WO1990011858A1 - Low temperature method of forming materials using one or more metal reactants and a halogen-containing reactant to form one or more reactive intermediates - Google Patents

Low temperature method of forming materials using one or more metal reactants and a halogen-containing reactant to form one or more reactive intermediates Download PDF

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Publication number
WO1990011858A1
WO1990011858A1 PCT/US1990/001720 US9001720W WO9011858A1 WO 1990011858 A1 WO1990011858 A1 WO 1990011858A1 US 9001720 W US9001720 W US 9001720W WO 9011858 A1 WO9011858 A1 WO 9011858A1
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metal
reactant
metals
containing reactant
reactants
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PCT/US1990/001720
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French (fr)
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Angel Sanjurjo
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Sri International
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Publication of WO1990011858A1 publication Critical patent/WO1990011858A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/20—Methods for preparing oxides or hydroxides in general by oxidation of elements in the gaseous state; by oxidation or hydrolysis of compounds in the gaseous state
    • C01B13/22—Methods for preparing oxides or hydroxides in general by oxidation of elements in the gaseous state; by oxidation or hydrolysis of compounds in the gaseous state of halides or oxyhalides
    • C—CHEMISTRY; METALLURGY
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    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
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    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0643—Preparation from boron halides
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    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
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    • C01B21/00—Nitrogen; Compounds thereof
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    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • C01B21/0682—Preparation by direct nitridation of silicon
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
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    • C01B35/04—Metal borides
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/121—Halogen, halogenic acids or their salts
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/123—Oxides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/124—Boron, borides, boron nitrides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/126—Carbides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/128—Nitrides, nitrogen carbides
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/0617—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with vanadium, niobium or tantalum
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    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/062—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with chromium, molybdenum or tungsten
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    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Definitions

  • This invention relates to the production of mater ⁇ ials in the form of coatings or powders using a 5 halogen-containing reactant which will react with a second reactant to form one or more reactive inter ⁇ mediates from which the powder or coating may be formed by disproportionation, decomposition, or reaction.
  • the powder or coating 10 is formed directly from the one or more reactive intermediates.
  • the one or more reactive intermediates react with a gaseous third reactant resulting in the formation of a powder or coating.
  • Metallic and ceramic powders and coatings can be formed by a variety of techniques including vapor deposition, chemical vapor deposition (CVD) , sput ⁇ tering, dip coating, slurry painting, pack cementa-
  • CVD chemical vapor deposition
  • sput ⁇ tering dip coating
  • slurry painting pack cementa-
  • the material may be milled or
  • the material may be applied as a vapor by first volatilizing the material, which may in some cases require very high temperatures, e.g. as high as 2000"C or higher for materials such as silicon and titanium, or the coating may be applied by other means mentioned above such as sputtering, coating, painting, or spraying which, while not requiring as high a temperature as the vaporization techniques, may not form a bond which is as satisfactory.
  • CVD is particularly well suited for many applications including deposition of semiconductor and metallic interconnects, deposition of hard coatings for tools and gears, and deposition of corrosion resis ⁇ tant coatings for aqueous and high temperature environments.
  • a gas mix such as, for example, TiCl 4 and NH 3 are passed over a substrate heated to high temperature, (>1000'C) so that a film of TiN, which is formed in situ, deposits on the substrate.
  • CVD chemical vapor deposition
  • a coating compris ⁇ ing a compound, e.g., of silicon nitride or titanium carbide, it is necessary to both form the compound as well as provide a means for depositing or forming the coating on a substrate.
  • a compound e.g., of silicon nitride or titanium carbide
  • an object of this invention to provide a low temperature process for forming a coating or powder comprising one or more metals or metal compounds by reacting the one or more metals with a halide-containing reactant in a moving bed reactor to form one or more reactive intermediates capable of forming a coating or powder with or without reaction with another material.
  • Figure 1 is a flow sheet illustrating a first embodiment of the process of the invention.
  • Figure 2 is a flow sheet illustrating a second embodiment of the process of the invention.
  • Figure 3 is a flow sheet illustrating a third embodiment of the process of the invention.
  • Figure 4 is a flow sheet illustrating a fourth embodiment of the process of the invention.
  • Figure 5 is a vertical cross section view of a moving bed reactor showing the production of metal powder from the decomposition of one or more reac ⁇ tive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
  • Figure 6 is a vertical cross section view of a moving bed reactor showing the formation of a metal coating on a substrate by the decomposition of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-contain ⁇ ing reactant.
  • Figure 7 is a vertical cross section view of a moving bed reactor showing the formation of a pow ⁇ der comprising one or more metal compounds by reac- tion with a third reactant, in a second zone, of one or more reactive intermediates formed by react ⁇ ing one or more metal reactants with a halogen- containing reactant.
  • Figure 8 is a vertical cross section view of a moving bed reactor showing the formation of a coat ⁇ ing on graphite fibers of one or more metal com ⁇ pounds by reaction with a third reactant, in a second zone, of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
  • Figure 9 is a vertical cross section view of a moving bed reactor showing the formation of a coat ⁇ ing on steel plates of one or more metal compounds by reaction with a third reactant, in a second zone, of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
  • Figure 12 is a graph showing the mass spectrum of species in the Si-H-Br system obtained when HBr is passed through silicon powder.
  • the invention provides a novel low temperature process for forming a powder or a coating compris ⁇ ing one or more metals or metal compounds by reacting the one or more metals with a halide- containing reactant in a moving bed reactor to form one or more reactive intermediates capable of form- ing a coating or powder.
  • the coating or powder may comprise one or more decomposition products of the one or more reactive intermediates comprising the one or more metals initially reacted with the halide-containing reactant.
  • the coating or powder may comprise the reaction product of the one or more reactive intermediates reacted with another reactant intro ⁇ quizzed into a second reaction zone of the reactor and selected from the class consisting of a boron- containing reactant, a carbon-containing reactant, a nitrogen-containing reactant, an oxygen-contain ⁇ ing reactant, and mixtures thereof to form the powder or coating which comprises, respectively, one or more metal borides, metal carbides, metal nitrides, metal oxides, or a mixture thereof, of the one or more metal reactants depending upon the other reactant.
  • the gravamen of the invention is the initial reaction of the one or more metal reactants with the halide-containing reactant at atmospheric pressure and at a low temperature to form one or more reactive intermediates. This low temperature formation of the reactive intermediates makes possible the subsequent low temperature for ⁇ mation of the powders or coatings.
  • low temperature herein to describe the initial reaction between the one or more metal reactants with the halide-containing reactant is meant a temperature ranging from about 200-C, but no higher than about 1000"C.
  • a prefer ⁇ able range for this reaction is from about 400 ⁇ C to about 800 ' C, but the term "low temperature", when used herein without further definition of the tem ⁇ perature, will be understood to mean the broader range of from about 200*C to about 1000*C.
  • low temperature to describe the reaction in a second zone of the reactor used in forming either the powder or coating comprising the boride, nitride, carbide, oxide, or mixture of the one or more metal reactants is intended to define a temperature range of from about room tem ⁇ perature, i.e., 20-25'C to about 1300'C.
  • the tem ⁇ perature in this second zone preferably ranges from about 600 to about 900-C.
  • This temperature range may be maintained within the one or more reaction zones within the reactor by any convenient heating means such as resistance heating, RF heating, microwave heating, radiation heating ⁇ laser heating, arc heating, or gas heating.
