US3837894A - Process for producing a corrosion resistant duplex coating - Google Patents

Process for producing a corrosion resistant duplex coating Download PDF

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Publication number
US3837894A
US3837894A US00255457A US25545772A US3837894A US 3837894 A US3837894 A US 3837894A US 00255457 A US00255457 A US 00255457A US 25545772 A US25545772 A US 25545772A US 3837894 A US3837894 A US 3837894A
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United States
Prior art keywords
chromium
undercoat
alloys
cobalt
iron
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US00255457A
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English (en)
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R Tucker
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Praxair ST Technology Inc
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Union Carbide Corp
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Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Priority to US00255457A priority Critical patent/US3837894A/en
Priority to CA171,616A priority patent/CA1000130A/en
Priority to DE19732325149 priority patent/DE2325149C3/de
Priority to CH720273A priority patent/CH574506A5/xx
Priority to JP5574273A priority patent/JPS5320931B2/ja
Priority to FR7318416A priority patent/FR2185696B1/fr
Priority to GB2404673A priority patent/GB1438381A/en
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Publication of US3837894A publication Critical patent/US3837894A/en
Assigned to MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. reassignment MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. MORTGAGE (SEE DOCUMENT FOR DETAILS). Assignors: STP CORPORATION, A CORP. OF DE.,, UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,, UNION CARBIDE CORPORATION, A CORP.,, UNION CARBIDE EUROPE S.A., A SWISS CORP.
Assigned to UNION CARBIDE CORPORATION, reassignment UNION CARBIDE CORPORATION, RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: MORGAN BANK (DELAWARE) AS COLLATERAL AGENT
Assigned to UNION CARBIDE COATINGS SERVICE TECHNOLOGY CORPORATION reassignment UNION CARBIDE COATINGS SERVICE TECHNOLOGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNION CARBIDE COATINGS SERVICE CORPORATION
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    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/94—Pressure bonding, e.g. explosive
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576—Boride, carbide or nitride component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12937—Co- or Ni-base component next to Fe-base component

Definitions

  • This invention relates to a process for producing a metallurgically sealed undercoat for a primary coated substrate which effectively protects the substrate from oxidation and/or corrosion attack.
  • coatings available for providing a substrate with a surface having specific characteristics suitable for a particular end use application.
  • the coating may be applied to increase the wearresistant characteristics of the substrate, decrease the contact-friction characteristics of the substrate, electrically or thermally insulate the substrate, or protect it from oxidation or other corrosive attack.
  • Many such coatings are inherently porous, as are the plasma deposited and detonation gun coatings, and thereby allow liquid or gas mediums in an end use environment to permeate to the substrate where the me dium can attack and corrode the substrate. Thus an otherwise perfectly good coating for a particular purpose may be ineffective due to inherent porosity.
  • Another method for sealing a porous type coating is to impregnate the coating with a low-melting metal which may effectively retard attack in some environments but would be ineffective in high temperature corrosive environments where it would very likely decompose, oxidize and/or melt. It may also react with and degrade the properties of either the coating or the substrate.
  • the present invention differs from the above approaches which attempt to effectively produce an overall impervious coating, by being directed to the introduction of a plasma-deposited metallurgically sealed undercoat between a primary coating and a substrate.
  • the undercoat comprises the simultaneous plasmadeposition of at least two materials which are deposited in the unreacted state so that when subjected to a heat treatment in a non-oxidizing atmosphere, a reaction/- diffusion will occur between the materials.
  • This invention is directed to a process for producing a coating having a metallurgically sealed undercoat Specifically. the invention relates to a process for producing a coating by simultaneously depositing. by plasma-spraying or detonation gun techniques, a first layer of two or more materials.
  • each of which is selected from at least one of the groups consisting of metals, alloys, and intermetallics, onto a substrate so as to form an interlocking lamellar structure composed of splats of the individual materials in a substantially unreacted state; followed by depositing a primary surface layer selected from at least one of the groups consisting of metals, metal alloys, intermetallics, metal oxides, metal nitrides, metal borides, metal silicides, metal carbides, and cermets, onto said first deposited layer; and thereafter subjecting the duplex deposited coating to an ele vated temperature in a non-contaminating atmosphere for a time period sufficient to react/diffuse the materials in said first layer to produce a metallurgically sealed undercoat of a substantially homogeneous alloy and/or intermetallic.
