WO1990014451A1 - Barbes de carbure et de nitrure de metal de transition dont la croissance est obtenue par depôt en phase vapeur par procede chimique - Google Patents

Barbes de carbure et de nitrure de metal de transition dont la croissance est obtenue par depôt en phase vapeur par procede chimique Download PDF

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Publication number
WO1990014451A1
WO1990014451A1 PCT/US1990/001755 US9001755W WO9014451A1 WO 1990014451 A1 WO1990014451 A1 WO 1990014451A1 US 9001755 W US9001755 W US 9001755W WO 9014451 A1 WO9014451 A1 WO 9014451A1
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Prior art keywords
whiskers
process according
metal
reaction chamber
operating temperature
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PCT/US1990/001755
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English (en)
Inventor
Charles Erik Bauer
William A. Bryant
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Kennametal Inc.
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Publication date
Application filed by Kennametal Inc. filed Critical Kennametal Inc.
Priority to KR1019910701629A priority Critical patent/KR920701535A/ko
Priority to DE1990911429 priority patent/DE472666T1/de
Publication of WO1990014451A1 publication Critical patent/WO1990014451A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/005Growth of whiskers or needles
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62Whiskers or needles
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/36Carbides
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/38Nitrides

Definitions

  • the present invention generally relates to a process for producing single crystal metal carbide, nitride, or carbonitride whiskers and, in particular, to a process for producing metal carbide, nitride, or carbonitride whiskers by a chemical vapor deposition process and the products thereof.
  • Whiskers are minute, high purity, single crystal fibers having strengths approaching interatomic bonding forces and improved resistance to high temperatures and greater toughness when compared to polycrystalline fibers. Due to their high modulus of elasticity, hardness, strength, and chemical stability, single crystal whiskers of such materials as carbides or nitrides of titanium, zirconium, hafnium, niobium, tantalum, and tungsten are candidate materials to reinforce and toughen metal, ceramic and glass matrix composites. Whiskers may be grown by a number of processes including chemical vapor deposition (CVD) .
  • CVD chemical vapor deposition
  • Typical temperatures in such reactors range from about 800 degrees to 1400 degrees C.
  • the reactor is first flushed with hydrogen gas.
  • reactant gases typically in a molar ratio of carbon or nitrogen to metal of about 1:1, are flowed through the heated reactor to form whiskers on the growth substrate.
  • the choice of the growth substrate materials can be critical to the formation and type of whiskers (see Wokulski et al., J. Crystal Growth, 62, pp. 439- 446 (1983)) .
  • the use of graphite as a growth substrate has been shown to produce a variance in the C/Ti mole ratio.
  • growth substrates of tungsten, molybdenum, and iron while not affecting the growth of the whiskers, do not produce significant numbers of whiskers.
  • iron- based growth substrates react vigorously with the reactants for producing the whiskers.
  • VLS vapor- liguid-solid
  • a liquid catalyst is used in place of a solid substrate.
  • the catalyst must display the ability, when molten, to take into solution the elements and compounds necessary to produce the desired whiskers.
  • transition metal and alloy powders have been satisfactory.
  • the reaction for the VLS process takes place at approximately 1400 degrees C or above the melting point of the catalyst.
  • the whiskers which can be grown by this process have been limited to those having a reaction temperature equal to or greater than the melting point of the catalyst.
  • residual catalyst may remain with the whiskers thereby adversely affecting the physical properties of the subsequent composite article. Attempts to remove the residual catalyst by chemical or physical means have resulted in damage to the whiskers.
  • U.S. Patent No. 4,686,197 issued to Elvin, discloses a process for demetallizing a petrochemical catalyst with chlorine gas at approximately 350 degrees C. According to Elvin, the process successfully removed Ni and/or V from a contaminated catalyst.
  • U.S. Patent No. 4,492,767 issued to Fung, discloses a process for reactivating a coked petrochemical catalyst which includes a halide pretreatment step at approximately 300 to 540 degrees C and a halogen redispersion step with a mixture of elemental halogen and water vapor at approximately 500 to 540 degrees C.
  • the metal of interest in Fung is iridium and it is directed to redispersing the iridium rather than removing it from the catalyst.
  • the present invention solves the aforementioned problems associated with the prior art by providing an improved process for producing metal carbide, nitride, or carbonitride whiskers of controlled dimensions, morphology, and quality by a CVD/VLS process.