  • the one or more metal reactants which are reacted with the halide-containing reactant may comprise any metal or metals capable of reacting with a halide-containing reactant to form one or more metal halide intermediates, regardless of the in ⁇ stability of the reaction intermediate.
  • metals include the transition metals Ti, V, Cr, Zr, Nb, Mo-, Hf, Ta, and W, as well as Al, Si and B. WJjile it is recognized that silicon and boron are not technically considered to be metals, the use of the terms "metaj. reactant” and/or "metal reactants” herein ill be understood to include Si and B as well as those elements traditionally recognized as metals.
  • the metal reactant is preferably provided in particulate form comprising particles having a size of from about 100 to about 1000 microns.
  • the metal reactant may also be provided in other forms such as foils and fibers and other shapes which provide dispersions with large surface to volume ratios.
  • the metal reactant is reacted with the halide-containing reactant by placing the metal reactant powder in a moving bed reactor such as a fluidized bed reactor.
  • An inert gas may be used to fluidize the bed or the powder may be rotated, moved by gravity, vibration, or any other suitable means which will move or agitate the particle bed.
  • the particle bed itself comprising the moving bed in the reactor comprises the metal reactant in particulate form, not an inert material.
  • the reactor may comprise any suitable non-reactive containment vessel capable of containing a moving bed such as, for example, a fluidized bed.
  • a suit- able containment vessel for example, would be a quartz cylinder.
  • the walls of the reactor are kept hotter than the bed to inhibit deposition on the walls.
  • a fluidized bed reactor 10 may comprise a cylindrical vessel 14 having an exit port 18 and a tapered lower portion 16 into which an inert fluidizing gas enters through a first port 20 and is mixed with the halogen-containing reactant in gaseous form which enters tapered portion 16 through a second port 24.
  • first reaction zone 34 The gaseous mixture then enters a first reaction zone 34 through a distribution plate 30 located just above tapered portion 16 in reactor 10. Above distribution plate 30 is located, in first reaction zone 34, the bed of particles comprising the one or more metal reactants, e.g., titanium particles.
  • a heating means 40 which may, for example, comprise a tubular resistance furnace which cooperates with thermocouple temperature sensor 42 to maintain first reaction zone 34 in reactor 10 within the temperature range of from about 200 ⁇ C to about
  • the metal reactant particles are both fluidized and brought into intimate contact with the one or more metal reactants to thereby form the one or more reactive intermediates.
  • these reactive intermediates then either form the powder or a coating deposited on a substrate; or pass on into a second reaction zone to react with a third reactant to form the powders or coatings of metal nitrides, metal carbides, or metal borides, or mixtures thereof as will also be described below.
  • reaction time, or residence time needed in the first reaction zone for the one or more metal reactants to react with the halogen-containing reactant to form the reactive intermediate varies from about 0.1 seconds up to 100 minutes, preferab- ly about 1 second to about 100 seconds.
  • the substrate may comprise any material capable of withstanding the temperatures which will be used in the reactor to form the coating.
  • most metals or ceramic materials for example, will be suitable substrate materials on which the coating may be deposited.
  • suitable substrate materials include metals such as Cu, Ni, Fe, alloys such as steels, super alloys, monolithic ceramics such as A1 2 0 3 , Zr0 2 , Si0 2 , SiC, Si 3 N 4 , TiN, etc., or fibers, whiskers, or powders of any of the above, or composites thereof.
  • the halide-containing reactant is a gaseous reac- tant which comprises one or more reactants contain ⁇ ing one or more of the halides selected from the class consisting of F, CI, Br, and I. Included in the definition of halide-containing reactants are compounds having the formula X 2 , HX, MX & , or MX a _ b ) H b where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of any of the metal reactants and Pb; a is the maximum oxida ⁇ tion state or valence of the metal M; and b has a value of from 1 to a-1.
  • gaseous By use of the term “gaseous” is meant that the halogen-containing reactant is introduced into the first reaction zone as a gas or a vapor at the temperature of operation.
  • the halogen-containing reactant is a vapor, for example, it may be introduced into the first reaction zone with a carrier gas.
  • all of the metal reactants may be present as particles or one or more of the metal reactants may be introduced into the reaction zone in the form of the fluidized particles, while one or more other metal reactants may form a part of the gaseous halogen-containing reactant, if de- sired.
  • the additional reactant may comprise a nitrogen, carbon, oxygen, or boron source, respec ⁇ tively, (or mixture of same when a mixed nitride, carbide, oxide, or boride is desired) which is in the gaseous state at the reaction pressure and temperature.
  • the reaction time in the second reaction zone needed for the one or more reactive intermediates to react with the third reactant to form a nitride, carbide, oxide, or boride of the one or more metal reactants or a mixture of such compounds, in the form of a powder deposit or a deposit of a coating on a suitable substrate varies from about 10 "16 seconds to about 100 seconds, preferably about 10 ⁇ 6 seconds to about 10 seconds.
  • the additional reactant may be any 1-20 carbon hydrocarbon containing hy ⁇ drogen and carbon such as, for example, methane, ethane, ethene, ethyne, propane, propene, propyne, butane, 1-butene, and 1-butyne, which will be gas ⁇ eous at the reaction temperature.
  • the additional reactant may be any boron-containing material which contains only boron and hydrogen or other materials already present in the first reaction zone such as a hal- ide.
  • the source of boron will be a borane such as diborane (B 2 H 6 ) .
  • the nitrogen, carbon, oxygen, and boron sources which may be used as the additional reactant may be greatly expanded, subject to the provisions discussed above with regard to the gaseous state of the reactant.
  • any organic material containing only carbon, hydrogen, and nitrogen may be used as the additional reactant when it is desired to form a mixture of at least one carbide and at least one nitride; while organic sources containing carbon, hydrogen and boron may be used to form mixtures containing at least one carbide and at least one boride.
  • mixtures of more than one additional reactant may be used, either to form solely a nitride, carbide, oxide, or boride, or, as will more likely be the case, to form various mixtures of nitrides, carbides, oxides, and borides.
  • the initial formation of one or more reactive in ⁇ termediates from the reaction between the metal reactant and the halogen-containing reactant is believed to form unstable intermediates which may then, in turn, either react with another reactant such as the nitrogen, carbon, oxygen, or boron- containing reactants discussed above to respective- ly form a nitride, carbide, oxide, or boride; or decompose to permit formation of a coating or pow ⁇ der consisting essentially of the initial metal reactant or reactants.
  • the metal reactant is silicon and the halide-containing reactant is bromine
  • the silicon may react with the silicon according to the following equation:
  • Si + 2 Br 2 > SiBr 4 may, in turn, then further react with the silicon present in the reactor to form equilibriums of the following species:
  • subhalide and halosilane species are very reactive and it is believed that they either decompose to form a powder deposit or a coating, if a coatable substrate is present, of the metal reac ⁇ tant, e.g., silicon; or, if another reactant is then introduced into the reactor, these unstable subhalide species react with the additional reac ⁇ tant, e.g., NH 3 to form a powder or coating com ⁇ prising the reaction product of the metal reactant and the other reactant, e.g., the formation of S ---3 N 4 -°y reaction of one or more of the reactive silicon-containing intermediate subhalide species with NH 3 .
  • the halogen-containing reactant is merely passed through the bed of metal reactant particles in the first reaction zone while main ⁇ taining this reaction zone at from about 200 ⁇ C to about 1000-C, preferably from about 400"C to about 800-C, for a period of from about 0.01 to about 100 minutes as shown in the apparatus in Figure 5.