  • the undercoat produced between the primary coating and the substrate will effectively provide a barrier that will be inert or highly corrosion resistant in high temperature corrosive environments, such as air and other oxidizing gases at high temperatures.
  • High temperature is intended to mean a temperature above which corrosion of an uncoated substrate material would begin, and which would rapidly continue. This temperature is a function of the medium in the environment and the composition of the substrate, and once both are known, an artisan can readily determine its numerical value.
  • coated articles of this invention can also admirably be used in lower temperature environments presenting a severe corrosion problem, but, however, economics may limit the use of such coated articles under such conditions.
  • the coating applied according to this invention would also be admirably suited for environments where the coated article would be subjected to thermal fatigue since the surface bond phenomenon of the plasma-deposited coating would be sufficient to substantially secure the coating to the substrate and thus effectively eliminate spalling which usually occurs with conventional types of coatings.
  • coated articles of this invention are also admirably suited for environments such as exist in the steel industry wherein the reaction between a steel substrate and molten zinc or aluminum is so great that any permeation of the molten medium or its vapor, through a porous type coating on the steel substrate will cause chemical attack at such a rate that the steel substrate will be rendered ineffective in a short time.
  • the metallurgical undercoat layer of this invention is essentially an as-deposited layer, applied by plasma or detonation gun techniques, comprising a mechanical mixture of two or more materials with significantly different chemical activity, such chemical activity being defined beginning on Page 91 of the text titled The Theory of Transformation in Metals and Alloys by J. W. Christian, Pergamon Press-Oxford, 1965 edition.
  • a driving force over and above the ordinary driving force of surface free energy that causes conventional sintering.
  • this additional energy appears to be necessary to achieve densification and scaling at temperatures and within reasonable time periods.
  • Conventional plasma-deposited coatings Conventional plasma-deposited coatings.
  • the undercoat serves as a buffer between the primary coating and the substrate. in some cases this buffering is insufficient to prevent the perpendicular cracking of the primary coating, but it does prevent'corrosive attack since the undercoat itself does not crack.
  • the strong bond between the primary coating and the undercoat, and between the undercoat and the substrate substantially eliminates failure due to shearing at these bonding lines.
  • the selection of a primary coating and the substrate will usually be somewhat dictated by the end use application of the coated article.
  • the primary coating can be deposited by conventional plasma-spraying as disclosed in US. Pat. Nos. 2,858,41 l and 3,016,447; by Detonation-Gun techniques as disclosed in US. Pat. Nos. 2,714,563, 2,950,867 and 2,964,420; by flame spraying techniques, by electro-deposition techniques, electrophoresis techniques, by slurry techniques, or the like.
  • the similarity in a final coating obtained by these techniques is that the coating has inherent porosity that makes the substrate vulnerable to attack by a corrosive medium.
  • a steel substrate such as a roll, coated with alumina by conventional techniques, and then employed in a molten zinc or aluminum environment, will last only a relatively short time since the zinc or aluminum will permeate the alumina coating and attack the substrate.
  • the useful life of alumina coated rolls in the steel industry is relatively short when exposed to a molten zinc or aluminum environment even though alumina does not react with either molten zinc or aluminum.
  • substrate materials used in various corrosive environments include, but not limited to, metals and alloys, such as steel, stainless steel, iron base alloys, aluminum, aluminum base alloys, nickel, nickel base alloys, cobalt, cobalt base alloys, copper, copper base alloys, chromium, chromium base alloys, refractory metals, and refractory base alloys.
  • metals and alloys such as steel, stainless steel, iron base alloys, aluminum, aluminum base alloys, nickel, nickel base alloys, cobalt, cobalt base alloys, copper, copper base alloys, chromium, chromium base alloys, refractory metals, and refractory base alloys.
  • primary coating materials suited for use in corrosive environment include, but not limited to the following: metal, metal alloys, intermetallics, cermets, metal oxides, metal nitrides, metal carbides, metal borides, and metal silicides in a combination known to produce a good coating.
  • Suitable metals include nickel (Ni), cobalt (Co), chromium (Cr), gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru) and the refractory metals.
