US3443978A - Method of coating metals with a silicide layer and an outer layer of aluminasilicate - Google Patents

Method of coating metals with a silicide layer and an outer layer of aluminasilicate Download PDF

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Publication number
US3443978A
US3443978A US476715A US3443978DA US3443978A US 3443978 A US3443978 A US 3443978A US 476715 A US476715 A US 476715A US 3443978D A US3443978D A US 3443978DA US 3443978 A US3443978 A US 3443978A
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United States
Prior art keywords
coating
silicide
percent
aluminasilicate
substrate
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Expired - Lifetime
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US476715A
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English (en)
Inventor
James Edward Restall
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Power Jets Research and Development Ltd
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Power Jets Research and Development Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/44—Siliconising
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/60—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

Definitions

  • alumina or an alumina-silicate is deposited on the silicide coating.
  • the invention relates to coatings for refractory metallic materials.
  • the oxidation problem can be oifset by the use of protective coatings which must be both dense and adherent to the alloy.
  • Ceramic materials such as alumina have high resistance to oxidation but are not altogether suitable for coating refractory metals due to difliculties in obtaining a satisfactory bond coupled with a uniformly dense (i.e., nonporous) coating.
  • a method of forming an overlay having high resistance to oxidation on a body of refractory metallic material including the step of bonding an intermediate coating of another material to the body.
  • the intermediate coating is of a material which also has a high resistance to oxidation.
  • the overlay is of ceramic material such as alumina or an alumina-silicate and the refractory metallic material is a niobium alloy.
  • a composite coating having high resistance to oxidation and formed on a body of refractory metallic material comprises an intermediate layer of a silicide diffusion bonded to the body.
  • the basic article i.e., substrate
  • nited States Patent 3,443,978 Patented May 13, 1969 is composed of the niobium alloy having the nominal composition W 15 percent, Mo 5 percent, Zr 1 percent and known as F48. This has a high temperature strength suitable for use in aircraft gas turbine rotor blading.
  • the substrate is packed in a mixture of silicon, iron and chromium powders of commercial purity in the proportions Si 58.54 percent, Fe 33.33 percent; Cr 8.13 percent. Variations in composition based on the siliconiron eutectic (i.e., 59 percent Si, 41 percent Fe) with chromium additions up to 15 percent have also given satisfactory results.
  • the pack is heated to 1100 C. in an iodine-hydrogen atmosphere and maintained under these conditions for five hours.
  • Iodides of the respective metals are formed but the presence of hydrogen causes reduction to the metallic state.
  • the reversability of the process causes great activity whereby the metals dilfuse readily into the surface of the substrate to form a modified niobium disilicide coating.
  • the resultant coating is basically niobium disilicide, diffusion bonded to the substrate. It is quite dense appearing to be single phase (except at the interface), and quite clean, with a thickness of 0.002 to 0.003 inch.
  • the silicide coated article is pyrolised on a fluidised bed where it is subjected to a vapourised stream of steam and aluminum chloride to give an overlay of alumina by the reaction or the other alumina-silicate (such as one according to the molecular formula:
  • silicide coating being ductile over a wide range of temperature and having a high resistance to oxidation, might appear to be a suitable protection in itself. It is true that silicide coatings potentially olfer the best protection at high temperatures in that they form a thin skin of silica glass on their outer surfaces during exposure to air or oxygen in such circumstances and as a rule this gives adequate protection in steady or slowly fluctuating working conditions.
  • silicide coatings are prone to pest failure in that cracks develop and extend through the coating.
  • the resultant ingress of oxygen and nitrogen to the substrate causes it to be embrittled and possibly to disintegrate with consequent spalling of the coating.
  • silicide as an intermediate layer has however a distinct advantage in that protection of the substrate is maintained in the event of pinhole failure of the ceramic overlay.
  • the combination of a silicide intermediate layer with a ceramic overlay thus aiiords twofold protection of the substrate.
  • the method is not necessarily limited to the use of a silicide as an intermediate coating-other suitable coatings may be obtained by the use of titanium, chromium, iron or aluminum either singly or in combination, the essential requirements being that the material selected will form a strong bond with the substrate and will not be subject to oxidation during the application of the overlay.
  • a method of producing a metallic article having a substrate of a refractory alloy selected from the group comprising molybdenum, niobium, tantalum, tungsten, nickel, cobalt and chromium which comprises (1) packing said substrate in a mitxure of silicon, iron, and chromium powders, (2) heating in an iodine-hydrogen atmosphere to produce a silicide coating chemically bonded to the substrate and having a thickness in the range of about 0.002 to about 0.003 inch and (3) chemically bonding an ilumina-silicate to the silicide coating.
  • alumina-silicate is a material having the molecular formula:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
US476715A 1964-08-14 1965-08-02 Method of coating metals with a silicide layer and an outer layer of aluminasilicate Expired - Lifetime US3443978A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB33187/64A GB1077735A (en) 1964-08-14 1964-08-14 Coatings for metallic materials