  • the one or more metal reactants react with the halogen-containing reactant to form the one or more reactive intermediates, as discussed above, which then react or disproportionate to form a powder of the one or more metal reactants.
  • This step may take place in a cooler zone 58 which may be pro ⁇ vided by a cold solid or a liquid substrate or, as shown in Figure 5, by a stream of cold gas flowing into cool zone 58 of reactor 10 through a plenum. 6.
  • the average temperature in cool zone 58 may J_>e 50 ⁇ C or more below that of first reaction z@ne 34.
  • the two zones may be part of the same chamber as
  • the resulting metal powder will be an alloy of the metal reac ⁇ tants with the ratio of the constituents of the alloy proportional to the ratio of the metal reac- tants in the reaction zone.
  • the resultant powder is a pure and ultrafine metal powder, typically having a particle size of from about 100 Angstroms to about 10 microns. This powder is light enough to pass out of the reactor entrained with the gas used to form the moving bed.
  • a titanium/aluminum alloy powder may be formed when titanium and alumi- num are both used as metal reactants. It should be noted that, in contrast to the prior art, the present process operates at atmospheric pressure, i.e., vacuum conditions are not needed.
  • the substrate to be coated may be placed in the reaction zone and, as the reaction between the one or more metal reactants and the halogen- containing reactant proceeds, the one or more reac ⁇ tive intermediates formed in this reaction will decompose and the resulting metal or metals will form a coating on the substrate.
  • Coatings are obtained on substrates placed inside the particle bed and immediately above it, i.e., less than 5 cm. above the bed.
  • the substrate temperature may be 50 ⁇ C higher than the bed with the rate of deposition increasing with temperature differences reaching a maximum for temperature differences of about 200'C.
  • This val ⁇ ue may change with the chemical system and reactor design, and is, therefore, given only for illustration purposes.
  • Coatings can also be obtained on substrates located immediately above the bed and maintained at temper ⁇ atures below that of the bed, typically 50 ⁇ C, but as much as 200 ⁇ C lower than the bed temperature.
  • coatings can be obtained in some cases even when the bed and the substrate are kept at the same temperature, for example, silicon can be coated on copper when both the bed and the sub ⁇ strate are kept at about 600'C. Silicon deposits and diffuses in the copper thus decreasing the silicon activity.
  • the gas phase in the bed acts as a transport agent for silicon from the bed with silicon activity of 1. In this mode, the driving force is the partial chemical gradient due to ac- tivity differences rather than temperature differ ⁇ ences.
  • copper tubes 50 are shown suspended in first reac ⁇ tion zone 34 where they are coated with the one or more metal reactants.
  • copper, steel, and silica substrates were coated respectively with silicon (copper substrate) , titanium (copper, steel, and silica substrates) and zirconium (steel substrate) as shown in the table below.
  • the one or more reactive intermediates formed in first reaction zone 34 may pass upward in the reactor into a second reaction zone 60 above the particle bed comprising first reactive zone 34 where a third reactant, comprising a material as previously described, which is intro ⁇ quizd therein through an inlet port 70, contacts the one or more reactive intermediates to form, respectively, one or more metal nitrides, carbides, oxides, borides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, " oxygen, boron, or a mixture of same, as powders which are then passed out of the reactor through exit port 18 with the gases leaving reactor 10.
  • a third reactant comprising a material as previously described, which is intro ⁇ quizd therein through an inlet port 70
  • silicon nitride (Si 3 N 4 ) powder was produced by fluidizing 325 mesh silicon particles in a 5 cm ID 50 cm long fluidized bed reactor by an argon flow of 4 liters/min having a bed height (in repose) of 10 cm.
  • the fluidized bed was heated externally to 600 ⁇ C for 1 hour, after which a flow of HBr gas was mixed with the argon fluidizing gas and coijijected into the bed as shown in Figure 7.
  • a flow of ammonia gas at a rate of 30-100 cm 3 /min was fed through the top of.
  • Figures 8 and 9 show, respectively, formation of coatings of metal compounds on a substrate in the second reaction zone in the reactor.
  • a first plug 80 of graphite fibers is inserted into reactor 10 just above first reaction zone 34 and a second plug 82 of graphite fibers is also inserted into reactor 10 a spaced distance from first plug 80 forming a second reaction zone 60' commencing with the bottom of first plug 80 and extending upward through second plug 82.
  • a coating is formed on at least the first plug 80 of graphite fibers comprising, respectively, one or more metal ni ⁇ trides, carbides, borides, oxides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, oxygen, boron, or a mixture of same.
  • a fluidized bed of 325 mesh silicon particles was formed in the reactor of Figure 8 by fluidizing the bed with nitrogen gas after preheat ⁇ ing the reactor bed to about 600'C.
  • HBr was mixed with the fluidizing gas as the halogen-containing reactant.
  • NH 3 was then injected through the upper graphite plug into the second reaction zone com ⁇ prising the space above the fluidized bed.
  • the resulting bromosilanes and subbromides formed in the first reaction zone (the fluidized bed) reacted with the NH 3 in the second reaction zone which was maintained at about 1200*C.
  • the process was al ⁇ lowed to proceed for 2.5 hours after which the process was stopped and the lower graphite plug removed for analysis.
  • the hard grayish brittle coating on the carbon fibers was studied using both scanning electron microscopy (SEM) and energy dis ⁇ persive x-ray analysis (EDAX) which confirmed the presence of a Si 3 N coating on the carbon fibers.
  • substrates 50 are shown suspended in second reaction zone 60 above reaction zone 34 and a third reactant is injected into this second zone, similarly to that shown in Figures 7 and 8, where it contacts the one or more reactive intermediates rising from first reaction zone 34 to form a coat- ing on the suspended substrate comprising, respectively, one or more metal nitrides, carbides, oxides, borides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, oxygen, boron, or a mixture of same.
  • a bed of 325 mesh titanium particles was formed and preheated to 750"C prior to being fluid ⁇ ized by a flow of argon gas at atmospheric press- ure.
  • HBr gas was then mixed with the argon fluid ⁇ izing gas to obtain a partial pressure of 7 torr.
  • Steel and silica substrates were suspended in the second reaction zone above the bed and a flow of NH 3 gas was injected into this zone from the top of the reactor while maintaining this second reaction zone at a temperature of 800'C.
  • Gold colored coatings were formed on the substrates and these coatings were confirmed by subsequent x- ray diffraction, SEM, and EDAX to be TiN.
  • the coated steel substrate was tested for corrosion resistance in aqueous chloride solutions and found to have an increase in corrosion resistance of approximately 30 times that of uncoated steel.
  • the invention provides a novel process for the formation of powders or coatings of either one or more metal reactants powders in a moving bed reactor initially reacted with a halogen-containing reactant to form reactive intermediates which dis ⁇ proportionate or decompose to form the metal powder or coating; or which reactive intermediates may react further with another reactant introduced into a second reaction zone to form one or more metal compounds in the form of either a powder or a coating.

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Abstract

A low temperature process is described for forming a coating or powder comprising one or more metals or metal compounds by first reacting one or more metal reactants with a halide-containing reactant to form one or more reactive intermediates capable of reacting, disproportionating, or decomposing to form a coating or powder comprising the one or more metal reactants. When one or more metal compounds are formed, either as powders or as coatings, a third reactant may be injected into a second reaction zone in the reactor to contact the one or more reactive intermediates formed in the first reaction zone to thereby form one or more metal compounds such as metal nitrides, carbides, oxides, borides, or mixtures of same.