  • the present invention is based on the surprising discovery that it is not necessary to be above the melting point of a powdered metal catalyst in order for whisker growth to occur. It is postulated that the catalyst combines with the reactant gases to produce a lower melting point eutectoid composition, thereby allowing whisker growth to occur.
  • the reaction chamber includes one or more growth substrate surfaces having nickel or high nickel alloy powder dispersed onto aluminum oxide plates to provide catalyzing and supporting substrates for nucleation and growth of the whiskers.
  • the melting point of the powder is approximately 1455 degrees C.
  • the growth substrate surfaces are maintained at an operating temperature of about 1120 to 1225 degrees C, preferably about 1190 to 1220 degrees C.
  • the process includes the steps of flushing the reaction chamber sealed from the ambient atmosphere with flowing hydrogen gas.
  • the hydrogen flowing through the reaction chamber is then mixed, at about ambient pressure, with reactants comprising a metal halide gas and one or more gases selected from the group consisting of aliphatic hydrocarbon gases pyrolyzable at the operating- temperature to form free carbon.
  • Nitrogen gas and/or ammonia may be substituted for or mixed with the hydrocarbon gases to produce nitride or carbonitride whiskers.
  • the atomic ratios of carbon and nitrogen to metal in the incoming gases is about 0.7:1 and 20:1, respectively, and the volume ratios of hydrocarbon and nitrogen gases to hydrogen is 1:37 and 1:1.6, respectively.
  • the flowing mixture of gases is maintained at a suitable linear velocity, preferably about 2-4 cm/sec, for a time sufficient- to nucleate and grow metal carbide, nitride, or carbonitride whiskers on the growth substrate material surfaces.
  • Suitable hydrocarbon gases are.compounds of the formulas c n H 2 n+2' c n H 2n' or c n H 2 n- 2 ' wnere n is a positive integer of 1 to .4.
  • the preferred hydrocarbon is methane.
  • the whiskers are subjected to a post-growth treatment to remove the residual nickel metal catalyst used to grow the whiskers.
  • the process is a two-step procedure.
  • the whiskers are treated at less than 427 degrees C, preferably between 350 to 400 degrees C, with 2.8 slm of HC1 in 11.4 slm of argon gas at one atmosphere pressure for approximately one hour to convert the elemental nickel residual catalyst to NiCl 2 •
  • the whiskers are then heated to at least 973 degrees C, preferably greater than 1000 degrees C, and treated with 11.4 slm of argon for one hour to cause the NiCl 2 to sublime.
  • the nickel content of the treated whiskers is reduced from 1-2 wt% to 0.2 wt%, an order of magnitude reduction.
  • one aspect of the present invention is to provide a process for producing metal carbide, nitride, or carbonitride whiskers comprising the steps of flushing a reaction chamber sealed from the ambient atmosphere with flowing hydrogen gas, wherein the reaction chamber includes one or more growth substrate surfaces formed from one or more materials suitable for providing catalyzing and supporting substrates for nucleation and growth of the whiskers, and wherein the growth substrate surfaces are maintained at an operating temperature suitable for growing the whiskers, and, wherein the one or more substrate materials is a high temperature material having a metal powder deposited upon a portion of its surface; and mixing with the hydrogen flowing through the reaction chamber, at about ambient pressure, reactants including one or more metal halide gases selected from the group consisting of halides of titanium, zirconium, hafnium, niobium, tantalum and tungsten and one or more gases selected from the group consisting of nitrogen, ammonia, and aliphatic hydrocarbon gases pyrolyzable at the operating temperature to form free carbon, in an atomic ratio
  • Another aspect of the present invention is to provide a process for producing metal carbide, nitride, or carbonitride whiskers comprising the steps of flushing a reaction chamber sealed from the ambient atmosphere with flowing hydrogen gas, wherein the reaction chamber includes one or more growth substrate surfaces formed from one or more materials suitable for providing catalyzing and supporting substrates for nucleation and growth of the whiskers, and wherein the growth substrate surfaces are maintained at an operating temperature of about 1120 to 1225 degrees C; and mixing with the hydrogen flowing through the reaction chamber, at about ambient pressure, reactants including one or more metal halide gases selected from the group consisting of halides of titanium, zirconium, hafnium, niobium, tantalum and tungsten and one or more gases selected from the group consisting of nitrogen, ammonia, and aliphatic hydrocarbon gases pyrolyzable at the operating temperature to form free carbon, in an atomic ratio of carbon plus nitrogen to metal of about 0.7:1 to 20:1 and a volume ratio of hydrocarbon plus nitrogen or ammonia