  • Suitable alloys would include the alloys of the above metals, and a suitable cerrnet would be a tungsten carbide cobalt composite or the like.
  • Suitable metal oxides would include alumina (A1 silica (SiO chromium sesquioxide (Cr O hafnium oxide (l-lfO beryllium oxide (BeO), zirconium oxide (ZrO stannic oxide (SnO magnesium oxide (MgO), yttrium oxide (Y OQ). rare earth oxides.
  • TiOg titanium dioxide
  • TiZrO Suitable metal carbides include silicon carbide (SiC). boron carbide (8 C). hafnium carbide (HFC 1. columbium carbide (CbCl. tantalum carbide (TaC). titanium carbide (TiC).
  • zirco nium carbide ZrCl, molybdenum carbide 1' Mo C).
  • Cr'gC-g chromium carbide
  • tungsten carbide WC
  • Suitable metal borides include titanium boride (TiB zirconium boride (ZrB- columbium boride (CbB molybdenum boride (M082).
  • tungsten boride W8 tantalum boride (TaBZ) and chromium boride ((frB).
  • Suitable metal nitrides include aluminum nitride (AIN), silicon nitride (Si N titanium nitride (TiN), zirconium nitride (ZrW), hafnium nitride (HfN). vanadium nitride (VN), niobium nitride (NbN), tantalum nitride (TaN) and chromium nitride (CrN).
  • Suitable silicides include molybdenum silicide (MgSifl. tantalum silicide (TaSiZ).
  • tungsten silicide WSi l, titanium silicide TiSi zirconium silicide (ZrSi vanadium silicide VSi niobium silicide (NbSi chromium silicide (CrSi and boron silicide (B,Si
  • the undercoat layer of this invention must be composed of at least two materials, each of which is selected from at least one of the groups consisting of ele mental metals, alloys. and intermetallics, and such materials must be deposited on the substrate in an unreacted state; i.e., an interlocking lamellar structure composed of splats of the individual materials.
  • the selec tion of the two or more materials for the undercoat is important since they must react/diffuse together at an elevated temperature so as to form a substantially homogeneous alloy and/or intermetallic; be compatible with the substrate such that they form a good bond while not significantly interdiffusing with the substrate upon being subjected to a heat treatment or when subjected to a particular end use environment; they must be compatible with the primary coating such that they do not significantly react and/or diffuse with such coating; and after reaction/diffusion has occurred, they must be capable of forming a substantially effective barrier between the substrate and any corrosive type medium that may exist in its intended end use environment which can permeate through the primary coating.
  • an undercoat composed of a substantially homogeneous alioy or intermetallic would be desirable although an undercoat composed of an intermetallic compound distributed substantially throughout an alloy matrix would be suitable in certain applicatrons.
  • the heat treatment and temperature required to achieve substantial homogenization and sealing during the reaction/diffusion step are a function of the materials of the undercoat. It is essential, however, that during deposition by plasma or detonation gun techniques, a minimum of oxidation of the materials occurs, and that the as-deposited composition consists of a mechanical mixture of discrete, essentially unreacted materials. If these requirements are not substantially met, the interaction between the materials during the reac tion/diffusion step will be impeded and complete sealing will not occur. Although interdiffusion between the undercoat and the substrate or the primary coating should be very small in most cases, a minor amount may tend to increase the bond strength.
  • the particular materials selected for the undercoat on a substrate should, after the reaction/diffusion step, be resistant to the corrosive medium that will exist in the intended end use environment of the coated substrate.
  • the selected reacted under coat material may not possess the corrosion resistant characteristics necessary for a particular end use application and therefore an additional process step may be required for enhancing such characteristics.
  • a conventional oxidizing, carburizing, nitriding, boriding, siliciding or the like, step may be sufficient to develop a corrosion resistant oxide, carbide, nitride, boride, silicide, or the like, respectively, on the undercoat segmented areas exposed to the exterior through the inherent porosity of the primary coating.
  • This process treatment of the exposed segmented areas on the undercoat layer may be carried out in a controlled environment so as to react only one of the materials in the undercoat and thereby control the formation of the layer thickness on said segmented areas, or produce a layer on the seg mented areas which has sufficient corrosion resistance.
