US3692554A - Production of protective layers on cobalt-based alloys - Google Patents

Production of protective layers on cobalt-based alloys Download PDF

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Publication number
US3692554A
US3692554A US94752A US3692554DA US3692554A US 3692554 A US3692554 A US 3692554A US 94752 A US94752 A US 94752A US 3692554D A US3692554D A US 3692554DA US 3692554 A US3692554 A US 3692554A
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United States
Prior art keywords
cobalt
based alloys
nickel
aluminum
metal
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US94752A
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English (en)
Inventor
Karl Bungardt
Gunter Lehnert
Helmut Meinhardt
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Deutsche Edelstahlwerke AG
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Deutsche Edelstahlwerke AG
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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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • 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
    • Y10S428/941—Solid state alloying, e.g. diffusion, to disappearance of an original layer
    • 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.]
    • Y10T428/12736—Al-base component
    • Y10T428/1275—Next to Group VIII or IB metal-base 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
    • Y10T428/12868—Group IB metal-base component alternative to platinum group metal-base component [e.g., precious metal, etc.]
    • 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
    • Y10T428/12944—Ni-base component

Definitions

  • Cobalt-based alloys have their surface treated to provide high-temperature corrosion resistance, by diffusing nickel, a metal of the Platinum Group, and aluminum into the surface of the alloy.
  • the metals may be heat-diffused simultaneously or in succession.
  • This invention relates to a method of producing on the surface of parts made of cobalt-based alloys protective, diffusion layers that are resistant at high temperatures to oxidation, scaling and corrosion.
  • the object of the present invention is to provide on parts made of high temperature metals, particularly cobalt-based alloys, a protective layer which imparts irnproved resistance to oxidation, scaling and corrosion at high temperatures.
  • the present invention consists in applying to the parts, possibly after they have been previously cleaned and degreased, nickel, one or more metals of the platinum group of metals of the ⁇ Periodic System of Elements (preferably platinum), and aluminum, either simultaneously or in succession, and to diffuse the said metals into the surface of the parts.
  • layers of nickel, of metal(s) of the platinum group and of aluminum may be consecutively applied to the surface of the part, for example by mechanical or electrolytic means, dipping, spraying or otherwise, and the metals in the layers thus formed diffused severally or jointly into the surface of the part by a diffusion heat treatment.
  • a layer of nickel and then a layer of one or more metals of the platinum group may be electrolytically deposited and the aluminum then deposited from a gas phase on the surface of the part and diffused into the surface of the part together with the nickel and the metal(s) of the platinum group.
  • the part that has first been provided with a nickel layer and then with a layer of metal(s) of the platinum group may be embedded in a powder mixture containing metallic aluminum possibly associated with a small proportion of a metal halide and an inert filler (e.g. alumina), the aluminum being then deposited on the part from a gas phase and finally diffused into the surface of the part together with the nickel and the metal(s) of the platinum group.
  • a mixture may for example comprise about of aluminum and about 95% of the inert filler.
  • Cobalt-based alloys that have been provided with a protective diffusion layer according to the invention last about twice as long as similar parts that have been provided with a protective aluminum diffusion layer without nickel and platinum.
  • the graph of the accompanying 4 Claims 3,692,554 Patentedv Sept. 19, 1972 drawing having time, expressed in hours', on the abscissa and change in weight, expressed in milligrams per square centimeter, on the ordinate shows, as a function of operating time, the change in weight-of test pieces that have been aluminized by a conventional method, and that have been protected by the method according to the invention.
  • the reduction in weight which indicates the rate at which material is lost from the surface of the tested part by oxidation, scaling and corrosion is less for p'arts protected according to the invention ⁇ than parts that have been merely aluminized, and that their useful life of 600 to 700 hours in scaling test when exposed to burnt natural gas at 1100 C. with an air factor of 1.2, is twice as long.
  • the material of all the tested parts was a cobalt alloy containing I0.45% carbon, less than 0.5% silicon, less than 0.5% manganese, r21.0% chromium, less than 1.0% nickel, 11.0% tungsten, 2.0% nio# bium or tantalum, 1.75% iron, balance cobalt.
  • the protective treatment of the parts accordingv to the invention was as follows: .4 v
  • NiClZ-HZO nickel chloride
  • PRELIMINARY SURFACE TREATMENT OF THE NICKEL BEFORE PLATINISATION Degreasing in a cyanide degreasing bath as hereinbefore described cathodically 10 seconds, anodically 2O seconds and cathodically l0 seconds at a temperature of 20 C. and a current density of 5 amps/ sq. dm., followed by pickling in 10% by weight caustic soda cathodically 3 seconds and anodically 10 seconds at a temperature of 50 C. and a current density of 10 amps/sq. dm., followed by pickling in 4% hydrochloric acid cathodically 2 seconds and anodically 30 seconds at a temperature of 40 C. and a current density of 2.5 amps/sq. dm., followed by washing in warm water at C.
  • the result of this treatment was an overall thickness of the protective diffusion layer of 60 microns.
  • a method of producing protective di'usion layers that are resistant to oxidation, scaling and-corrosion at high temperatures on the surface of a cobalt-based alloy part comprising the steps of depositing successively first nickel,r and then one or more metals of the group consisting of platinum, rhodium, ruthenium and palladium onto the surface of the said metal part, heating said coated part to, diiusion temperature while at the same time ⁇ aluminum from a gas phase is diffused into the surfaceA of the said coated metal part.
  • a method according to claim 1 in 4 which the said metal part4 coated with nickel and then with a metal layer of one or more metals of the group consisting of platinum, rhodium, ruthenium and palladium is embedded in a powder mixture comprising metallic aluminum and anfinert filler, and subjected in said powder mixture to a, diffusion treatment whereby aluminum from the gas phase diffuses ,into the surface of the said metal part.
  • a method according to claim 2 wherein the said powder mixture comprises about 5% by weight of metallic aluminum and about 95% by weight of inert filler.
  • a method according Ainert filler is alumina.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US94752A 1969-12-05 1970-12-03 Production of protective layers on cobalt-based alloys Expired - Lifetime US3692554A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691961047 DE1961047B2 (de) 1969-12-05 1969-12-05 Verfahren zur herstellung von diffusionsschutzschichten auf gegenstaenden aus legierungen auf kobaltbasis