  • Still another aspect of the present invention is to provide a process for removing the residual metal catalyst from metal carbide, nitride, or carbonitride whiskers in a reaction chamber sealed from the ambient atmosphere, the chamber including one or more substrate surfaces for supporting the whiskers, comprising the steps of supplying the reaction chamber with a reactant including one or more gases selected from the group consisting of halogens, hydrogen halides, or chlorocarbons at a first operating temperature for a first predetermined time, the first operating temperature being sufficient to form a halide with the metal catalyst, and flushing the reaction chamber at a second operating temperature for a second predetermined time to remove the metal halide from the reaction chamber, the second operating temperature being sufficient to cause the metal halide to sublime.
  • a reactant including one or more gases selected from the group consisting of halogens, hydrogen halides, or chlorocarbons
  • Another aspect of the present invention is to provide metal carbide, nitride, or carbonitride whiskers produced by chemical vapor deposition and treated to remove the residual catalyst, the treated whiskers having substantially the same physical properties as untreated whiskers.
  • the present invention may be practiced using a conventional reactor.
  • One particularly suitable reactor is a model TI-100-V reactor manufactured by TI Coatings, Inc., Mt. Clemens, Michigan.
  • the total volume of the reactor is approximately 1400 in 3 .
  • the reactor includes inlet and outlet means in the reaction vessel to permit the flowing gas to enter and exit the vessel in such a way that gas flow is established permitting optimum contact of the flowing gases with the surface of the growth substrate.
  • the growth substrate is preferably nickel powder dispersed onto aluminum oxide plates or nickel electrolytically deposited onto TiC or TiN coated aluminum oxide plates.
  • the growth substrate is prepared by ultrasonically suspending nickel powder having a particle size of approximately 2 microns in isopropyl alcohol and then spraying the solution onto 72 4"x4"xl/8" aluminum oxide plates with an air gun. The plates were weighed before and after spraying and it was calculated that the substrate surfaces received approximately 2.7 gms/meter 2 of nickel powder.
  • the use of aluminum oxide instead of graphite helps to eliminate an extra, uncontrollable source of carbon in the gas phase.
  • the growth plates are arranged radially and axially within a support structure.
  • the reactor includes conventional heating means to heat the growth substrates to the operating temperature. Typically, the operating temperature may be monitored by thermocouples disposed adjacent to the surface of the support structure. Also, as is well known in the art, the entire reactor is sealed from the ambient atmosphere to prevent contamination of the whiskers grown therein.
  • metal carbide whiskers are grown on an aluminum oxide growth substrate surface on which nickel powder has been dispersed or electrolytically deposited in a reactor having a controlled atmosphere.
  • the growth substrate surface is heated to an operating temperature of about 1120 to 1225 degrees C, preferably 1190 to 1220 degrees C, while being flushed with hydrogen gas at ambient pressure.
  • the pressure within the reaction chamber preferably is maintained at about 1 atmosphere throughout the operation of the reactor.
  • the flow of hydrogen is increased, with the addition of a suitable metal halide in an amount suitable for whisker growth.
  • the atomic ratio of carbon to metal in the reactant gases is maintained at about 0.7:1 and the volume ratio of hydrocarbon to hydrogen at about 1:37.
  • the flow of reactant gases is maintained, preferably at a linear velocity of about 2 cm/sec, for a time sufficient for whisker nucleation and growth, normally about 2 hours. Following the whisker growth, the flows of reactant gases are stopped, and the flow of hydrogen gas is maintained while the growth substrate surface is cooled to ambient temperature.
  • the reaction chamber is flushed with an inert gas, such as argon, prior to removal of the whiskers.
  • metal nitride whiskers also may be grown in the reactor, as described above, with respect to the metal carbide whiskers and the dispersed nickel on aluminum oxide growth substrate.
  • the process is substantially the same as that for growing the metal carbide whiskers with the exception that the hydrocarbon for whisker growth is replaced by nitrogen gas.
  • the atomic ratio of nitrogen with respect to metal is about 20:1 and the volume ratio of nitrogen to hydrogen is about 1:1.6.
  • the whiskers are subjected to a post-growth treatment to remove the residual nickel catalyst used to grow the whiskers.
  • the process is a two-step procedure. In the first step, the whiskers are treated at between 350 to 400 degrees C at one atmosphere pressure with 2.8 slm of HC1 in 11.4 slm of argon gas, based on a total available amount of nickel catalyst of approximately 2 gms, for approximately one hour to convert the elemental nickel residual catalyst to NiCl 2 . In the second step, the whiskers are then heated to 1000 degrees C and treated with 11.4 slm of argon for one hour to cause the NiCl 2 to sublime.