  • the formation of a thicker layer than necessary, may result in the spalling of the primary coating.
  • Suitable materials for use in the undercoated layer include elemental metals such as nickel, aluminum, cobalt, iron, chromium, copper, molybdenum, tungsten, niobium, tantalum, titanium, antimony, calcium, manganese, zirconium, vanadium, hafnium, magnesium, zinc and palladium, and alloys or intermetallics of the above elemental metals such as nickel-chromium, ironchromium, cobalt-chromium, iron-chromium alloys containing rare earth additions, nickel-chromium alloys containing rare earth additions, cobalt-chromium alloys containing rare earth additions, and copperaluminum.
  • elemental metals such as nickel, aluminum, cobalt, iron, chromium, copper, molybdenum, tungsten, niobium, tantalum, titanium, antimony, calcium, manganese, zirconium, vanadium, hafnium, magnesium, zinc and palladium, and
  • any artisan can determine the choice of the undercoat materials that can be deposited in an unreacted state and thereafter upon being subjected to a heat treatment produce a substantially homogeneous alloy and/or intermetallic impervious undercoat, once the substrate and primary coating materials are selected, and the intended end use environment is known.
  • the temperature at which the reaction/diffusion occurs between the selected materials of the undercoat is a function of such materials and can be readily determined from any good metallurgical text reference.
  • a non-contaminating atmosphere is required during the heat treatment of this inventive process to prevent a layer, such as an oxide layer, from interfering with the reaction/diffusion step of the process.
  • a suitable noncontaminating atmosphere would be an inert atmosphere such as argon, helium, or vacuum, or a reducing atmosphere such as hydrogen.
  • the segmented areas of the undercoat exposed to the exterior through the porosity of the primary coating can be oxidized by exposure to a mixture of H 0 and H in such ratios that only the desired component of the undercoat is oxidized, such as aluminum in a nickelaluminum undercoat.
  • Nitriding of the exposed areas of the undercoat can be accomplished by exposure to nitrogen or ammonia at elevated temperature.
  • the exposed areas of the undercoat could be carburized by exposure to methane at elevated temperature.
  • siliciding or boriding of the exposed areas can be accomplished by conventional techniques.
  • the degree of formation of the oxide, nitride, carbide, silicide, boride or the like layer should be sufficient to produce the desired corrosion resistant characteristics necessary for the undercoat when exposed in a particular environment, while insufficient to cause the primary coating to spall.
  • a mixture of 85 to 96% by weight of an iron-chromium alloy iron, 20% chromium) and 4 to 15% by weight aluminum could be simultaneously plasma-deposited on the carbon steel roll and then over-coated with alumina by conventional techniques.
  • the coated rolls could then be heat treated at a temperature between about 700C. and about 900C. in a hydrogen or argon atmosphere for a sufficient time period, about 4 to 20 hours, to allow reaction/diffusion of the components of the undercoat to seal the coating and form an essentially homogeneous alloy undercoat.
  • the coated roll could be oxidized in an air atmosphere at a temperature of between about 700C. and about 900C. for a sufficient time period, about 4 hours, to from an oxide layer on the exposed areas of the undercoat. Since the oxide is not attacked by zinc. the coated roll is ideally suited for use in a molten zinc environment. Even though cracks.
  • the oxidation step should be performed in an atmosphere containing a partial pressure of oxygen, such oxygen being present only in an amount that would be sufficient to substantially oxidize the aluminum in the alloy, but not sufficient to effectively oxidize the iron or chromium.
  • the undercoat layer heat treated prior to depositing the primary layer.
  • the primary layer may be deposited by any conventional technique to produce a duplex coating having excellent corrosion resistant characteristics.
  • EXAMPLE I consisting of exposing the bars to room temperature for one-half hour followed by subjecting them to an air environment heated to 900C. for 2 /2 hours. After only 120 hours of this cyclic testing, the plasma-deposited alumina coating spalled from both samples. A conventional pre-alloyed undercoat of nichrome (Ni-80%; Cr 20%), 0.002-0.003 inches thick, was deposited on identical bars as described above, followed by a 0.0045 inch thick primary coating of alumina. The duplex coated bars upon being subjected to the same cyclic oxidation test and for the same duration as above, resulted in the cracking of both layers of the dual coating, and the exposed substrate was extensively oxidized.