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US3692554A true US3692554A (en) 1972-09-19

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US (1) US3692554A (xx)
JP (1) JPS4931609B1 (xx)
AT (1) AT296715B (xx)
BE (1) BE759275A (xx)
CA (1) CA924970A (xx)
CH (1) CH552682A (xx)
DE (1) DE1961047B2 (xx)
FR (1) FR2072284A5 (xx)
GB (1) GB1282530A (xx)
IL (1) IL35730A (xx)
NL (1) NL7017774A (xx)
SE (1) SE358420B (xx)
ZA (1) ZA708014B (xx)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819338A (en) * 1968-09-14 1974-06-25 Deutsche Edelstahlwerke Ag Protective diffusion layer on nickel and/or cobalt-based alloys
US3961910A (en) * 1973-05-25 1976-06-08 Chromalloy American Corporation Rhodium-containing superalloy coatings and methods of making same
US3979273A (en) * 1975-05-27 1976-09-07 United Technologies Corporation Method of forming aluminide coatings on nickel-, cobalt-, and iron-base alloys
DE2601129A1 (de) * 1975-02-21 1976-09-09 Chromalloy American Corp Verfahren zur verbesserung der waerme- und korrosionswiderstandsfaehigkeit von formkoerpern aus waermeresistenten legierungen auf nickel-, kobalt- und nickel-kobalt-basis
WO1983003988A1 (en) * 1982-05-07 1983-11-24 Turbine Metal Technology, Inc. Corrosion, erosion and wear resistant alloy structures and method thereof
US4962005A (en) * 1988-10-26 1990-10-09 Office National D'etudes Et De Recherches Aerospatiales Method of protecting the surfaces of metal parts against corrosion at high temperature, and a part treated by the method
US5057196A (en) * 1990-12-17 1991-10-15 General Motors Corporation Method of forming platinum-silicon-enriched diffused aluminide coating on a superalloy substrate
US5334416A (en) * 1991-12-30 1994-08-02 Pohang Iron & Steel Co., Ltd. Heat resistant stainless steel coated by diffusion of aluminum and the coating method thereof
US5427866A (en) * 1994-03-28 1995-06-27 General Electric Company Platinum, rhodium, or palladium protective coatings in thermal barrier coating systems
US5645893A (en) * 1994-12-24 1997-07-08 Rolls-Royce Plc Thermal barrier coating for a superalloy article and method of application
US5650235A (en) * 1994-02-28 1997-07-22 Sermatech International, Inc. Platinum enriched, silicon-modified corrosion resistant aluminide coating
US5652044A (en) * 1992-03-05 1997-07-29 Rolls Royce Plc Coated article
US5658614A (en) * 1994-10-28 1997-08-19 Howmet Research Corporation Platinum aluminide CVD coating method
US5667663A (en) * 1994-12-24 1997-09-16 Chromalloy United Kingdom Limited Method of applying a thermal barrier coating to a superalloy article and a thermal barrier coating
US5759380A (en) * 1989-04-04 1998-06-02 General Electric Company Method of preparing oxidation resistant coatings
US5897966A (en) * 1996-02-26 1999-04-27 General Electric Company High temperature alloy article with a discrete protective coating and method for making
US6066405A (en) * 1995-12-22 2000-05-23 General Electric Company Nickel-base superalloy having an optimized platinum-aluminide coating
US6207297B1 (en) 1999-09-29 2001-03-27 Siemens Westinghouse Power Corporation Barrier layer for a MCrAlY basecoat superalloy combination
EP1111091A1 (en) * 1999-12-21 2001-06-27 United Technologies Corporation Method of forming an active-element containing aluminide as stand alone coating and as bond coat and coated article
EP1939318A2 (en) 2006-12-27 2008-07-02 General Electric Company Carburization process for stabilizing nickel-based superalloys
US10030298B2 (en) 2015-08-21 2018-07-24 General Electric Company Method for altering metal surfaces