Description

LOW TEMPERATURE METHOD OF FORMING MATERIALS USING ONE OR MORE METAL REACTANTS AND A HALOGEN-CONTAINING REACTANT TO FORM ONE OR MORE REACTIVE INTERMEDIATES
Background of the Invention
1. Field of the Invention
This invention relates to the production of mater¬ ials in the form of coatings or powders using a 5 halogen-containing reactant which will react with a second reactant to form one or more reactive inter¬ mediates from which the powder or coating may be formed by disproportionation, decomposition, or reaction. In one embodiment, the powder or coating 10 is formed directly from the one or more reactive intermediates. In a second embodiment, the one or more reactive intermediates react with a gaseous third reactant resulting in the formation of a powder or coating.
15 2. Description of the Related Art
Metallic and ceramic powders and coatings can be formed by a variety of techniques including vapor deposition, chemical vapor deposition (CVD) , sput¬ tering, dip coating, slurry painting, pack cementa-
20 tion, thermal spraying, grinding, milling, etc. Each technique has some advantages and disadvan¬ tages that dictate their major area of applications.
For example, when a powder of a particular material is to be formed, the material may be milled or
25 ground. However, when the desired powder is an element such as aluminum, silicon, titanium, etc., such milling or grinding may require implementation of additional safety requirements. Additionally, the formation of powders from compounds usually
30 requires additional steps to produce the compound from which the powder will be formed. When a coating of a particular material is desired, the material may be applied as a vapor by first volatilizing the material, which may in some cases require very high temperatures, e.g. as high as 2000"C or higher for materials such as silicon and titanium, or the coating may be applied by other means mentioned above such as sputtering, coating, painting, or spraying which, while not requiring as high a temperature as the vaporization techniques, may not form a bond which is as satisfactory.
Stinton et al in "Advanced Ceramics by Chemical Vapor Deposition Techniques", Ceramic Bulletin. Volume 67, No. 2 (1988), pages 350-355, describes the use of CVD techniques to form a number of carbides, nitrides, oxides, and borides of various metals.
When a coating of a compound is desired, CVD is particularly well suited for many applications including deposition of semiconductor and metallic interconnects, deposition of hard coatings for tools and gears, and deposition of corrosion resis¬ tant coatings for aqueous and high temperature environments, Typically a gas mix such as, for example, TiCl4 and NH3 are passed over a substrate heated to high temperature, (>1000'C) so that a film of TiN, which is formed in situ, deposits on the substrate.
Some of the factors which limit the use of CVD are cost (capital equipment cost and operating cost) , and, in some cases, the need to operate at high temperatures that may degrade the properties of the substrate. Another limitation of CVD, in some cases, may be the difficulty in maintaining con¬ stant temperature on the substrate and constant composition of the gas phase, especially if the substrate has a convoluted geometry.
To reduce the effects of these disadvantages and limitations, improvement have been proposed in the past such as, for example, the use of plasma as¬ sisted CVD. Unfortunately, the use of such plasma assisted CVD requires working at low pressures which results in higher coating costs.
Other improvements aimed at improving the homo¬ geneity of the coatings consisted of modifying the flowdyna ics of the gas around the piece to be coated and careful design of the heating unit.
Such approaches can result in expensive, one-of-a- kind systems, and low utilization of the reactants.
Another approach is described in Japka et al U.S. Patent 4,623,400 wherein a gas mix containing va- pors of the coating precursor is injected into a fluidized bed containing inert particles. The piece to be coated is immersed in the bed. The use of a flowing bed reactor (FBR) with its fast heat transfer permits the piece to be coated to be maintained at a uniform temperature by the bed, resulting in a more uniform coating. Unfortunate¬ ly, in this process, much of the coating material is deposited on the inert fluidized bed particles and the reaction requires expensive reactants.
Using silicon as an example, when it is desired to form a powder compound such as silicon nitride or silicon carbide, it is not usually possible to form such compounds directly from silicon without the use of high temperatures. For example, Jennings, in an article entitled "On Reactions Between Sili¬ con and Nitrogen", published in the Journal of Materials Science. Volume 18, (1963), pages 951- 967, states that typical nitriding involves heating silicon, usually a powder compact, and nitrogen to temperatures between 1300 and 1500βC, although
Pugar et al, in an article entitled "Low Tempera¬ ture Direct Reactions Between Elemental Silicon and Liquid Ammonia or Amines for Ceramics and Chemical Intermediates", Materials Research Society Sympos- ium Proceedings. Volume 21, 1988, pages 439-447, reports direct reactions between elemental silicon and either ammonia or hydrazine at low temperatures.
In the prior art, however, it has been conventional to use more reactive materials such as silicon halides or εilanes as the source of silicon for forming .silicon compounds such as silicon nitride, silicon carbide, etc. For example, Mazdiyasni et al U.S. patent 3,959,446 describes a process for producing silicon nitride powder using liquid sili- con tetrachloride and ammonia as the initial reac¬ tants to "form a mixture of silicon diimide and ammonium chloride which is then heated under a vacuum of from 10~3 to 10"4 torr to a temperature of 1200 to 1350*C to form the silicon nitride from this intermediate.
Similarly, when a coating is to be formed compris¬ ing a compound, e.g., of silicon nitride or titanium carbide, it is necessary to both form the compound as well as provide a means for depositing or forming the coating on a substrate.
It would, therefore, be desirable to provide a process wherein powders or coatings comprising either a single element, or the reaction product of an element with another reactant, could be formed without the need for use of expensive reactants and/or high temperatures and/or pressures and the need for carefully controlled reaction conditions.
Summary of the Invention
It is, therefore, an object of this invention to provide a low temperature process for forming a coating or powder comprising one or more metals or metal compounds by reacting the one or more metals with a halide-containing reactant in a moving bed reactor to form one or more reactive intermediates capable of forming a coating or powder with or without reaction with another material.
It is another object of this invention to provide a low temperature process for forming a coating or powder comprising one or more metals by reacting the one or more metals with a halide-containing reactant in a moving bed reactor to form one or more unstable reactive intermediates capable of disproportionating, decomposing, or reacting to form a coating or powder of the one or more metals.
It is yet another object of this invention to provide a low temperature process for forming on a substrate a coating comprising one or more metals by reacting the one or more metals with a halide- containing reactant in a moving bed reactor to form one or nore unstable reactive intermediates capable of disproportionating, decomposing, or reacting to deposit a coating of the one or more metals on the substrate.
It is still another object of this invention to provide a low temperature process for forming a powder comprising one or more metals by reacting the one or more metals with a halide-containing reactant in a first reaction zone of a moving bed reactor to form one or more unstable reactive in¬ termediates capable of disproportionating, decom- posing, or reacting in a second zone of the reactor to form a powder of the one or more metals.
It is a further object of this invention to provide a low temperature process for forming a coating or powder comprising one or more metal compounds by reacting one or more metals with a halide-contain¬ ing reactant in a moving bed reactor to form one or more reactive intermediates capable of dispropor¬ tionating, decomposing, or reacting with another reactant to form a coating or powder comprising one or more.metal compounds of the one or more metal reactants.