  • the duplex coated bars were heat treated for 10 hours at 900C. in hydrogen, and then selectively oxidized at 900C. for 26 hours in a mixture of hydrogen and water vapor with a dew point of about l0C., which was sufficient to form Cr O- but insufficient to form NiO, on the surface areas of the undercoat layer that were exposed through the porosity in the alumina primary coating.
  • the metallurgically sealed undercoat on both bars showed no degradation after hours.
  • a duplex coating produced by plasma-depositing a 0.002 to 0.003 inch thick undercoat of a mechanical mixture of 76 wt/o iron, 20 wt/o chromium, and 4 wt/o aluminum, followed by a 0.0045 inch thick primary coating of alumina, was deposited on a 4l0 stainless steel bar and on a 1018 steel bar as above. The bars were then heat treated for 10 hours in hydrogen at 900C. for 26 hours in a mixture of hydrogen and water vapor with a dew point of about 45C., which was sufficient to form A1 0 but inhibit the formation of FeO, F6203, Fe O or Cr O or their spinels.
  • the 410 stainless steel coated bar showed no degradation but the coating on the 1018 steel bar buckled due to thermal fatigue.
  • a duplex coating produced by plamadepositing a 0.002 to 0.003 inch thick undercoat of a mechanical mixture of 65 wt/o iron, 20 wt/o chromium, and 15 wt/o aluminum, followed by a 0.0045 inch thick primary coating of alumina, was deposited on a 1018 steel bar.
  • the coated bar was heat treated to 700C. for 12 hours in hydrogen and then selectively oxidized at 700C. for 8 hours in a hydrogen and water vapor mix ture with a dew point of 45C.
  • the bar was subjected to the same cyclic oxidation test for the same duration as above, and upon being examined it exhibited no apparent damage as evidenced by metallographic examination.
  • EXAMPLE 2 Two 4l0 stainless steel rings and two 1018 steel rings, measuring 1 inch outside diameter, 0.9 inch inside diameter by l/2 inch wide, were given either a conventional 0.002 to 0.003 inch thick nichrome undercoat or a 0.002 to 0.003 inch nickel aluminide undercoat as described in Example 1 so that each of the same type rings had a different undercoat. A primary plasma coating of alumina, 0.0045 inch thick, was then deposited on all four rings. The coated rings were then cut in half along a diameter and subjected to a 120 hour cyclic oxidation test as described in Example 1.
  • the four rings were then plasma coated with a 0.0045 inch thick primary coating of alumina.
  • the four rings were then heat treated in hydrogen at 800C. for 4 hours.
  • the duplex coated rings were thereupon cut in half along in diameter and subjected to a 120 hour cyclic oxidation test as described in Example 1 and upon being examined, they exhibited no significant damage whatsoever as evidenced by metallographic examination.
  • EXAMPLE 3 A 1095 steel substrate, measuring 1 inch diameter by 6 inches long with a hemispherical end, was given a plasma deposited 0.002-0.004 inch thick undercoat of a mixture of 80 wt/o nickel and wt/o chromium, followed by a primary plasma coating, 0.004-0.006 inches thick.
  • the coated substrate was heat treated for 8 hours at 900C. in a hydrogen atmosphere and then heat treated at 800C. for 4 hours in air.
  • the coated substrate was placed in a molten zinc atmosphere at a temperature of 585C. to 600C. for 428 hours and upon being examined, it exhibited no evidence of failure.
  • EXAMPLE 4 A 0.0045 inch thick coating of alumina was plasma deposited on a 1018 steel substrate, a 1095 steel substrate and a 304 stainless steel substrate, each of which had the dimensions of the substrate in Example 3. The three coated specimens were then subjected to a cyclic corrosion test by being submerged in a molten aluminum at 700C. The coated specimens were submerged in the aluminum bath for about 125 hours and then exposed to air at room temperature for 2 hours before resubmerging them back into the bath. The 1018 and 1095 steel coated specimens failed in less than 125 hours, such failure being the spalling of the alumina coating and attack of the substrate by the aluminum. In less than 400 hours of the cyclic testing,-the 304 stainless steel specimen failed in the same manner.