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5310704U (xx) * 1976-07-09 1978-01-28
JPS5345908U (xx) * 1976-09-22 1978-04-19
US4501776A (en) * 1982-11-01 1985-02-26 Turbine Components Corporation Methods of forming a protective diffusion layer on nickel, cobalt and iron base alloys
WO1996041068A1 (en) * 1995-06-07 1996-12-19 National Research Council Of Canada Anti-fretting barrier
FR2745590B1 (fr) * 1996-02-29 1998-05-15 Snecma Revetement de barriere thermique a sous-couche amelioree et pieces revetues par une telle barriere thermique
US6228510B1 (en) * 1998-12-22 2001-05-08 General Electric Company Coating and method for minimizing consumption of base material during high temperature service
EP1123987A1 (en) * 2000-02-11 2001-08-16 General Electric Company Repairable diffusion aluminide coatings

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819338A (en) * 1968-09-14 1974-06-25 Deutsche Edelstahlwerke Ag Protective diffusion layer on nickel and/or cobalt-based alloys
US3961910A (en) * 1973-05-25 1976-06-08 Chromalloy American Corporation Rhodium-containing superalloy coatings and methods of making same
DE2601129A1 (de) * 1975-02-21 1976-09-09 Chromalloy American Corp Verfahren zur verbesserung der waerme- und korrosionswiderstandsfaehigkeit von formkoerpern aus waermeresistenten legierungen auf nickel-, kobalt- und nickel-kobalt-basis
US3999956A (en) * 1975-02-21 1976-12-28 Chromalloy American Corporation Platinum-rhodium-containing high temperature alloy coating
US4070507A (en) * 1975-02-21 1978-01-24 Chromalloy American Corporation Platinum-rhodium-containing high temperature alloy coating method
US3979273A (en) * 1975-05-27 1976-09-07 United Technologies Corporation Method of forming aluminide coatings on nickel-, cobalt-, and iron-base alloys
US4439470A (en) * 1980-11-17 1984-03-27 George Kelly Sievers Method for forming ternary alloys using precious metals and interdispersed phase
US4656099A (en) * 1982-05-07 1987-04-07 Sievers George K Corrosion, erosion and wear resistant alloy structures and method therefor
WO1983003988A1 (en) * 1982-05-07 1983-11-24 Turbine Metal Technology, Inc. Corrosion, erosion and wear resistant alloy structures and method thereof
US4962005A (en) * 1988-10-26 1990-10-09 Office National D'etudes Et De Recherches Aerospatiales Method of protecting the surfaces of metal parts against corrosion at high temperature, and a part treated by the method
US5759380A (en) * 1989-04-04 1998-06-02 General Electric Company Method of preparing oxidation resistant coatings
US5057196A (en) * 1990-12-17 1991-10-15 General Motors Corporation Method of forming platinum-silicon-enriched diffused aluminide coating on a superalloy substrate
US5334416A (en) * 1991-12-30 1994-08-02 Pohang Iron & Steel Co., Ltd. Heat resistant stainless steel coated by diffusion of aluminum and the coating method thereof
US5846605A (en) * 1992-03-05 1998-12-08 Rolls-Royce Plc Coated Article
US5652044A (en) * 1992-03-05 1997-07-29 Rolls Royce Plc Coated article