It is a yet further object of this invention to provide a low temperature process for forming a coating or powder comprising one or more metal compounds by reacting one or more metals with a halide-containing reactant in a first zone of a oving bed reactor to form one or more reactive intermediates which then disproportionate, decom¬ pose, or react, in a second zone of the reactor, with another reactant selected from the class con- sisting of a boron-containing reactant, a carbon- containing reactant, a nitrogen-containing reac¬ tant, an oxide-containing reactant, and mixtures thereof to form a coating or powder comprising, respectively, one or more metal borides, carbides, nitrides, oxides, or a mixture thereof, of the one or more metal reactants depending upon the other reactant.
It is still a further object of this invention to provide a low temperature process for forming on a substrate a coating comprising one or more com¬ pounds of one or more metals by reacting the one or more metals with a halide-containing reactant, in a first zone of a moving bed reactor, to form one or more reactive intermediates which then dispropor- tionate, decompose, or react, in a second zone of the reactor, with another reactant selected from the class consisting of a boron-containing reac¬ tant, a carbon-containing reactant, a nitrogen- containing reactant, an oxide-containing reactant, and mixtures thereof to deposit on the substrate a coating of one or more metal compounds comprising, respectively, one or more metal borides, metal carbides, metal nitrides, metal oxides, or a mix¬ ture thereof, of the one or more metal reactants depending upon the other reactant.
It is another object of this invention to provide a low temperature process for forming a powder comprising one or more compounds of one or more metals by reacting the one or more metals with a halide-containing reactant in a first zone of a moving,bed reactor to form one or more reactive intermediates which then disproportionate, decom¬ pose, or react, in a second zone of the reactor, with another reactant selected from the class con¬ sisting* of a boron-containing reactant, a carbon- contajjxing reactant, a nitrogen-containing re- actant, an oxygen-containing reactant, and mixtures thereof to form a powder comprising, respectively, one or more metal borides, metal carbides, metal nitrides, metal oxides, or a mixture thereof, of the one or more metal reactants depending upon the other reactant.
These and other objects of the invention will be apparent from the following description and accom¬ panying illustrations.
Brief Description of the Drawings
Figure 1 is a flow sheet illustrating a first embodiment of the process of the invention.
Figure 2 is a flow sheet illustrating a second embodiment of the process of the invention.
Figure 3 is a flow sheet illustrating a third embodiment of the process of the invention.
Figure 4 is a flow sheet illustrating a fourth embodiment of the process of the invention. Figure 5 is a vertical cross section view of a moving bed reactor showing the production of metal powder from the decomposition of one or more reac¬ tive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
Figure 6 is a vertical cross section view of a moving bed reactor showing the formation of a metal coating on a substrate by the decomposition of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-contain¬ ing reactant.
Figure 7 is a vertical cross section view of a moving bed reactor showing the formation of a pow¬ der comprising one or more metal compounds by reac- tion with a third reactant, in a second zone, of one or more reactive intermediates formed by react¬ ing one or more metal reactants with a halogen- containing reactant.
Figure 8 is a vertical cross section view of a moving bed reactor showing the formation of a coat¬ ing on graphite fibers of one or more metal com¬ pounds by reaction with a third reactant, in a second zone, of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
Figure 9 is a vertical cross section view of a moving bed reactor showing the formation of a coat¬ ing on steel plates of one or more metal compounds by reaction with a third reactant, in a second zone, of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
Figure 10 is a graph showing the thermodynamic estimate of equilibrium partial pressures of species in the Si-H-Br system as a function of temperature for Br/H = 0.01.
Figure 11 is a graph showing the mass spectrum obtained when mixtures of H2/SiBr4 are passed through silicon powder Br/H •= 0.0063.
Figure 12 is a graph showing the mass spectrum of species in the Si-H-Br system obtained when HBr is passed through silicon powder.
Detailed Description of the Invention
The invention provides a novel low temperature process for forming a powder or a coating compris¬ ing one or more metals or metal compounds by reacting the one or more metals with a halide- containing reactant in a moving bed reactor to form one or more reactive intermediates capable of form- ing a coating or powder. The coating or powder may comprise one or more decomposition products of the one or more reactive intermediates comprising the one or more metals initially reacted with the halide-containing reactant.
Alternatively, the coating or powder may comprise the reaction product of the one or more reactive intermediates reacted with another reactant intro¬ duced into a second reaction zone of the reactor and selected from the class consisting of a boron- containing reactant, a carbon-containing reactant, a nitrogen-containing reactant, an oxygen-contain¬ ing reactant, and mixtures thereof to form the powder or coating which comprises, respectively, one or more metal borides, metal carbides, metal nitrides, metal oxides, or a mixture thereof, of the one or more metal reactants depending upon the other reactant.
While the foregoing formations of either coatings or powders of either the initial one or more metal reactants or reaction products containing the one or more metal reactants as borides, carbides, ni¬ trides, oxides, or mixtures thereof will be des- cribed separately below for purposes of clarity, it must be noted that the gravamen of the invention is the initial reaction of the one or more metal reactants with the halide-containing reactant at atmospheric pressure and at a low temperature to form one or more reactive intermediates. This low temperature formation of the reactive intermediates makes possible the subsequent low temperature for¬ mation of the powders or coatings.
By the use of the term "low temperature" herein to describe the initial reaction between the one or more metal reactants with the halide-containing reactant is meant a temperature ranging from about 200-C, but no higher than about 1000"C. A prefer¬ able range for this reaction is from about 400βC to about 800 ' C, but the term "low temperature", when used herein without further definition of the tem¬ perature, will be understood to mean the broader range of from about 200*C to about 1000*C.
The use of the term "low temperature" to describe the reaction in a second zone of the reactor used in forming either the powder or coating comprising the boride, nitride, carbide, oxide, or mixture of the one or more metal reactants is intended to define a temperature range of from about room tem¬ perature, i.e., 20-25'C to about 1300'C. The tem¬ perature in this second zone preferably ranges from about 600 to about 900-C.
This temperature range may be maintained within the one or more reaction zones within the reactor by any convenient heating means such as resistance heating, RF heating, microwave heating, radiation heating^ laser heating, arc heating, or gas heating.
The one or more metal reactants which are reacted with the halide-containing reactant may comprise any metal or metals capable of reacting with a halide-containing reactant to form one or more metal halide intermediates, regardless of the in¬ stability of the reaction intermediate. Such metals include the transition metals Ti, V, Cr, Zr, Nb, Mo-, Hf, Ta, and W, as well as Al, Si and B. WJjile it is recognized that silicon and boron are not technically considered to be metals, the use of the terms "metaj. reactant" and/or "metal reactants" herein ill be understood to include Si and B as well as those elements traditionally recognized as metals.
The metal reactant is preferably provided in particulate form comprising particles having a size of from about 100 to about 1000 microns. However, the metal reactant may also be provided in other forms such as foils and fibers and other shapes which provide dispersions with large surface to volume ratios. The metal reactant is reacted with the halide-containing reactant by placing the metal reactant powder in a moving bed reactor such as a fluidized bed reactor. An inert gas may be used to fluidize the bed or the powder may be rotated, moved by gravity, vibration, or any other suitable means which will move or agitate the particle bed. It should be noted in this regard that the particle bed itself comprising the moving bed in the reactor comprises the metal reactant in particulate form, not an inert material.