Publications (1)

Publication Number Publication Date
US3443978A true US3443978A (en) 1969-05-13

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US476715A Expired - Lifetime US3443978A (en) 1964-08-14 1965-08-02 Method of coating metals with a silicide layer and an outer layer of aluminasilicate

Country Status (4)

Country Link
US (1) US3443978A (fr)
DE (1) DE1294136B (fr)
FR (1) FR1445882A (fr)
GB (1) GB1077735A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050153833A1 (en) * 2004-01-14 2005-07-14 Engelhard Corporation Coated metal substrate
GB2427204A (en) * 2005-06-13 2006-12-20 Gen Electric Intermediate bond coat for silicon containing substrate
GB2427205A (en) * 2005-06-13 2006-12-20 Gen Electric Intermediate bond coat for silicon containing substrate
US20090304564A1 (en) * 2006-11-29 2009-12-10 Basf Catalysts Llc NOx Storage Materials and Traps Resistant to Thermal Aging
CN105296918A (zh) * 2015-11-11 2016-02-03 厦门理工学院 一种金属钨表面Al2O3-SiO2高温绝缘涂层及其制备方法
WO2019192800A1 (fr) * 2018-04-06 2019-10-10 Siemens Aktiengesellschaft Protection anti-oxydation destinée à des phases max

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297150A (en) * 1979-07-07 1981-10-27 The British Petroleum Company Limited Protective metal oxide films on metal or alloy substrate surfaces susceptible to coking, corrosion or catalytic activity
US5514482A (en) * 1984-04-25 1996-05-07 Alliedsignal Inc. Thermal barrier coating system for superalloy components
GB2285632B (en) * 1985-08-19 1996-02-14 Garrett Corp Thermal barrier coating system for superalloy components
US4889776A (en) * 1987-08-17 1989-12-26 Barson Corporation Refractory metal composite coated article
DE19604844C2 (de) 1996-02-10 1998-02-26 Forschungszentrum Juelich Gmbh Verklebung von nichtoxidischen keramischen, keramometallischen oder metallischen Körpern sowie verfahrensgemäß hergestellte Körper
GB2439313B (en) * 2006-06-24 2011-11-23 Siemens Ag Method of protecting a component against hot corrosion and a component protected by said method