US5650235A (en) * 1994-02-28 1997-07-22 Sermatech International, Inc. Platinum enriched, silicon-modified corrosion resistant aluminide coating
US5427866A (en) * 1994-03-28 1995-06-27 General Electric Company Platinum, rhodium, or palladium protective coatings in thermal barrier coating systems
US5658614A (en) * 1994-10-28 1997-08-19 Howmet Research Corporation Platinum aluminide CVD coating method
US5981091A (en) * 1994-12-24 1999-11-09 Rolls-Royce Plc Article including thermal barrier coated superalloy substrate
US5763107A (en) * 1994-12-24 1998-06-09 Rolls-Royce Plc Thermal barrier coating for a superalloy article
US5645893A (en) * 1994-12-24 1997-07-08 Rolls-Royce Plc Thermal barrier coating for a superalloy article and method of application
US5667663A (en) * 1994-12-24 1997-09-16 Chromalloy United Kingdom Limited Method of applying a thermal barrier coating to a superalloy article and a thermal barrier coating
US20070048538A1 (en) * 1995-12-22 2007-03-01 General Electric Company Nickel-base superalloy having an optimized platinum-aluminide coating
US6066405A (en) * 1995-12-22 2000-05-23 General Electric Company Nickel-base superalloy having an optimized platinum-aluminide coating
US20040025978A1 (en) * 1995-12-22 2004-02-12 Schaeffer Jon C. Nickel-base superalloy having an optimized platinum-aluminide coating
US20040197597A1 (en) * 1995-12-22 2004-10-07 Schaeffer Jon C. Nickel-base superalloy having an optimized platinum-aluminide coating
US7083827B2 (en) 1995-12-22 2006-08-01 General Electric Company Nickel-base superalloy having an optimized platinum-aluminide coating
US20070082221A1 (en) * 1995-12-22 2007-04-12 General Electric Company Nickel-base superalloy having an optimized platinum-aluminide coating
US5897966A (en) * 1996-02-26 1999-04-27 General Electric Company High temperature alloy article with a discrete protective coating and method for making
US6207297B1 (en) 1999-09-29 2001-03-27 Siemens Westinghouse Power Corporation Barrier layer for a MCrAlY basecoat superalloy combination
EP1111091A1 (en) * 1999-12-21 2001-06-27 United Technologies Corporation Method of forming an active-element containing aluminide as stand alone coating and as bond coat and coated article
SG98436A1 (en) * 1999-12-21 2003-09-19 United Technologies Corp Method of forming an active-element containing aluminide as stand alone coating and as bond coat and coated article
EP1939318A2 (en) 2006-12-27 2008-07-02 General Electric Company Carburization process for stabilizing nickel-based superalloys
US10030298B2 (en) 2015-08-21 2018-07-24 General Electric Company Method for altering metal surfaces

Also Published As

Publication number Publication date
ZA708014B (en) 1971-08-25
DE1961047A1 (de) 1971-07-15
DE1961047B2 (de) 1971-12-09
IL35730A (en) 1973-11-28
SE358420B (xx) 1973-07-30
CA924970A (en) 1973-04-24
GB1282530A (en) 1972-07-19
BE759275A (fr) 1971-04-30
IL35730A0 (en) 1971-01-28
AT296715B (de) 1972-02-25
FR2072284A5 (xx) 1971-09-24
NL7017774A (xx) 1971-06-08
JPS4931609B1 (xx) 1974-08-23
CH552682A (de) 1974-08-15

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