  • a duplex coated article was prepared in the following manner.
  • the surface was mechanically roughened by grit-blasting with 60 mesh A1 0 abrasive (Fast-Blast 60).
  • the roll was then positioned in a machine capable of rotating a piece at 159 rpm and traversing a plasma torch at 0.33 inch/second.
  • the undercoat material was sprayed as a mechanical mixture of two powders, 96 w/o of an alloy of FeCr and 4 w/o of unalloyed A1.
  • the FeCr alloy was 80w/o Fe and 20 w/o Cr.
  • the thickness of the undercoat was 0.003 inch.
  • the overcoat 0.0032 inch thick, was sprayed immediately after and on top of the freshly deposited undercoat and was composed of pure A1 0
  • a plasma torch fitted with a copper anode was also used for this overcoat.
  • the same rotation and traverse speeds used for the undercoat were also used for the overcoat of A1 0
  • the roll was heat-treated in the following manner.
  • a retort was constructed of 1020 steel which had the following dimensions: 24 inches ID and 10 feet long. Gas and thermocouple connections were provided at one end of the retort. The roll was placed in the retort and supported on journals at its ends. The retort was then welded closed and leak-tested.
  • the retort was evacuated with a vacuum pump and back-filled with argon twice to remove oxygen from the container.
  • the retort containing the roll was positioned in a gas-fired furnace and pure hydrogen gas was fed to the retort as the temperature was raised in the furnace to 800C. and held there for a 4-hour soak to effect sealing of the undercoat by reaction/diffusion.
  • the roll and retort were furnace-cooled to room temperature and the retort opened for inspection. The furnace temperature was again raised to 800C. with the roll exposed to air and held again for a 4-hour soak to form an oxide barrier on the exposed areas of the undercoat.
  • the roll was then allowed to cool to room temperature whereupon it exhibited a smooth surface of white A1
  • the roll was preheated in a clamshell-type glow-bar furnace to a temperature of 300C. and then installed in a continuous aluminizing line which was capable of aluminizing steel strip at a line speed of approximately 150 feet per minute.
  • This roll was tested in excess of 176 hours, afterwhich it was inspected and found to exhibit no deterioration. As a result of this test the useful life of thisroll was estimated to be in excess of 350 hours.
  • An uncoated roll made of 1080 steel has 72 hours of useful life before replacement and thus a 250 to 300 percent improvement in life of a coated roll over an uncoated roll can be expected using the process of this invention.
  • EXAMPLE 6 To determine the effects of a continuous thermal gradient combined with both an oxidizing and moltenmetai environment, a steel heater probe made of A181 1080 steel was prepared for testing in the following manner. The surface of the probe was cleaned with trichloroethylene to remove surface grease and contamination. The surface was mechanically roughened by grit-blasting with 60 mesh A1 0 abrasive. The probe was held in a rotation and traversing mechanism. The rotation speed was 800 rpm, and the traverse rate was 24 inches/minute. A plasma torch fitted with a copper anode was used for spraying the undercoat material. An inert gas shield with argon was used to prevent oxidation of the material during spraying.
  • the undercoat consisted of a mechanical mixture of 96 w/o of an Fe-Cr alloy and 4 w/o of unalloyed Al.
  • the F e-Cr alloy was 80 w/o Fe and 20 w/o Cr.
  • the thickness of the undercoat was 0.006 inch.
  • the overcoat composed of pure A1 0 was sprayed on top of the undercoat. No surface preparation was required. A plasma arc torch was used with a copper anode as above. The overcoat of M 0 was deposited to a thickness of 0.0045 inch. The same rotation and traverse speeds as used for the undercoat, were used for the overcoat of A1 0
  • the probe was heat-treated in the following manner. The probe was held vertically on a steel pedestal and loaded in a resistance heated vacuum furnace. The furnace was evacuated to a pressure of 10' to torr to effect reaction/diffusion of the undercoat. The probe was furnace-cooled to room temperature and removed.
  • the surface was smooth and white with no cracks or discoloration.
  • the probe was installed in an aluminizing line and functioned to melt dross and slag at the exit end of the chute which carries the strip.
  • the probe was fitted with a silicon carbide resistance heater to provide heat for melting the slag or dross.