  • Tables 1 and 2 shown below.
  • Ni (s) + 2 HCl (g) yields NiCl 2(s) + H 2 (g)
  • any of the chlorine compounds will react with free nickel to produce NiCl 2 over a wide range of temperatures.
  • the hydrogen halides are particularly suitable for NiX 2 formation since the free energy values for this family of reactions become positive (i.e. non-reactive) above specific temperatures. This transition from a reactive to nonreactive region allows the reaction with nickel to be controlled by varying the temperature in the reactor.
  • the hydrogen halide HCl is particularly suitable since its free energy value with respect to Tic goes positive (i.e. non-reactive) above approximately 900 degrees C.
  • the rate of reaction of HCl with TiC below 900 degrees C is apparently slow enough that the whiskers are not affected.
  • the transitions from reactive to nonreactive regions allow both the reactions with nickel and TiC to be controlled by varying the temperature in the reactor.
  • the residual nickel catalyst content of the whiskers, produced according to the subject invention, and then treated, as discussed above, is reduced from 1-2 wt% to 0.2 wt%, an order of magnitude reduction.
  • the heating and hydrogen flushing steps, and the introduction of the reactant gases are carried out as described above.
  • the flowing gases enter the reaction chamber through inlet means, flow upwardly past the growth substrates, and exit the reactor through outlet means.
  • the temperature in the reactor is monitored by a thermocouple.
  • the reactor is then shut down, cooled and opened.
  • the shape, and morphology of the whiskers were observed by a scanning electron microscope.
  • the whiskers were found to vary in diameter from 1 to 5 micrometers and were straight to alternating surface morphologies on the faces parallel to the growth axis. Typical results are shown in Table 3.
  • the yield of TiC whiskers was relatively independent with respect to temperature and TiCl 4 .
  • lower total flow rates require an increase in the amount of TiCl 4 in order to produce an equivalent yield as higher flow rates.
  • EXAMPLES 6-8 Growth of titanium nitride whiskers was carried out at about 1 atm pressure in a sealed reactor. The reactor was heated while being flushed with hydrogen at 10 slm. The hydrogen flow was then increased. Titanium tetrachloride liquid was flash evaporated at about 130 to 260 degrees C and then mixed with the hydrogen-nitrogen mixture for 2 hours for whisker growth. The atomic ratio of nitrogen to metal in the reactant gases was maintained at about 20:1 and the volume ratio of nitrogen to hydrogen at about 1:1.6. The flow of reactant gases was maintained, preferably at a linear velocity of about 2 cm/see.
  • the flow of nitrogen and titanium tetrachloride was shut off, and the hydrogen was allowed to flow at 19 slm until the reactor cooled to ambient temperature.
  • the system was evacuated to about 30 torr and backfilled with argon before removal of the TiN whiskers.
  • the shape and morphology of the whiskers were observed by a scanning electron microscope. The whiskers were found to vary in diameter from 1 to 10 micrometers and were straight to alternating surface morphologies on the faces parallel to the growth axis. Typical results are shown in Table 4.
  • the metal halide reactant gases may include halides of titanium, zirconium, hafnium, niobium, tantalum, or tungsten and be mixed with a hydrocarbon gas to produce carbide whiskers.
  • a mixture of metal halides may be used to produce whiskers comprising a solid solution of metal carbides, nitrides, or carbonitrides.
  • Nitrogen gas and/or ammonia may be substituted for or mixed with the hydrocarbon gas to produce nitride or carbonitride whiskers of titanium, zirconium, hafnium, niobium or tantalum.
  • the whiskers produced according to the present invention were subjected to a post-growth treatment prior to removal of the whiskers from the reactor to remove residual nickel catalyst used to grow the whiskers.
  • the process was a two-step procedure. First, the whiskers were treated at between 350 to 400 degrees C at one atmosphere pressure with 2.8 slm of HCl in 11.4 slm of argon gas for approximately one hour to convert the elemental nickel residual catalyst to NiCl 2 . Second, the whiskers were then heated to 1000 degrees C and treated with 11.4 slm of argon for one hour to cause the NiCl 2 to sublime. The nickel content of the treated whiskers was reduced from 1-2 wt% to 0.2 wt%, an order of magnitude reduction.
  • the present invention provides an improved CVD process for producing high purity, single crystal metal carbide, nitride, or carbonitride whiskers useful for composite applications.
  • whiskers produced according to the present invention and incorporated in composite materials are expected to provide composite materials having increased fracture toughness, hardness, and wear resistance for such applications as cutting tools, wear parts, dies, turbines, nozzles and the like.