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711975A (en) * 1949-07-01 1955-06-28 Thompson Prod Inc Vitreous coated refractory metals, method for producing the same, and vitreous enamel composition
US2857297A (en) * 1951-10-25 1958-10-21 Nat Res Corp Process of coating molybdenum
US3006782A (en) * 1956-03-09 1961-10-31 Norton Co Oxide coated articles with metal undercoating
US3029162A (en) * 1959-05-21 1962-04-10 Chromalloy Corp Process for the production of metallic borides on the surface of metals
US3117846A (en) * 1960-01-28 1964-01-14 Pfaudler Permutit Inc Multi layer difusion coatings and method of applying the same
US3175920A (en) * 1961-05-08 1965-03-30 North American Aviation Inc Corrosion protection at intermediate temperatures
US3249462A (en) * 1961-10-23 1966-05-03 Boeing Co Metal diffusion coating utilizing fluidized bed
US3251337A (en) * 1963-07-16 1966-05-17 Robert E Latta Spiral fluidized bed device and method for coating particles
US3269856A (en) * 1962-06-07 1966-08-30 Lockheed Aircraft Corp Coating for refractory metal

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE895848C (de) * 1950-01-11 1953-11-05 Metallwerk Plansee G M B H Verfahren zur Herstellung festhaftender, gasdichter UEberzuege auf Formkoerpern aus vorzugsweise hochschmelzenden Metallen

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711975A (en) * 1949-07-01 1955-06-28 Thompson Prod Inc Vitreous coated refractory metals, method for producing the same, and vitreous enamel composition
US2857297A (en) * 1951-10-25 1958-10-21 Nat Res Corp Process of coating molybdenum
US3006782A (en) * 1956-03-09 1961-10-31 Norton Co Oxide coated articles with metal undercoating
US3029162A (en) * 1959-05-21 1962-04-10 Chromalloy Corp Process for the production of metallic borides on the surface of metals
US3117846A (en) * 1960-01-28 1964-01-14 Pfaudler Permutit Inc Multi layer difusion coatings and method of applying the same
US3175920A (en) * 1961-05-08 1965-03-30 North American Aviation Inc Corrosion protection at intermediate temperatures
US3249462A (en) * 1961-10-23 1966-05-03 Boeing Co Metal diffusion coating utilizing fluidized bed
US3269856A (en) * 1962-06-07 1966-08-30 Lockheed Aircraft Corp Coating for refractory metal
US3251337A (en) * 1963-07-16 1966-05-17 Robert E Latta Spiral fluidized bed device and method for coating particles

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050153833A1 (en) * 2004-01-14 2005-07-14 Engelhard Corporation Coated metal substrate
US7271125B2 (en) * 2004-01-14 2007-09-18 Engelhard Corporation Coated metal substrate
US7704915B2 (en) 2004-01-14 2010-04-27 Basf Catalysts Llc Methods for preparing coated metal substrates
GB2427204A (en) * 2005-06-13 2006-12-20 Gen Electric Intermediate bond coat for silicon containing substrate
GB2427205A (en) * 2005-06-13 2006-12-20 Gen Electric Intermediate bond coat for silicon containing substrate
GB2427205B (en) * 2005-06-13 2011-06-15 Gen Electric Bond coat for corrosion resistant EBC for silicon-containing substrate and processes for preparing same
US20090304564A1 (en) * 2006-11-29 2009-12-10 Basf Catalysts Llc NOx Storage Materials and Traps Resistant to Thermal Aging
US8022010B2 (en) 2006-11-29 2011-09-20 Basf Corporation NOx storage materials and traps resistant to thermal aging
US8592337B2 (en) 2006-11-29 2013-11-26 Basf Corporation NOx storage materials and traps resistant to thermal aging
CN105296918A (zh) * 2015-11-11 2016-02-03 厦门理工学院 一种金属钨表面Al2O3-SiO2高温绝缘涂层及其制备方法
CN105296918B (zh) * 2015-11-11 2018-08-14 厦门理工学院 一种金属钨表面Al2O3-SiO2高温绝缘涂层及其制备方法
WO2019192800A1 (fr) * 2018-04-06 2019-10-10 Siemens Aktiengesellschaft Protection anti-oxydation destinée à des phases max

Also Published As

Publication number Publication date
FR1445882A (fr) 1966-07-15
GB1077735A (en) 1967-08-02
DE1294136B (de) 1969-04-30

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