  • the probe lasted in excess of two weeks while an uncoated probe would last only 2 to 3 days. Thus a 450 percent increase in the life of a coated probe over an uncoated probe would be realized by using the process of this invention.
  • EXAMPLE 7 To determine the combined effects of impact loading and a molten metal with a high vapor pressure, a stabi- The surface of a high carbon steel roll which was 8 inches in diameter and 74 inches long was cleaned with N-D-l 50, a degreasing fluid. The surface was mechanically roughened by grit-blasting with 60 mesh A1 0 abrasive. The roll was positioned in a rotation and traverse mechanism. The rotation speed was 397 rpm, and the traverse speed was 0.41 inch/second. A plasma torch with a copper anode was used for spraying the undercoat material. An inert gas shield with argon was used to protect the molten particles from oxidation during spraying.
  • the undercoat consisted of a mechanical mixture of 96 w/o of an alloy of Fe-Cr and 4 w/o of unalloyed A1.
  • the Fe-Cr alloy was 80 wfo Fe and 20 w/o Cr.
  • the thickness of the deposited undercoat was 0.003 inch.
  • the overcoat composed of pure A1 0 was sprayed on top of the undercoat. No surface preparation was required prior to spraying the A1 0
  • the rotation and traverse speeds used were the same as those used for the undercoat.
  • a plasma torch with a copper anode was used, as above, to deposit the A1 0 to a thickness of 0.003 inchv
  • the roill was heat-treated under the following conditions.
  • a mild steel retort 24 inches lD by i0 feet long was fabricated. Gas and thermocouple connections were provided at one end of the retort. The roll was supported at each end on the journals. The retort was welded closed and leak-tested with a soap solution.
  • the retort was evacuated with a vacuum pump and backfilled with argon twice to remove oxygen from the container.
  • the retort containing the roll was positioned in a gas-fired furnace and pure hydrogen gas was fed to the retort as the temperature was raised in the furnace to 800C. and held there for a 4-hour soak period.
  • the roll and retort were furnace-cooled to room temperature and the retort opened.
  • the furnace temperature was again raised to 800C. with the roll exposed to air and held again for a 4-hour soak to oxidize the exposed areas on the undercoat.
  • the roll was allowed to cool to room temperature.
  • the roll was preheated to about 3001 v and installed in a continuous galvanizing line. This line galvanizes steel sheet at a line speed of approximately l50200 feet per minute. After 7 days the roll was still functioning and showed no sign of apparent damage.
  • EXAMPLE 8 Two T-shaped cross-sectional area test specimens made of PIA-188*, a cobalt-base superalloy, and each measuring 4 inches long, three-eighths inches wide on its top face, one-sixteenth inch thick and having a three-eighth inch center leg, were first plasma coated on their top faces with a 0.003 to 0.005 inch layer of a mixture of 80 wtlo of an alloy of wtfo Co and 25 W10 Cr, and 20 wt/o of unalloyed A1, An overcoat, 0.002 to 0.003 inches thick of MgZrO- was then plasma deposited onto the first coat on each specimen. The specimens were then heated to 1,079C. in hydrogen and held at this temperature for 5 hours so as to seal the undercoat by reactionldiffusion.
  • a process for producing a corrosion resistant duplex coated article comprising:
  • a primary coating selected from at least one of the groups consisting of metals, metal alloys, intermetallics, metal oxides, metal carbides, metal nitrides, metal borides, metal silicides, and cermets, onto the as-deposited undercoat; and
  • step (a) is deposited by plasma deposition techniques, and wherein the metals are selected from a group consisting of nickel, aluminum, cobalt, iron, chromium, copper, molybdenum, tungsten, niobium, tantalum, zirconium, vanadium, hafnium, magnesium, zinc, titanium, antimony, calcium, manganese and palladium; wherein the alloys are selected from a group consisting of the alloys of the above metals, and wherein the intermetallics are selected from a group consisting of the intermetallics of the above metals.
