc. Method of manufacturing bulk metallic structures with submicron grain sizes and structures made with such method
US8043655B2 (en) 2008-10-06 2011-10-25 H.C. Starck, Inc. Low-energy method of manufacturing bulk metallic structures with submicron grain sizes
US20120063947A1 (en) * 2009-04-10 2012-03-15 Saint-Gobain Coating Solutions Molybdenum-based target and process for producing a target by thermal spraying
US9951413B2 (en) * 2009-04-10 2018-04-24 Saint-Gobain Coating Solutions Molybdenum-based target and process for producing a target by thermal spraying
US8703233B2 (en) 2011-09-29 2014-04-22 H.C. Starck Inc. Methods of manufacturing large-area sputtering targets by cold spray
US8734896B2 (en) 2011-09-29 2014-05-27 H.C. Starck Inc. Methods of manufacturing high-strength large-area sputtering targets
US9108273B2 (en) 2011-09-29 2015-08-18 H.C. Starck Inc. Methods of manufacturing large-area sputtering targets using interlocking joints
US9120183B2 (en) 2011-09-29 2015-09-01 H.C. Starck Inc. Methods of manufacturing large-area sputtering targets
US9293306B2 (en) 2011-09-29 2016-03-22 H.C. Starck, Inc. Methods of manufacturing large-area sputtering targets using interlocking joints
US9412568B2 (en) 2011-09-29 2016-08-09 H.C. Starck, Inc. Large-area sputtering targets
CN102615288A (en) * 2012-03-26 2012-08-01 宁波福沃德新材料科技有限公司 Method for preparing spherical metal molybdenum particles for cold spraying
CN103658670A (en) * 2014-01-16 2014-03-26 山东昊轩电子陶瓷材料有限公司 Ultrafine titanium powder and preparation method thereof
US10023953B2 (en) 2014-04-11 2018-07-17 H.C. Starck Inc. High purity refractory metal powders and their use in sputtering targets which may have random texture
US11458519B2 (en) * 2016-03-03 2022-10-04 H.C. Stark Solutions Coldwater, LLC High-density, crack-free metallic parts
US11826822B2 (en) 2016-03-03 2023-11-28 H.C. Starck Solutions Coldwater LLC High-density, crack-free metallic parts
WO2020091854A1 (en) * 2018-10-31 2020-05-07 Arconic Inc. Method and system for processing metal powders, and articles produced therefrom
CN109518141A (en) * 2019-01-16 2019-03-26 广州市尤特新材料有限公司 A kind of niobium rotary target material and preparation method thereof
US12091730B2 (en) 2019-07-19 2024-09-17 Global Advanced Metals Usa, Inc. Spherical tantalum-titanium alloy powder, products containing the same, and methods of making the same
CN111118460A (en) * 2020-01-10 2020-05-08 广州市尤特新材料有限公司 Rotary titanium target and preparation method thereof
CN113981390A (en) * 2021-10-29 2022-01-28 宁波江丰半导体科技有限公司 Preparation method of high-purity low-oxygen tantalum target material

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CN101522342B (en) 2012-07-18
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RU2009116616A (en) 2010-11-10
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US8226741B2 (en) 2012-07-24
US8715386B2 (en) 2014-05-06

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