The reactor may comprise any suitable non-reactive containment vessel capable of containing a moving bed such as, for example, a fluidized bed. A suit- able containment vessel, for example, would be a quartz cylinder. The walls of the reactor are kept hotter than the bed to inhibit deposition on the walls. As shown in Figure 5, by way of example, a fluidized bed reactor 10 may comprise a cylindrical vessel 14 having an exit port 18 and a tapered lower portion 16 into which an inert fluidizing gas enters through a first port 20 and is mixed with the halogen-containing reactant in gaseous form which enters tapered portion 16 through a second port 24.
The gaseous mixture then enters a first reaction zone 34 through a distribution plate 30 located just above tapered portion 16 in reactor 10. Above distribution plate 30 is located, in first reaction zone 34, the bed of particles comprising the one or more metal reactants, e.g., titanium particles. Around the outside walls of reactor 10 is placed a heating means 40 which may, for example, comprise a tubular resistance furnace which cooperates with thermocouple temperature sensor 42 to maintain first reaction zone 34 in reactor 10 within the temperature range of from about 200βC to about
800*C. When the fluidizing gas mixture containing the halogen-containing reactant enters first reac¬ tion zone 34 through distribution plate 30, the metal reactant particles are both fluidized and brought into intimate contact with the one or more metal reactants to thereby form the one or more reactive intermediates.
As will be further described below, these reactive intermediates then either form the powder or a coating deposited on a substrate; or pass on into a second reaction zone to react with a third reactant to form the powders or coatings of metal nitrides, metal carbides, or metal borides, or mixtures thereof as will also be described below.
The reaction time, or residence time needed in the first reaction zone for the one or more metal reactants to react with the halogen-containing reactant to form the reactive intermediate varies from about 0.1 seconds up to 100 minutes, preferab- ly about 1 second to about 100 seconds.
When a coating is to be formed on a substrate, either comprising a metal coating formed by decom¬ position of the one or more reactive intermediates formed by reaction between the one or more metal reactants and the halogen-containing reactant, or by a reaction between the one or more reactive intermediates and a third reactant to form one or more metal compounds, as will be described below, the substrate may comprise any material capable of withstanding the temperatures which will be used in the reactor to form the coating. Thus, most metals or ceramic materials, for example, will be suitable substrate materials on which the coating may be deposited. Examples of other suitable substrate materials include metals such as Cu, Ni, Fe, alloys such as steels, super alloys, monolithic ceramics such as A1203, Zr02, Si02, SiC, Si3N4, TiN, etc., or fibers, whiskers, or powders of any of the above, or composites thereof.
The halide-containing reactant is a gaseous reac- tant which comprises one or more reactants contain¬ ing one or more of the halides selected from the class consisting of F, CI, Br, and I. Included in the definition of halide-containing reactants are compounds having the formula X2, HX, MX&, or MX a_ b) Hb where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of any of the metal reactants and Pb; a is the maximum oxida¬ tion state or valence of the metal M; and b has a value of from 1 to a-1.
By use of the term "gaseous" is meant that the halogen-containing reactant is introduced into the first reaction zone as a gas or a vapor at the temperature of operation. When the halogen- containing reactant is a vapor, for example, it may be introduced into the first reaction zone with a carrier gas.
It should be noted that when more than one metal reactant is to be used, either to form a powder or coating alloy, or to form a mixture of nitrides, carbides, oxides, and/or borides, as will be des¬ cribed below, all of the metal reactants may be present as particles or one or more of the metal reactants may be introduced into the reaction zone in the form of the fluidized particles, while one or more other metal reactants may form a part of the gaseous halogen-containing reactant, if de- sired.
When another reactant is added to a second reaction zone in the reactor to react with the reactive intermediate formed in the first zone to thereby form a nitride, carbide, oxide, or boride of the one or more metal reactants or a mixture of such compounds; the additional reactant may comprise a nitrogen, carbon, oxygen, or boron source, respec¬ tively, (or mixture of same when a mixed nitride, carbide, oxide, or boride is desired) which is in the gaseous state at the reaction pressure and temperature.
The reaction time in the second reaction zone needed for the one or more reactive intermediates to react with the third reactant to form a nitride, carbide, oxide, or boride of the one or more metal reactants or a mixture of such compounds, in the form of a powder deposit or a deposit of a coating on a suitable substrate, varies from about 10"16 seconds to about 100 seconds, preferably about 10~6 seconds to about 10 seconds.
When a nitride is to be formed, the nitrogen source, for example, may comprise N2, or an ammonia or hydrazine reactant having the formula
Figure imgf000019_0001
where n = 1-4, and m = 2 when the nitrogen-hydrogen reactant is a straight chain and 0 when the nitrogen-hydrogen reactant is cyclic.
When a carbide is desired, the additional reactant may be any 1-20 carbon hydrocarbon containing hy¬ drogen and carbon such as, for example, methane, ethane, ethene, ethyne, propane, propene, propyne, butane, 1-butene, and 1-butyne, which will be gas¬ eous at the reaction temperature.
When a boride is desired, the additional reactant may be any boron-containing material which contains only boron and hydrogen or other materials already present in the first reaction zone such as a hal- ide. Preferably, the source of boron will be a borane such as diborane (B2H6) .
It must be further noted that if it is desired to form a mixture of nitrides, carbides, oxides, and borides, in any combination, then the nitrogen, carbon, oxygen, and boron sources which may be used as the additional reactant may be greatly expanded, subject to the provisions discussed above with regard to the gaseous state of the reactant. For example, any organic material containing only carbon, hydrogen, and nitrogen may be used as the additional reactant when it is desired to form a mixture of at least one carbide and at least one nitride; while organic sources containing carbon, hydrogen and boron may be used to form mixtures containing at least one carbide and at least one boride.
In addition, mixtures of more than one additional reactant may be used, either to form solely a nitride, carbide, oxide, or boride, or, as will more likely be the case, to form various mixtures of nitrides, carbides, oxides, and borides.
The initial formation of one or more reactive in¬ termediates from the reaction between the metal reactant and the halogen-containing reactant is believed to form unstable intermediates which may then, in turn, either react with another reactant such as the nitrogen, carbon, oxygen, or boron- containing reactants discussed above to respective- ly form a nitride, carbide, oxide, or boride; or decompose to permit formation of a coating or pow¬ der consisting essentially of the initial metal reactant or reactants.
By way of illustration, and not of limitation, for example, when the metal reactant is silicon and the halide-containing reactant is bromine, the silicon may react with the silicon according to the following equation:
Si + 2 Br2 > SiBr4 The SiBr4 may, in turn, then further react with the silicon present in the reactor to form equilibriums of the following species:
3 SiBr4 + si <■-=> 4 SiBr3 SiBr4 + Si <•=-> 2 SiBr2
SiBr4 + 3 Si <=> 4 SiBr
When H2 is also present in the equilibrium, for example by the use of HBr as the halogen-containing reactant, then the following equations are also possible:
SiBr4 + H2 <=> Si + 4 HBr Si + 3 HBr <=> SiHBr + H2 Si + 2 HBr <=> SiH2Br2 Si + 3 HBr <=> SiH3Br + Br2
Some of these subhalide and halosilane species are very reactive and it is believed that they either decompose to form a powder deposit or a coating, if a coatable substrate is present, of the metal reac¬ tant, e.g., silicon; or, if another reactant is then introduced into the reactor, these unstable subhalide species react with the additional reac¬ tant, e.g., NH3 to form a powder or coating com¬ prising the reaction product of the metal reactant and the other reactant, e.g., the formation of S---3N4 -°y reaction of one or more of the reactive silicon-containing intermediate subhalide species with NH3.