  • each of the materials in step (a) is selected from one of the groups consisting of nickel, aluminum, cobalt, iron, chromium, copper, molybdenum, tungsten, niobium, tantalum, titanium, zirconium, vanadium, hafnium, magnesium, zinc, antimony, calcium, manganese, palladium, nichrome, iron-chromium alloys, iron-chromium intermetallics, cobalt-chromium alloys, cobalt-chromium intermetallics, iron-chromium alloys containing rare earth additions, nickel-chromium alloys containing rare earth additions, cobalt-chromium alloys containing rare earth additions, copper-aluminum alloys and copper-aluminum intermetallics.
  • step (a) the material of the article is selected from a group consisting of steel and cast iron; wherein in step (a) one of the materials is aluminum and the other material is selected from a group consisting of iron-chromium alloys, nickelchromium alloys and cobalt-chromium alloys; and wherein in step (b) said primary coating is alumina.
  • the duplex coated article d. subjecting the duplex coated article to an oxidizing atmosphere, a carburizing atmosphere, a nitriding atmosphere, a boriding atmosphere. or a siliciding atmosphere for a time period and at a temperature sufficient to react the medium in the atmosphere with segmented areas on the surface of the undercoat that are exposed to the exterior through the porosity of the primary coating thereby providing a layer of the reacted medium on said exposed areas.
  • step (c) the following step is added:
  • step (a) the two materials are aluminum, and a cobalt-chromium alloy containing rare earth additions; and wherein in step (b) said primary coating is MgZrQ 9.
  • a process for producing a corrosion resistant du' plex coated article comprising:
  • a primary coating selected from at least one of the groups consisting of metals, metal alloys, intermetallics, metal oxides, metal carbides, metal nitrides, metal borides, metals silicides, and cermets, onto the substantially sealed undercoat layer thereby producing a duplex layer having excellent corrosion-resistant characteristics.
  • each of the materials in step a) is selected from the group consisting of nickel, aluminum, cobalt, iron, chromium, copper, molybdenum, tungsten, niobium, tantalum, titanium, zirconium, vanadium, halfnium, magnesium, zinc, antimony, calcium, manganese, palladium, nickelchromium, iron-chromium alloys, iron-chromium intermetallics, cobalt-chromium alloys, cobalt-chromium intermetallics, iron-chromium alloys containing rare earth additions, nickel-chromium alloys containing rare earth additions, cobalt-chromium alloys containing rare earth additions, copper-aluminum alloys and copper-aluminum intermetallics.

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DE19732325149 DE2325149C3 (de) 1972-05-22 1973-05-18 Verfahren zum Beschichten von Metallgegenständen
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FR7318416A FR2185696B1 (enrdf_load_stackoverflow) 1972-05-22 1973-05-21
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EP0024912A1 (en) * 1979-08-29 1981-03-11 Special Metals Corporation Method of heat treating nickel base alloys
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WO1981001983A1 (en) * 1980-01-07 1981-07-23 United Technologies Corp Columnar grain ceramic thermal barrier coatings on polished substrates
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US4401697A (en) * 1980-01-07 1983-08-30 United Technologies Corporation Method for producing columnar grain ceramic thermal barrier coatings
US4405659A (en) * 1980-01-07 1983-09-20 United Technologies Corporation Method for producing columnar grain ceramic thermal barrier coatings
US4405660A (en) * 1980-01-07 1983-09-20 United Technologies Corporation Method for producing metallic articles having durable ceramic thermal barrier coatings
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US4414249A (en) * 1980-01-07 1983-11-08 United Technologies Corporation Method for producing metallic articles having durable ceramic thermal barrier coatings
US4417097A (en) * 1981-06-04 1983-11-22 Aluminum Company Of America High temperature, corrosion resistant coating and lead for electrical current
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DE3318999A1 (de) * 1983-05-25 1984-11-29 M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 8000 München Beschichteter metallischer gegenstand sowie verfahren zu dessen herstellung
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FR2185696A1 (enrdf_load_stackoverflow) 1974-01-04
CH574506A5 (enrdf_load_stackoverflow) 1976-04-15
GB1438381A (en) 1976-06-03
JPS5320931B2 (enrdf_load_stackoverflow) 1978-06-29
CA1000130A (en) 1976-11-23
FR2185696B1 (enrdf_load_stackoverflow) 1976-05-28
DE2325149B2 (de) 1976-12-23
DE2325149A1 (de) 1973-12-06
JPS4942533A (enrdf_load_stackoverflow) 1974-04-22

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