Abstract

L'invention se rapporte à un procédé de dépôt en phase vapeur par voie chimique, destiné à produire des barbes à monocristaux de carbures, nitrures ou carbonitrures métalliques. Le procédé consiste à soumettre à un écoulement de rinçage une chambre de réaction présentant une surface de substrat de croissance appropriée, qui est chauffée à une température comprise entre 1120 et 1225°C, et à faire couler les gaz réactifs sur le substrat de croissance, pour entraîner la formation de barbes. Les gaz réactifs sont constitués par un gaz d'halogénure métallique et par un ou plusieurs gaz d'azote et de méthane. Le rapport atomique du carbone et de l'azote au métal est compris entre environ 0,7/1 et 20/1, respectivement. Le rapport volumique de l'hydrocarbure et de l'azote à l'hydrogène est compris entre environ 1/37 et 1/1,6, respectivement. Les matériaux préférés du substrat de croissance sont constitués par de la poudre de nickel dispersée sur des plaques d'oxyde d'alumine ou par du nickel déposé par électrolyse sur des plaques d'oxyde d'aluminium recouvertes de TiC ou de TiN. Les barbes peuvent être soumises à un traitement de post-croissance, destiné à retirer le catalyseur de nickel résiduel utilisé pour la croissance des barbes. Ce procédé s'effectue en deux étapes. Dans la première étape, les barbes sont traitées à une température comprise entre 350 et 400°C à une pression atmosphérique égale à 1 avec 2,8 slm de HCl dans 11,4 slm d'argon, pendant approximativement 1 heure de façon à convertir le catalyseur résiduel de nickel en NiCl2. Dans la seconde phase, les barbes sont chauffées à une température de 1000°C et traitées avec 11,4 slm d'argon, pendant 1 heure, de façon à entraîner la sublimation du NiCl2. Il en résulte une réduction de la teneur en nickel résiduel des barbes de 1-2 % en poids à 0,2% en poids, soit d'un ordre de grandeur, cette réduction n'affectant pas négativement les propriétés physiques des barbes.
PCT/US1990/001755 1989-05-19 1990-03-29 Barbes de carbure et de nitrure de metal de transition dont la croissance est obtenue par depôt en phase vapeur par procede chimique WO1990014451A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019910701629A KR920701535A (ko) 1989-05-19 1990-03-29 화학적 증착(cvd)으로 성장된 천이금속 탄화물 및 질화물 휘스커
DE1990911429 DE472666T1 (de) 1989-05-19 1990-03-29 Mittels chemical-vapor-deposition (cvd) gezuechtete whisker aus karbiden und nitriden von uebergangsmetallen.