I. Formation of Metal Powder
When it is desired to form a metal powder consist- ing of the one or more metal reactants in the particle bed, the halogen-containing reactant is merely passed through the bed of metal reactant particles in the first reaction zone while main¬ taining this reaction zone at from about 200βC to about 1000-C, preferably from about 400"C to about 800-C, for a period of from about 0.01 to about 100 minutes as shown in the apparatus in Figure 5.
The one or more metal reactants react with the halogen-containing reactant to form the one or more reactive intermediates, as discussed above, which then react or disproportionate to form a powder of the one or more metal reactants. This step may take place in a cooler zone 58 which may be pro¬ vided by a cold solid or a liquid substrate or, as shown in Figure 5, by a stream of cold gas flowing into cool zone 58 of reactor 10 through a plenum. 6. The average temperature in cool zone 58 may J_>e 50βC or more below that of first reaction z@ne 34.
.The two zones may be part of the same chamber as
.fhσwn in Figure 5 wherein the fluidized bed consti- * tutes first reaction zone 34 and the space above it constitutes cooling zone 58 which is cooled by add¬ ing a cold gas through the walls of the reactor above the bed. The powder product be then be formed in this cooler zone 58 and then entrained in the gas flowing out of reactor 10 through outlet 18 for collection outside of reactor 10.
When more than a single metal reactant is used, either in the particle bed or in the particle bed in-combination with one or more metal reactants in the halogen-containing reactant, the resulting metal powder will be an alloy of the metal reac¬ tants with the ratio of the constituents of the alloy proportional to the ratio of the metal reac- tants in the reaction zone.
The resultant powder is a pure and ultrafine metal powder, typically having a particle size of from about 100 Angstroms to about 10 microns. This powder is light enough to pass out of the reactor entrained with the gas used to form the moving bed.
When more than one metal reactant is present, fine powder metal alloys are produced at relatively low temperatures. For example, a titanium/aluminum alloy powder may be formed when titanium and alumi- num are both used as metal reactants. It should be noted that, in contrast to the prior art, the present process operates at atmospheric pressure, i.e., vacuum conditions are not needed.
II. Formation of Metal Coating
As shown in Figure 6, when it is desired to form a coating of one or more metal reactants on a sub¬ strate, the substrate to be coated may be placed in the reaction zone and, as the reaction between the one or more metal reactants and the halogen- containing reactant proceeds, the one or more reac¬ tive intermediates formed in this reaction will decompose and the resulting metal or metals will form a coating on the substrate.
Coatings are obtained on substrates placed inside the particle bed and immediately above it, i.e., less than 5 cm. above the bed. In some cases, i.e., deposition of silicon or titanium on steel, the substrate temperature may be 50βC higher than the bed with the rate of deposition increasing with temperature differences reaching a maximum for temperature differences of about 200'C. This val¬ ue, however, may change with the chemical system and reactor design, and is, therefore, given only for illustration purposes.
Coatings can also be obtained on substrates located immediately above the bed and maintained at temper¬ atures below that of the bed, typically 50βC, but as much as 200βC lower than the bed temperature.
Finally, coatings can be obtained in some cases even when the bed and the substrate are kept at the same temperature, for example, silicon can be coated on copper when both the bed and the sub¬ strate are kept at about 600'C. Silicon deposits and diffuses in the copper thus decreasing the silicon activity. The gas phase in the bed acts as a transport agent for silicon from the bed with silicon activity of 1. In this mode, the driving force is the partial chemical gradient due to ac- tivity differences rather than temperature differ¬ ences.
In the illustrated embodiment shown in Figure 6, copper tubes 50 are shown suspended in first reac¬ tion zone 34 where they are coated with the one or more metal reactants. In specific examples, using apparatus similar to that shown in Figure 6, copper, steel, and silica substrates were coated respectively with silicon (copper substrate) , titanium (copper, steel, and silica substrates) and zirconium (steel substrate) as shown in the table below.
Table I
Temp Time
Substrate Coating fβC) ( in) Remarks
Cu Si 750 120 totally siliconized
CU Si 600 15 very thin
Cu Si 600 37 excellent
Cu Ti 750 45 excellent
Steel Ti 750 45 good, TiC* interface
Silica Ti 750 45 good
Steel Zr 900 120 ZrC* interface
*Carbon initially present in the steel III. Formation of Powder of Metal Compound
As shown in Figure 7, the one or more reactive intermediates formed in first reaction zone 34 may pass upward in the reactor into a second reaction zone 60 above the particle bed comprising first reactive zone 34 where a third reactant, comprising a material as previously described, which is intro¬ duced therein through an inlet port 70, contacts the one or more reactive intermediates to form, respectively, one or more metal nitrides, carbides, oxides, borides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon," oxygen, boron, or a mixture of same, as powders which are then passed out of the reactor through exit port 18 with the gases leaving reactor 10.
For example, silicon nitride (Si3N4) powder was produced by fluidizing 325 mesh silicon particles in a 5 cm ID 50 cm long fluidized bed reactor by an argon flow of 4 liters/min having a bed height (in repose) of 10 cm. The fluidized bed was heated externally to 600βC for 1 hour, after which a flow of HBr gas was mixed with the argon fluidizing gas and coijijected into the bed as shown in Figure 7. A flow of ammonia gas at a rate of 30-100 cm3/min was fed through the top of. the reactor so that the NH3 and bromosilane reactive intermediates from the first reactive zone (the fluidized bed) mixed in the second reactive zone (the hot zone above the fluidized bed) which is kept at about 1000*C. A sample of white powder formed which was entrained with the fluidizing gas as it passed out of the reactor. Analysis of this white powder by x-ray diffraction showed that it contained a mixture of Si3N4 and silicon.
IV. Formation of Coating of Metal Compound
Figures 8 and 9 show, respectively, formation of coatings of metal compounds on a substrate in the second reaction zone in the reactor. In Figure 8, a first plug 80 of graphite fibers is inserted into reactor 10 just above first reaction zone 34 and a second plug 82 of graphite fibers is also inserted into reactor 10 a spaced distance from first plug 80 forming a second reaction zone 60' commencing with the bottom of first plug 80 and extending upward through second plug 82. When a third reac- tant, comprising a material as previously des¬ cribed, is introduced therein through an inlet port 70, as in Figure 7, and contacts the one or more reactive intermediates, a coating is formed on at least the first plug 80 of graphite fibers comprising, respectively, one or more metal ni¬ trides, carbides, borides, oxides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, oxygen, boron, or a mixture of same.
To illustrate the formation of a metal coating on a substrate, a fluidized bed of 325 mesh silicon particles was formed in the reactor of Figure 8 by fluidizing the bed with nitrogen gas after preheat¬ ing the reactor bed to about 600'C. HBr was mixed with the fluidizing gas as the halogen-containing reactant. NH3 was then injected through the upper graphite plug into the second reaction zone com¬ prising the space above the fluidized bed. The resulting bromosilanes and subbromides formed in the first reaction zone (the fluidized bed) reacted with the NH3 in the second reaction zone which was maintained at about 1200*C. The process was al¬ lowed to proceed for 2.5 hours after which the process was stopped and the lower graphite plug removed for analysis. The hard grayish brittle coating on the carbon fibers was studied using both scanning electron microscopy (SEM) and energy dis¬ persive x-ray analysis (EDAX) which confirmed the presence of a Si3N coating on the carbon fibers.