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US35464189A 1989-05-19 1989-05-19
US354,641 1989-05-19

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EP (1) EP0472666A4 (fr)
JP (1) JPH04507394A (fr)
KR (1) KR920701535A (fr)
CA (1) CA2015609A1 (fr)
WO (1) WO1990014451A1 (fr)

Cited By (7)

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US5160574A (en) * 1991-05-30 1992-11-03 Aluminum Company Of America Process for production of small diameter titanium carbide whiskers
US5256243A (en) * 1990-11-26 1993-10-26 Tokai Carbon Co., Ltd. Process for producing titanium carbide whisker
EP0712946A2 (fr) * 1994-11-17 1996-05-22 Sumitomo Electric Industries, Ltd. Film céramique poreux et procédé pour sa fabrication
WO2000044965A1 (fr) * 1999-01-26 2000-08-03 Sandvik Ab (Publ) Fabrication de trichites de carbure et carbonitrure de metaux de transition appauvris en oxygene residuel et en phase oxydes intermediaires
EP2599749A1 (fr) 2011-11-30 2013-06-05 Neoker, S.L Procédé de purification des fibres d'alpha-alumine
WO2017008625A1 (fr) * 2015-07-15 2017-01-19 田东 Procédé de fabrication de matériau d'électrode négative à base d'étain par dépôt en phase vapeur
CN114988388A (zh) * 2022-06-08 2022-09-02 电子科技大学 电火花合成催化剂的声悬浮cvd制备碳材料一体化装置

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Cited By (11)

* Cited by examiner, † Cited by third party
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US5256243A (en) * 1990-11-26 1993-10-26 Tokai Carbon Co., Ltd. Process for producing titanium carbide whisker
US5160574A (en) * 1991-05-30 1992-11-03 Aluminum Company Of America Process for production of small diameter titanium carbide whiskers
EP0712946A2 (fr) * 1994-11-17 1996-05-22 Sumitomo Electric Industries, Ltd. Film céramique poreux et procédé pour sa fabrication
EP0712946A3 (fr) * 1994-11-17 1996-06-05 Sumitomo Electric Industries
US5858523A (en) * 1994-11-17 1999-01-12 Sumitomo Electric Industries, Ltd. Porous ceramic film and process for producing the same
WO2000044965A1 (fr) * 1999-01-26 2000-08-03 Sandvik Ab (Publ) Fabrication de trichites de carbure et carbonitrure de metaux de transition appauvris en oxygene residuel et en phase oxydes intermediaires
EP2599749A1 (fr) 2011-11-30 2013-06-05 Neoker, S.L Procédé de purification des fibres d'alpha-alumine
WO2013079620A1 (fr) 2011-11-30 2013-06-06 Neoker, S.L. Procédé de purification de fibres d'alpha-alumine
WO2017008625A1 (fr) * 2015-07-15 2017-01-19 田东 Procédé de fabrication de matériau d'électrode négative à base d'étain par dépôt en phase vapeur
CN114988388A (zh) * 2022-06-08 2022-09-02 电子科技大学 电火花合成催化剂的声悬浮cvd制备碳材料一体化装置
CN114988388B (zh) * 2022-06-08 2023-09-15 电子科技大学 电火花合成催化剂的声悬浮cvd制备碳材料一体化装置

Also Published As

Publication number Publication date
EP0472666A1 (fr) 1992-03-04
KR920701535A (ko) 1992-08-12
EP0472666A4 (en) 1995-03-29
CA2015609A1 (fr) 1990-11-19
JPH04507394A (ja) 1992-12-24

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