In Figure 9, substrates 50 are shown suspended in second reaction zone 60 above reaction zone 34 and a third reactant is injected into this second zone, similarly to that shown in Figures 7 and 8, where it contacts the one or more reactive intermediates rising from first reaction zone 34 to form a coat- ing on the suspended substrate comprising, respectively, one or more metal nitrides, carbides, oxides, borides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, oxygen, boron, or a mixture of same.
To further illustrate the formation of a coating of a metal compound on a substrate such as shown in Figure 9, a bed of 325 mesh titanium particles was formed and preheated to 750"C prior to being fluid¬ ized by a flow of argon gas at atmospheric press- ure. HBr gas was then mixed with the argon fluid¬ izing gas to obtain a partial pressure of 7 torr. Steel and silica substrates were suspended in the second reaction zone above the bed and a flow of NH3 gas was injected into this zone from the top of the reactor while maintaining this second reaction zone at a temperature of 800'C.
Gold colored coatings were formed on the substrates and these coatings were confirmed by subsequent x- ray diffraction, SEM, and EDAX to be TiN. The coated steel substrate was tested for corrosion resistance in aqueous chloride solutions and found to have an increase in corrosion resistance of approximately 30 times that of uncoated steel.
Thus, the invention provides a novel process for the formation of powders or coatings of either one or more metal reactants powders in a moving bed reactor initially reacted with a halogen-containing reactant to form reactive intermediates which dis¬ proportionate or decompose to form the metal powder or coating; or which reactive intermediates may react further with another reactant introduced into a second reaction zone to form one or more metal compounds in the form of either a powder or a coating.
Having thus described the invention, what is claimed is:

Claims

Claims :
1. A low temperature process for forming a powder or a coating comprising one or more metals or metal compounds which comprises reacting one or more metal reactants with a halide-containing reactant to form one or more reactive intermediates capable of forming a coating or powder.
2. The process of claim 1 wherein said one or more metal reactants are selected from the class consis¬ ting of Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Si, and B. ,
3. The process of claim 2 wherein said halogen- containing reactant is selected from the class con¬ sisting of X2, HX, MXa, or MX/a_bxHj:) where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of said metal reactants of claim 2 and Pb; a is the maximum oxidation state or valence of said one or more metals M; and b has a value of from 1 to a-1.
4. Thexprøcess of claim 3 wherein said coating or powder is formed by decomposing one or more of said one or more reactive intermediates to form a coat¬ ing or powder comprising said one or more metals reactants initially reacted with the halide- containing reactant.
5. The process of claim 3 wherein said coating or powder is formed by reacting said one or more reactive intermediates with a third reactant selec¬ ted from the class consisting of a boron-containing reactant, a carbon-containing reactant, an oxygen- containing reactant, a nitrogen-containing reac¬ tant, and mixtures thereof to form said powder or coating comprising respectively, one or more metal borides, metal carbides, metal oxides, metal ni- trides, or a mixture thereof, of said one or more metal reactants depending upon said third reactant.
6. The process of claim 5 wherein said coating or powder is formed by reacting said one or more metal reactants with said halogen-containing reactant in a first reaction zone in a reactor and then intro- ducing the resultant one or more reactive intermed¬ iates into a second reaction zone of said reactor to react with said third reactant to form said one or more metal borides, metal carbides, metal ni¬ trides, or mixture thereof, of said one or more metal reactants depending upon the other reactant.
7. A low temperature process for forming a powder comprising one or more metals which comprises re¬ acting one or more metal reactants with a halide- containing reactant in a reactor to form one or more reactive intermediates and decomposing said one or more reactive intermediates in said reactor to form a powder consisting essentially of said one or more metals.
8. The process of claim 7 wherein said one or more metal reactants are selected from the class consis¬ ting of Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Si, and B.
9. The process of claim 8 wherein said halogen- containing reactant is selected from the class con¬ sisting of X2, HX, MXa, or
Figure imgf000032_0001
where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of said metal reactants of claim 8 and Pb; a is the maximum oxidation state or valence of said one or more metals M; and b has a value of from 1 to a-1.
10. A low temperature process for forming a coat¬ ing comprising one or more metals which comprises reacting one or more metal reactants with a halide- containing reactant in a reactor to form one or more reactive intermediates and reacting, decompos¬ ing, or disproportionating said one or more reac¬ tive intermediates in said reactor to form, on a substrate in said reactor, a coating consisting essentially of said one or more metals.
11. The process of claim 10 wherein said one or more metal reactants are selected from the class consis¬ ting of-Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Si, and B.
12. The process of claim 11 wherein said halogen- containing reactant is selected from the class con¬ sisting of X2, HX, MXa, or MX(a_b)Hb where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of the metal reactants of claim 8 and Pb; a is the maximum oxidation state or valence of said one or more metals M; and b has a value of from 1 to a-1.
13. A low temperature process for forming a powder comprising one or more metals compounds which com¬ prises reacting one or more metal reactants with a halide-containing reactant in a first reaction zone of a reactor to form one or more reactive intermed¬ iates and contacting said one or more reactive intermediates in a second reaction zone in said reactor with a third reactant selected from the class consisting of a boron-containing reactant, a carbon-containing reactant, an oxygen-containing reactant, a nitrogen-containing reactant, and mix¬ tures thereof to form said metal compound powder comprising respectively, one or more metal borides, metal carbides, metal nitrides, or a mixture there- of.
14. The process of claim 13 wherein the tempera¬ ture in said first reaction zone is maintained within a range of from about 200βC to about 1000βC; and the temperature in said second reaction zone is maintained within a range of from about 500"C to about 1300-C.
15. The process of claim 14 wherein said one or more metal reactants are selected from the class consisting of Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Si, and B.
,
16. The process of claim 15 wherein said halogen- containing reactant is selected from the class con¬ sisting of X2, HX, MXa, or MX a_bvHb where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of said metal reactants of claim 15 and Pb; a is the maximum oxidation state or valence of said one or more metals M; and b has a value of from 1 to a-1.
17. A low temperature process for forming on a substrate a coating comprising one or more metals compounds which comprises reacting one or more metal reactants with a halide-containing reactant . in a first reaction zone of a reactor to form one _. or more reactive intermediates and contacting said one- or more reactive intermediates in a second reaction zone in said reactor with a third reactant selected from the class consisting of a boron- containing reactant, a carbon-containing reactant, an oxygen-containing reactant, a nitrogen-contain¬ ing reactant, and mixtures thereof to form said coating on said substrate in said second reaction zone comprising respectively, one or more metal borides, metal carbides, metal oxides, metal ni¬ trides or a mixture thereof.
18. The process of claim 17 wherein the tempera¬ ture in said first reaction zone is maintained within a range of from about 200"C to about 1000βC; and the temperature in said second reaction zone is maintained within a range of from about 500βC to about 1300°C.
19. The process of claim 18 wherein said one or more metal reactants are selected from the class consisting of Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W, Si, and B.
20. The process of claim 19 wherein said halogen- containing reactant is selected from the class con¬ sisting of X2, HX, MXa, or
Figure imgf000035_0001
where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of the metal reactants of claim 19 and Pb; a is the maximum oxidation state or valence of said one or more metals M; and b has a value of from 1 to a-1.
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